Effect of Fe{sub 3}O{sub 4} nanoparticles on space charge distribution in propylene carbonate under impulse voltage

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

Sima, Wenxia, E-mail: cqsmwx@cqu.edu.cn; Song, He; Yang, Qing

2015-12-15

Addition of nanoparticles of the ferromagnetic material Fe{sub 3}O{sub 4} can increase the positive impulse breakdown voltage of propylene carbonate by 11.65%. To further investigate the effect of ferromagnetic nanoparticles on the space charge distribution in the discharge process, the present work set up a Kerr electro-optic field mapping measurement system using an array photodetector to carry out time-continuous measurement of the electric field and space charge distribution in propylene carbonate before and after modification. Test results show that fast electrons can be captured by Fe{sub 3}O{sub 4} nanoparticles and converted into relatively slow, negatively charged particles, inhibiting the generationmore » and transportation of the space charge, especially the negative space charge.« less

Ionic association of lithium salts in propylene carbonate/ 1,2-dimethoxyethane mixed systems for lithium batteries

NASA Astrophysics Data System (ADS)

Ishikawa, Masashi; Wen, Shi-Qui; Matsuda, Yoshiharu

1993-06-01

The ionic association constants of lithium perchlorate, lithium trifluoremethylsulfate, lithium hexafluorophosphate, and lithium tetrafluoroborate have been determined experimentally (by Shedlovsky's method) in various mixtures of propylene carbonate and 1,2-dimethoxyethane as typical electrolyte systems for rechargeable lithium batteries. The association constants vary extensively for different mixing ratios of propylene to 1,2-dimethoxyethane and for different species of salts. These values are compared with the theoretical values as predicted by the Fuoss and Bjerrum equations. On the basis of this comparison and some physical properties of the solution, the variation in the ionic association constants may be ascribed to the charge of ionic association species, i.e., a contact ion-pair and a solvent-separated ion-pair.

Early Stage Anodic Instability of Glassy Carbon Electrodes in Propylene Carbonate Solvent Containing Lithium Hexafluorophosphate.

PubMed

Carino, Emily V; Newman, Daniel J; Connell, Justin G; Kim, Chaerin; Brushett, Fikile R

2017-10-31

Irreversible changes to the morphology of glassy carbon (GC) electrodes at potentials between 3.5 and 4.5 V vs Li/Li + in propylene carbonate (PC) solvent containing lithium hexafluorophosphate (LiPF 6 ) are reported. Analysis of cyclic voltammetry (CV) experiments in the range of 3.0 to 6.0 V shows that the capacitance of the electrochemical double-layer increased irreversibly beginning at potentials as low as 3.5 V. These changes resulted from nonfaradaic interactions, and were not due to oxidative electrochemical decomposition of the electrode and electrolyte, anion intercalation, nor caused by the presence of water, a common impurity in organic electrolyte solutions. Atomic force microscopy (AFM) images revealed that increasing the potential of a bare GC surface from 3.0 to 4.5 V resulted in a 6× increase in roughness, in good agreement with the changes in double-layer capacitance. Treating the GC surface via exposure to trichloromethylsilane vapors resulted in a stable double-layer capacitance between 3.0 and 4.5 V, and this treatment also correlated with less roughening. These results inform future efforts aimed at controlling surface composition and morphology of carbon electrodes.

Nonlinear dielectric spectroscopy of propylene carbonate derivatives

NASA Astrophysics Data System (ADS)

Casalini, R.; Roland, C. M.

2018-04-01

Nonlinear dielectric measurements were carried out on two strongly polar liquids, 4-vinyl-1,3-dioxolan-2-one (VPC) and 4-ethyl-1,3-dioxolan-2-one (EPC), having chemical structures differing from propylene carbonate (PC) only by the presence of a pendant group. Despite their polarity, the compounds are all non-associated, "simple" liquids. From the linear component of the dielectric response, the α relaxation peak breadth was found to be invariant at a fixed value of the relaxation time, τα. From spectra from the nonlinear component, the number of dynamically correlated molecules was determined; it was also constant at fixed τα. Thus, two manifestations of dynamic heterogeneity depend only on the time constant for structural reorientation. More broadly, the cooperativity of molecular motions for non-associated glass-forming materials is connected to (i.e., reciprocally governs) the time scale. The equation of state for the two liquids was also obtained from density measurements made over a broad range of pressures and temperatures. Using these data, it was determined that the relaxation times of both liquids conform to density scaling. The effect of density, relative to thermal effects, on the α relaxation increases going from PC < VPC < EPC.

Early Stage Anodic Instability of Glassy Carbon Electrodes in Propylene Carbonate Solvent Containing Lithium Hexafluorophosphate

DOE PAGES

Carino, Emily V.; Newman, Daniel J.; Connell, Justin G.; ...

2017-09-19

In this paper, irreversible changes to the morphology of glassy carbon (GC) electrodes at potentials between 3.5 and 4.5 V vs Li/Li + in propylene carbonate (PC) solvent containing lithium hexafluorophosphate (LiPF 6) are reported. Analysis of cyclic voltammetry (CV) experiments in the range of 3.0 to 6.0 V shows that the capacitance of the electrochemical double -layer increased irreversibly beginning at potentials as low as 3.5 V. These changes resulted from nonfaradaic interactions, and were not due to oxidative electrochemical decomposition of the electrode and electrolyte, anion intercalation, nor caused by the presence of water, a common impurity inmore » organic electrolyte solutions. Atomic force microscopy (AFM) images revealed that increasing the potential of a bare GC surface from 3.0 to 4.5 V resulted in a 6X increase in roughness, in good agreement with the changes in double -layer capacitance. Treating the GC surface via exposure to trichloromethylsilane vapors resulted in a stable double -layer capacitance between 3.0 and 4.5 V, and this treatment also correlated with less roughening. Lastly, these results inform future efforts aimed at controlling surface composition and morphology of carbon electrodes.« less

Solvent Dependence of Lateral Charge Transfer in a Porphyrin Monolayer

DOE PAGES

Brennan, Bradley J.; Regan, Kevin P.; Durrell, Alec C.; ...

2016-12-19

Lateral charge transport in a redox)active monolayer can be utilized for solar energy harvesting. We chose the porphyrin system to study the influence of the solvent on lateral hole hopping, which plays a crucial role in the charge)transfer kinetics. We also examined the influence of water, acetonitrile, and propylene carbonate as solvents. Hole)hopping lifetimes varied by nearly three orders of magnitude among solvents, ranging from 3 ns in water to 2800 ns in propylene carbonate, and increased nonlinearly as a function of added acetonitrile in aqueous solvent mixtures. Our results elucidate the important roles of solvation, molecular packing dynamics, andmore » lateral charge)transfer mechanisms that have implications for all dye)sensitized photoelectrochemical device designs.« less

Reaction of CO2 with propylene oxide and styrene oxide catalyzed by a chromium(III) amine-bis(phenolate) complex.

PubMed

Dean, Rebecca K; Devaine-Pressing, Katalin; Dawe, Louise N; Kozak, Christopher M

2013-07-07

A diamine-bis(phenolate) chromium(III) complex, {CrCl[O2NN'](BuBu)}2 catalyzes the copolymerization of propylene oxide with carbon dioxide. The synthesis of this metal complex is straightforward and it can be obtained in high yields. This catalyst incorporates a tripodal amine-bis(phenolate) ligand, which differs from the salen or salan ligands typically used with Cr and Co complexes that have been employed as catalysts for the synthesis of such polycarbonates. The catalyst reported herein yields low molecular weight polymers with narrow polydispersities when the reaction is performed at room temperature. Performing the reaction at elevated temperatures causes the selective synthesis of propylene carbonate. The copolymerization activity for propylene oxide and carbon dioxide, as well as the coupling of carbon dioxide and styrene oxide to give styrene carbonate are presented.

Ultrafast Decay of the Solvated Electron in a Neat Polar Solvent: The Unusual Case of Propylene Carbonate.

PubMed

Le Caër, Sophie; Ortiz, Daniel; Marignier, Jean-Louis; Schmidhammer, Uli; Belloni, Jacqueline; Mostafavi, Mehran

2016-01-07

The behavior of carbonates is critical for a detailed understanding of aging phenomena in Li-ion batteries. Here we study the first reaction stages of propylene carbonate (PC), a cyclical carbonate, by picosecond pulse radiolysis. An absorption band with a maximum around 1360 nm is observed at 20 ps after the electron pulse and is shifted to 1310 nm after 50 ps. This band presents the features of a solvated electron absorption band, the solvation lasting up to 50 ps. Surprisingly, in this polar solvent, the solvated electron follows an ultrafast decay and disappears with a half time of 360 ps. This is attributed to the formation of a radical anion PC(-•). The yield of the solvated electron is low, suggesting that the radical anions are mainly directly produced from presolvated electrons. These results demonstrate that the initial electron transfers mechanisms are strongly different in linear compared with cyclical carbonates.

Conversion of 1,2-Propylene Glycol on Rutile TiO2(110)

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

Chen, Long; Li, Zhenjun; Smith, R. Scott

2014-07-17

We have studied the reactions of 1,2-propylene glycol (1,2-PG), DOCH(CH3)CH2OD, on partially reduced, hydroxylated and oxidized TiO2(110) surfaces using temperature programmed desorption. On reduced TiO2(110), propylene, propanal, and acetone are identified as primary carbon-containing products. While the propylene formation channel dominates at low 1,2-PG coverages, all of the above-mentioned products are observed at high coverages. The carbon-containing products are accompanied by the formation of D2O and D2. The observation of only deuterated products shows that the source of hydrogen (D) is from the 1,2-PG hydroxyls. The role of bridging oxygen vacancy (VO) sites was further investigated by titrating them viamore » hydroxylation and oxidation. The results show that hydroxylation does not change the reactivity because the VO sites are regenerated at 500 K, which is a temperature lower than the 1,2-PG product formation temperature. In contrast, surface oxidation causes significant changes in the product distribution, with increased acetone and propanal formation and decreased propylene formation. Additionally D2 is completely eliminated as an observed product at the expense of D2O formation.« less

Propylene oxidation mechanisms and intermediates using in situ soft X-ray fluorescence methods on the Pt(111) surface

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

Gabelnick, A.M.; Capitano, A.T.; Kane, S.M.

2000-01-12

The oxidation of propylene preabsorbed on the Pt(111) surface has been characterized in oxygen pressures up to 0.02 Torr using fluorescence yield near-edge spectroscopy (FYNES) and temperature-programmed fluorescence yield near-edge spectroscopy (TP-FYNES) above the carbon K edge. During oxidation of adsorbed propylene, a stable intermediate was observed and characterized using these soft X-ray methods. A general in situ method for determining the stoichiometry of carbon-containing reaction intermediate species has been developed and demonstrated for the first time. Total carbon concentration measured during temperature-programmed reaction studies clearly indicates a reaction intermediate is formed in the 300 K temperature range with amore » surface concentration of 0.55 x 10{sup 15} carbon atoms/cm{sup 2}. By comparing the intensity of the C-H {sigma}* resonance at the magic angle with the intensity in the carbon continuum, the stoichiometry of this intermediate can be determined unambiguously. Based on calibration with molecular propylene (C{sub 3}H{sub 6}) and propylidyne (C{sub 3}H{sub 5}), the intermediate has a C{sub 3}H{sub 5} stoichiometry for oxygen pressures up to 0.02 Torr. A set of normal and glancing angle FYNES spectra above the carbon K edge was used to characterize the bonding and structure of this intermediate. Spectra of known coverages of adsorbed propylene and propylidyne served as standards. The spectra of di-{sigma} propylene, propylidyne, and the intermediate were curve fit as a group with consistent energies and widths of all primary features. Based on this procedure, the intermediate is 1,1,2-tri-{sigma} 1-methylvinyl. The stoichiometry and temperature stability range of the 1-methylvinyl intermediate formed in oxygen pressures up to 0.02 Torr is identical with the stoichiometry and stability of the same intermediate formed during oxidation of preadsorbed propylene by excess coadsorbed atomic oxygen.« less

Evaluation of activated sludge for biodegradation of propylene glycol as an aircraft deicing fluid.

PubMed

Delorit, Justin D; Racz, LeeAnn

2014-04-01

Aircraft deicing fluid used at airport facilities is often collected for treatment or disposal in order to prevent serious ecological threats to nearby surface waters. This study investigated lab scale degradation of propylene glycol, the active ingredient in a common aircraft deicing fluid, by way of a laboratory-scale sequencing batch reactor containing municipal waste water treatment facility activated sludge performing simultaneous organic carbon oxidation and nitrification. The ability of activated sludge to remove propylene glycol was evaluated by studying the biodegradation and sorption characteristics of propylene glycol in an activated sludge medium. The results indicate sorption may play a role in the fate of propylene glycol in AS, and the heterotrophic bacteria readily degrade this compound. Therefore, a field deployable bioreactor may be appropriate for use in flight line applications.

Combined Quantum Chemical/Raman Spectroscopic Analyses of Li+ Cation Solvation: Cyclic Carbonate Solvents - Ethylene Carbonate and Propylene Earbonate

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

Allen, Joshua L.; Borodin, Oleg; Seo, D. M.

2014-12-01

Combined computational/Raman spectroscopic analyses of ethylene carbonate (EC) and propylene carbonate (PC) solvation interactions with lithium salts are reported. It is proposed that previously reported Raman analyses of (EC)n-LiX mixtures have utilized faulty assumptions. In the present studies, density functional theory (DFT) calculations have provided corrections in terms of both the scaling factors for the solvent's Raman band intensity variations and information about band overlap. By accounting for these factors, the solvation numbers obtained from two different EC solvent bands are in excellent agreement with one another. The same analysis for PC, however, was found to be quite challenging. Commerciallymore » available PC is a racemic mixture of (S)- and (R)-PC isomers. Based upon the quantum chemistry calculations, each of these solvent isomers may exist as multiple conformers due to a low energy barrier for ring inversion, making deconvolution of the Raman bands daunting and inherently prone to significant error. Thus, Raman spectroscopy is able to accurately determine the extent of the EC...Li+ cation solvation interactions using the provided methodology, but a similar analysis of PC...Li+ cation solvation results in a significant underestimation of the actual solvation numbers.« less

HETERODIMERIZATION OF PROPYLENE AND VINYLARENES: FUNCTIONAL GROUP COMPATIBILITY IN A HIGHLY EFFICIENT NI-CATALYZED CARBON-CARBON BOND-FORMING REACTION. (R826120)

EPA Science Inventory

Abstract

Unlike heterodimerization reactions of ethylene and vinylarenes, no such synthetically useful reactions using propylene are known. We find that propylene reacts with various vinylarenes in the presence of catalytic amounts of [(allyl)NiBr]₂, triphen...

21 CFR 172.858 - Propylene glycol alginate.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Propylene glycol alginate. 172.858 Section 172.858... CONSUMPTION Multipurpose Additives § 172.858 Propylene glycol alginate. The food additive propylene glycol... information required by the act: (1) The name of the additive, “propylene glycol alginate” or “propylene...

21 CFR 172.858 - Propylene glycol alginate.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Propylene glycol alginate. 172.858 Section 172.858... CONSUMPTION Multipurpose Additives § 172.858 Propylene glycol alginate. The food additive propylene glycol... information required by the act: (1) The name of the additive, “propylene glycol alginate” or “propylene...

21 CFR 172.858 - Propylene glycol alginate.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Propylene glycol alginate. 172.858 Section 172.858... Propylene glycol alginate. The food additive propylene glycol alginate (CAS Reg. No. 9005-37-2) may be used... the act: (1) The name of the additive, “propylene glycol alginate” or “propylene glycol ester of...

Solvation of the fluorine containing anions and their lithium salts in propylene carbonate and dimethoxyethane.

PubMed

Chaban, Vitaly

2015-07-01

Electrolyte solutions based on the propylene carbonate (PC)-dimethoxyethane (DME) mixtures are of significant importance and urgency due to emergence of lithium-ion batteries. Solvation and coordination of the lithium cation in these systems have been recently attended in detail. However, analogous information concerning anions (tetrafluoroborate, hexafluorophosphate) is still missed. This work reports PM7-MD simulations (electronic-structure level of description) to include finite-temperature effects on the anion solvation regularities in the PC-DME mixture. The reported result evidences that the anions appear weakly solvated. This observation is linked to the absence of suitable coordination sites in the solvent molecules. In the concentrated electrolyte solutions, both BF4(-) and PF6(-) prefer to exist as neutral ion pairs (LiBF4, LiPF6).

77 FR 28493 - Propylene Oxide; Tolerance Actions

Federal Register 2010, 2011, 2012, 2013, 2014

2012-05-15

... pine nuts for both the fumigant propylene oxide and the reaction product from the use of propylene... oxide and the reaction product from the use of propylene oxide, known as propylene chlorohydrin. Also... Pistachio 300 Plum, prune, dried 2.0 (2) Tolerances are established for residues of the reaction product...

Acetonitrile

Integrated Risk Information System (IRIS)

Acetonitrile ; CASRN 75 - 05 - 8 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic Effec

Controlled synthesis of multi-arm star polyether-polycarbonate polyols based on propylene oxide and CO2.

PubMed

Hilf, Jeannette; Schulze, Patricia; Seiwert, Jan; Frey, Holger

2014-01-01

Multi-arm star copolymers based on a hyperbranched poly(propylene oxide) polyether-polyol (hbPPO) as a core and poly(propylene carbonate) (PPC) arms are synthesized in two steps from propylene oxide (PO), a small amount of glycidol and CO2 . The PPC arms are prepared via carbon dioxide (CO2 )/PO copolymerization, using hbPPO as a multifunctional macroinitiator and the (R,R)-(salcy)CoOBzF5 catalyst. Star copolymers with 14 and 28 PPC arms, respectively, and controlled molecular weights in the range of 2700-8800 g mol(-1) are prepared (Mw /Mn = 1.23-1.61). Thermal analysis reveals lowered glass transition temperatures in the range of -8 to 10 °C for the PPC star polymers compared with linear PPC, which is due to the influence of the flexible polyether core. Successful conversion of the terminal hydroxyl groups with phenylisocyanate demonstrates the potential of the polycarbonate polyols for polyurethane synthesis. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

21 CFR 582.4666 - Propylene glycol.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 6 2011-04-01 2011-04-01 false Propylene glycol. 582.4666 Section 582.4666 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Propylene glycol. (a) Product. Propylene glycol. (b) Conditions of use. This substance is generally...

21 CFR 582.4666 - Propylene glycol.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 21 Food and Drugs 6 2013-04-01 2013-04-01 false Propylene glycol. 582.4666 Section 582.4666 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Propylene glycol. (a) Product. Propylene glycol. (b) Conditions of use. This substance is generally...

21 CFR 582.4666 - Propylene glycol.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 21 Food and Drugs 6 2012-04-01 2012-04-01 false Propylene glycol. 582.4666 Section 582.4666 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Propylene glycol. (a) Product. Propylene glycol. (b) Conditions of use. This substance is generally...

21 CFR 582.4666 - Propylene glycol.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 6 2014-04-01 2014-04-01 false Propylene glycol. 582.4666 Section 582.4666 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Propylene glycol. (a) Product. Propylene glycol. (b) Conditions of use. This substance is generally...

21 CFR 582.4666 - Propylene glycol.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Propylene glycol. 582.4666 Section 582.4666 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Propylene glycol. (a) Product. Propylene glycol. (b) Conditions of use. This substance is generally...

21 CFR 582.1666 - Propylene glycol.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 6 2014-04-01 2014-04-01 false Propylene glycol. 582.1666 Section 582.1666 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Additives § 582.1666 Propylene glycol. (a) Product. Propylene glycol. (b) Conditions of use. This substance...

21 CFR 582.1666 - Propylene glycol.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 21 Food and Drugs 6 2012-04-01 2012-04-01 false Propylene glycol. 582.1666 Section 582.1666 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Additives § 582.1666 Propylene glycol. (a) Product. Propylene glycol. (b) Conditions of use. This substance...

21 CFR 582.1666 - Propylene glycol.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 21 Food and Drugs 6 2013-04-01 2013-04-01 false Propylene glycol. 582.1666 Section 582.1666 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Additives § 582.1666 Propylene glycol. (a) Product. Propylene glycol. (b) Conditions of use. This substance...

Anomalous Capacitance Maximum of the Glassy Carbon-Ionic Liquid Interface through Dilution with Organic Solvents.

PubMed

Bozym, David J; Uralcan, Betül; Limmer, David T; Pope, Michael A; Szamreta, Nicholas J; Debenedetti, Pablo G; Aksay, Ilhan A

2015-07-02

We use electrochemical impedance spectroscopy to measure the effect of diluting a hydrophobic room temperature ionic liquid with miscible organic solvents on the differential capacitance of the glassy carbon-electrolyte interface. We show that the minimum differential capacitance increases with dilution and reaches a maximum value at ionic liquid contents near 5-10 mol% (i.e., ∼1 M). We provide evidence that mixtures with 1,2-dichloroethane, a low-dielectric constant solvent, yield the largest gains in capacitance near the open circuit potential when compared against two traditional solvents, acetonitrile and propylene carbonate. To provide a fundamental basis for these observations, we use a coarse-grained model to relate structural variations at the double layer to the occurrence of the maximum. Our results reveal the potential for the enhancement of double-layer capacitance through dilution.

Novel polymer composites from waste ethylene-propylene-diene-monomer rubber by supercritical CO2 foaming technology.

PubMed

Jeong, Keuk Min; Hong, Yeo Joo; Saha, Prosenjit; Park, Seong Ho; Kim, Jin Kuk

2014-11-01

In this study, a composite has been prepared by mixing waste rubber, such as ethylene-propylene-diene-monomer and low-density poly ethylene foaming, with supercritical carbon dioxide. In order to optimise the foaming process of the waste ethylene-propylene-diene-monomer-low-density poly ethylene composite, the variations of pressure and temperature on the foamed Microcell formation were studied. As indicated in scanning electron microscope photographs, the most uniform microcellular pattern was found at 200 bar and 100 °C using 30% by weight of waste ethylene-propylene-diene-monomer. Carbon dioxide could not be dissolved uniformly during foaming owing to extensive cross-linking of the waste ethylene-propylene-diene-monomer used for the composite. As a result the presence of un-uniform microcells after foaming were observed in the composite matrix to impart inferior mechanical properties of the composite. This problem was solved with uniform foaming by increasing the cross-link density of low-density poly ethylene using 1.5 parts per hundred dicumyl peroxide that enhances composite tensile and compressive strength up to 57% and 15%, respectively. The composite has the potential to be used as a foaming mat for artificial turf. © The Author(s) 2014.

Potentiometric chemical sensors from lignin-poly(propylene oxide) copolymers doped by carbon nanotubes.

PubMed

Rudnitskaya, Alisa; Evtuguin, Dmitry V; Costa, Luis C; Graça, M Pedro F; Fernandes, António J S; Correia, M Rosario P; Gomes, M Teresa S R; Oliveira, J A B P

2013-01-21

Hardwood and softwood lignins obtained from industrial sulphite and kraft and laboratory oxygen-organosolv pulping processes were employed in co-polymerization with tolylene 2,4-diisocyanate terminated poly(propylene glycol). The obtained lignin-based polyurethanes were doped with 0.72 w/w% of multiwall carbon nanotubes (MWCNTs) with the aim of increasing their electrical conductivity to the levels suitable for sensor applications. Effects of the polymer doping with MWCNTs were assessed using electrical impedance (EIS) and UV-Resonance Raman (UV-RR) spectroscopy. Potentiometric sensors were prepared by drop casting of liquid polymer on the surface of carbon glass or platinum electrodes. Lignin-based sensors displayed a very low or no sensitivity to all alkali, alkali-earth and transition metal cations ions except Cr(VI) at pH 2. Response to Cr(VI) values of 39, 50 and 53 mV pX(-1) for the sensors based on kraft, organosolv and lignosulphonate lignins, respectively, were observed. Redox sensitivity values close to the theoretical values of 20 and 21 mV pX(-1) for organosolv and lignosulphonate based sensors respectively were detected in the Cr(III)/Cr(VI) solutions while a very low response was observed in the solutions containing Fe(CN)(6)(3-/4-). Conducting composite lignin-based polyurethanes doped with MWCNTs were suggested as being promising materials for Cr(VI)-sensitive potentiometric sensors.

Haemoglobinuria caused by propylene glycol in sheep

PubMed Central

Potter, B. J.

1958-01-01

Haemoglobinuria occurred in sheep anaesthetized by an intravenous injection of pentobarbitone sodium containing propylene glycol: an equivalent dose failed to cause haemoglobinuria in rabbits. Intravenous injection of an aqueous solution of 20% propylene glycol caused haemoglobinaemia and haemoglobinuria in sheep. Neither distilled water nor 20% glycerol in water administered under identical conditions produced these effects. Haemoglobinuria occurred on some occasions when an aqueous 20% solution of propylene glycol was administered to sheep after an injection of saline: it never occurred when a solution of 20% propylene glycol prepared with physiological saline was injected. It is suggested that saline may protect against the haemolytic action of propylene glycol in sheep and that propylene glycol should be avoided as a menstruum for pharmaceutical preparations to be used for injection into the blood stream of these animals. PMID:13618540

Propylene Glycol Poisoning From Excess Whiskey Ingestion

PubMed Central

Ku, Kevin; Sue, Gloria R.

2015-01-01

In this report, we describe a case of high anion gap metabolic acidosis with a significant osmolal gap attributed to the ingestion of liquor containing propylene glycol. Recently, several reports have characterized severe lactic acidosis occurring in the setting of iatrogenic unintentional overdosing of medications that use propylene glycol as a diluent, including lorazepam and diazepam. To date, no studies have explored potential effects of excess propylene glycol in the setting of alcohol intoxication. Our patient endorsed drinking large volumes of cinnamon flavored whiskey, which was likely Fireball Cinnamon Whisky. To our knowledge, this is the first case of propylene glycol toxicity from an intentional ingestion of liquor containing propylene glycol. PMID:26904700

Effect of water and alkali modifications on ETS-10 for the cycloaddition of CO2 to propylene oxide.

PubMed

Doskocil, Eric J

2005-02-17

Sodium oxide (NaOx) impregnated Engelhard Titanosilicate-10 (ETS-10) molecular sieve catalysts were prepared to enhance the basicity associated with ETS-10 and subsequently investigated for the cycloaddition of carbon dioxide to propylene oxide to produce propylene carbonate. For dry NaOx-modified ETS-10 catalysts that contained no adsorbed water, a maximum yield of propylene carbonate was achieved at a loading of 2.0 excess NaOx species per unit cell. However, the greatest enhancements in the rate of reaction were observed when small amounts of water were adsorbed onto the unmodified ETS-10 catalyst immediately prior to reaction. Surface-bound water appears to enhance the surface Bronsted acidity of the unmodified ETS-10 catalyst via the formation of surface -OH groups at lower water loadings, producing a surface of better-tuned acid-base bifunctional characteristics for the cycloaddition reaction. At levels of hydration greater than 12.5% by mass, the yield of propylene carbonate was further enhanced, but at a smaller rate than that observed at lower rehydration levels, which is more indicative of an enhanced transport effect. Adsorption microcalorimetry of carbon dioxide indicated that, at loadings less than 2.0 NaOx per unit cell, the total uptake of the CO2 adsorption sites required for the reaction were less than in the parent ETS-10 material. However, at higher levels of NaOx occlusion, where the total uptake and strength of the adsorption sites exceeded those observed for the as-received ETS-10 material, the cycloaddition activity of this catalyst suffered due to the reduced pore volume and surface area. It appears that precise tuning of both the surface acidity and basicity is crucial in creating an effective acid-base bifunctional ETS-10 catalyst for the cycloaddition reaction investigated.

Propylene glycol intoxication in a dog.

PubMed

Claus, Melissa A; Jandrey, Karl E; Poppenga, Robert H

2011-12-01

To describe the clinical course, treatment, and outcome of a dog with propylene glycol intoxication. An adult castrated male Australian cattle dog presented to an emergency clinic for an acute onset of ataxia and disorientation after roaming a construction site unsupervised. He tested positive for ethylene glycol using a point-of-care test kit. Treatment for ethylene glycol intoxication included intermittent intravenous boluses of 20% ethanol and hemodialysis. Predialysis and postdialysis blood samples were submitted to the toxicology lab to assess for both ethylene and propylene glycol. The patient tested negative for ethylene glycol and positive for propylene glycol at 1100 mg/dL predialysis and 23 mg/dL postdialysis. The dog made a full recovery. To the authors' knowledge, this is the first report of documented propylene glycol intoxication in a dog, as well as the first report to describe hemodialysis as treatment for propylene glycol intoxication in a dog. © Veterinary Emergency and Critical Care Society 2011.

Low-temperature growth of nitrogen-doped carbon nanofibers by acetonitrile catalytic CVD using Ni-based catalysts

NASA Astrophysics Data System (ADS)

Iwasaki, Tomohiro; Makino, Yuri; Fukukawa, Makoto; Nakamura, Hideya; Watano, Satoru

2016-11-01

To synthesize nitrogen-doped carbon nanofibers (N-CNFs) at high growth rates and low temperatures less than 673 K, nickel species (metallic nickel and nickel oxide) supported on alumina particles were used as the catalysts for an acetonitrile catalytic chemical vapor deposition (CVD) process. The nickel:alumina mass ratio in the catalysts was fixed at 0.05:1. The catalyst precursors were prepared from various nickel salts (nitrate, chloride, sulfate, acetate, and lactate) and then calcined at 1073 K for 1 h in oxidative (air), reductive (hydrogen-containing argon), or inert (pure argon) atmospheres to activate the nickel-based catalysts. The effects of precursors and calcination atmosphere on the catalyst activity at low temperatures were studied. We found that the catalysts derived from nickel nitrate had relatively small crystallite sizes of nickel species and provided N-CNFs at high growth rates of 57 ± 4 g-CNF/g-Ni/h at 673 K in the CVD process using 10 vol% hydrogen-containing argon as the carrier gas of acetonitrile vapor, which were approximately 4 times larger than that of a conventional CVD process. The obtained results reveal that nitrate ions in the catalyst precursor and hydrogen in the carrier gas can contribute effectively to the activation of catalysts in low-temperature CVD. The fiber diameter and nitrogen content of N-CNFs synthesized at high growth rates were several tens of nanometers and 3.5 ± 0.3 at.%, respectively. Our catalysts and CVD process may lead to cost reductions in the production of N-CNFs.

Assessment of Simple Models for Molecular Simulation of Ethylene Carbonate and Propylene Carbonate as Solvents for Electrolyte Solutions.

PubMed

Chaudhari, Mangesh I; Muralidharan, Ajay; Pratt, Lawrence R; Rempe, Susan B

2018-02-12

Progress in understanding liquid ethylene carbonate (EC) and propylene carbonate (PC) on the basis of molecular simulation, emphasizing simple models of interatomic forces, is reviewed. Results on the bulk liquids are examined from the perspective of anticipated applications to materials for electrical energy storage devices. Preliminary results on electrochemical double-layer capacitors based on carbon nanotube forests and on model solid-electrolyte interphase (SEI) layers of lithium ion batteries are considered as examples. The basic results discussed suggest that an empirically parameterized, non-polarizable force field can reproduce experimental structural, thermodynamic, and dielectric properties of EC and PC liquids with acceptable accuracy. More sophisticated force fields might include molecular polarizability and Buckingham-model description of inter-atomic overlap repulsions as extensions to Lennard-Jones models of van der Waals interactions. Simple approaches should be similarly successful also for applications to organic molecular ions in EC/PC solutions, but the important case of Li[Formula: see text] deserves special attention because of the particularly strong interactions of that small ion with neighboring solvent molecules. To treat the Li[Formula: see text] ions in liquid EC/PC solutions, we identify interaction models defined by empirically scaled partial charges for ion-solvent interactions. The empirical adjustments use more basic inputs, electronic structure calculations and ab initio molecular dynamics simulations, and also experimental results on Li[Formula: see text] thermodynamics and transport in EC/PC solutions. Application of such models to the mechanism of Li[Formula: see text] transport in glassy SEI models emphasizes the advantage of long time-scale molecular dynamics studies of these non-equilibrium materials.

Surface Nanobubbles in Nonaqueous Media: Looking for Nanobubbles in DMSO, Formamide, Propylene Carbonate, Ethylammonium Nitrate, and Propylammonium Nitrate.

PubMed

An, Hongjie; Liu, Guangming; Atkin, Rob; Craig, Vincent S J

2015-07-28

Surface nanobubbles produced by supersaturation during the exchange of ethanol for water are routinely observed on hydrophobic surfaces, are stable for days, and have contact angles that are very much greater than observed macroscopically. Here, we test the hypothesis that nanobubbles can also be observed in nonaqueous solvents in order to ascertain if their anomalous lifetimes and contact angles are related to properties of the solvent. Nanobubbles were seen in the protic solvents formamide, ethylammonium nitrate, and propylammonium nitrate, but not in propylene carbonate or dimethyl sulfoxide. Solvents in which nanobubbles were observed exhibit a three-dimensional hydrogen-bonding network. Like in aqueous systems, the nanobubbles were stable for days and exhibited high contact angles (∼165°).

76 FR 79146 - Propylene Oxide; Proposed Tolerance Actions

Federal Register 2010, 2011, 2012, 2013, 2014

2011-12-21

... and pine nuts for both the fumigant propylene oxide and the reaction product from the use of propylene..., prune, dried 2.0 (2) Tolerances are established for residues of the reaction product, propylene...

The Role of Cesium Cation in Controlling Interphasial Chemistry on Graphite Anode in Propylene Carbonate-Rich Electrolytes

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

Xiang, Hongfa; Mei, Donghai; Yan, Pengfei

2015-09-10

Propylene carbonate (PC) is seldom used in lithium-ion batteries (LIBs) due to its sustained co-intercalation into graphene structure and the eventual graphite exfoliation, despite potential advantages it brings, such as wider liquid range and lower cost. Here we discover that cesium cation (Cs+), originally used to suppress dendrite growth of Li metal anode, directs the formation of solid electrolyte interphase (SEI) on graphitic anode in PC-rich electrolytes through preferential solvation. Effective suppression of PC-decomposition and graphite-exfoliation was achieved when the ratio of ethylene carbonate (EC)/PC in electrolytes was so adjusted that the reductive decomposition of Cs+-(EC)m (1≤m≤2) complex precedes thatmore » of Li+-(PC)n (3≤n≤5). The interphase directed by Cs+ is stable, ultrathin and compact, leading to significant improvements in LIB performances. In a broader context, the accurate tailoring of SEI chemical composition by introducing a new solvation center represents a fundamental breakthrough in manipulating interfacial reactions processes that once were elusive.« less

Solubilities of carbon dioxide in aqueous potassium carbonate solutions mixed with physical solvents

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

Park, S.B.; Lee, H.; Lee, K.H.

1998-09-01

The removal of acidic gases such as CO{sub 2}, H{sub 2}S, and COS from gas streams is a very important operation for petrochemical, oil refineries, ammonia manufacture, coal gasification, and natural gas purification plants. Here, the solubilities of carbon dioxide in aqueous potassium carbonate (K{sub 2}CO{sub 3}) solutions mixed with physical solvents were measured at 298.2 and 323.2 K with a CO{sub 2} partial-pressure range of 5 kPa to 2 MPa. 1,2-propanediol and propylene carbonate were selected as physical solvents. The aqueous solutions treated in this study were 5 mass% K{sub 2}CO{sub 3}-15 mass% 1,2-propanediol and propylene carbonate were selectedmore » as physical solvents. The aqueous solutions treated in this study were 5 mass% K{sub 2}CO{sub 3}-15 mass% propylene carbonate. The experimental solubility results were presented by the mole ratio of CO{sub 2} and K{sub 2}CO{sub 3} contained in the liquid mixture. The addition of 1,2-propanediol to 5 mass% K{sub 2}CO{sub 3} solution lowered the solubility of CO{sub 2} at constant temperature and pressure conditions when CO{sub 2} partial-pressure range of 5 kPa to 2 MPa. In the case of propylene carbonate the addition of propylene carbonate increased the experimental solubilities in the region of low CO{sub 2} partial pressures and decreased as the CO{sub 2} partial pressure was increased above atmospheric. The solubilities of CO{sub 2} decreased with increasing temperature in the range of 298.2 to 323.2 K.« less

Microstructure and hydrogen bonding in water-acetonitrile mixtures.

PubMed

Mountain, Raymond D

2010-12-16

The connection of hydrogen bonding between water and acetonitrile in determining the microheterogeneity of the liquid mixture is examined using NPT molecular dynamics simulations. Mixtures for six, rigid, three-site models for acetonitrile and one water model (SPC/E) were simulated to determine the amount of water-acetonitrile hydrogen bonding. Only one of the six acetonitrile models (TraPPE-UA) was able to reproduce both the liquid density and the experimental estimates of hydrogen bonding derived from Raman scattering of the CN stretch band or from NMR quadrupole relaxation measurements. A simple modification of the acetonitrile model parameters for the models that provided poor estimates produced hydrogen-bonding results consistent with experiments for two of the models. Of these, only one of the modified models also accurately determined the density of the mixtures. The self-diffusion coefficient of liquid acetonitrile provided a final winnowing of the modified model and the successful, unmodified model. The unmodified model is provisionally recommended for simulations of water-acetonitrile mixtures.

Role of PF6- in the radiolytical and electrochemical degradation of propylene carbonate solutions

NASA Astrophysics Data System (ADS)

Ortiz, Daniel; Jimenez Gordon, Isabel; Legand, Solène; Dauvois, Vincent; Baltaze, Jean-Pierre; Marignier, Jean-Louis; Martin, Jean-Frédéric; Belloni, Jacqueline; Mostafavi, Mehran; Le Caër, Sophie

2016-09-01

The behavior under irradiation of neat propylene carbonate (PC), a co-solvent usually used in Li-ion batteries (LIB), and also of Li salt solutions is investigated. The decomposition of neat PC is studied using radiolysis in the pulse and steady state regime and is assigned to the ultrafast formation, in the reducing channel, of the radical anion PCrad - by electron attachment, followed by the ring cleavage, leading to CO. In the oxidative channel, the PC(sbnd H)rad radical is formed, generating CO2. The CO2 and CO yields are both close to the ionization yield of PC. The CO2 and CO productions in LiClO4, LiBF4 and LiN(CF3)2(SO2)2 solutions are similar as in neat PC. In contrast, in LiPF6/PC a strong impact on PC degradation is measured with a doubling of the CO2 yield due to the high reactivity of the electron towards PF6- observed in the picosecond range. A small number of oxide phosphine molecules are detected among the various products of the irradiated solutions, suggesting that most of them, observed in carbonate mixtures used in LIBs, arise from linear rather than from cyclical molecules. The similarity between the degradation by radiolysis or electrolysis highlights the interest of radiolysis as an accelerated aging method.

Disulfiram inhibition of cyanide formation after acetonitrile poisoning.

PubMed

De Paepe, Peter; Colin, Pieter; Depuydt, Pieter; Decavele, An-Sofie; De Smet, Julie; Boussery, Koen; Stove, Christophe; Benoit, Dominique; Verstraete, Alain; Van Bocxlaer, Jan; Buylaert, Walter

2016-01-01

Cyanide poisoning may be caused by acetonitrile, a common industrial organic solvent and laboratory agent. To describe the potential use of disulfiram in treating acetonitrile poisoning in a human clinical case and to further study its effect in human liver microsomes in vitro. A 30-year-old man initially presented with a cholinergic toxic syndrome following ingestion of aldicarb. Toxicological analysis revealed coingestion of ethanol. He subsequently developed severe metabolic acidosis caused by the cyanogenic compound acetonitrile which was erroneously interpreted as acetone in the chromatogram. After three treatments with hydroxocobalamin (5 g i.v.) and sodium thiosulfate (12.5 g i.v.) on days 2, 3, and 5, he had transient improvement but recurrent lactic acidosis. Treatment with disulfiram was associated on day 7 with resolution of metabolic acidosis and slowing of the decrease in acetonitrile concentration. He recovered from acetonitrile toxicity completely. The time course of acetonitrile, thiocyanate, and cyanide concentrations suggested that disulfiram inhibited cyanide formation. In vitro experiments with human liver microsomes showed the cyanide concentration was significantly lower after incubation with acetonitrile and disulfiram than acetonitrile alone (a mean 60% reduction in cyanide level). Although disulfiram was given late in the course of the poisoning it is possible that it contributed to the recovery.

Modification of carbon nanotubes with fluorinated ionic liquid for improving processability of fluoro-ethylene-propylene

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

Ma, Hongyang; Chu, Benjamin; Hsiao, Benjamin S.

Fluorinated ionic liquid (F-IL), 1-(3-perfluorooctylpropyl)-3-methylimidazolium bis(perfluoroethylsufonyl)amine, had been successfully prepared and employed to modify multi-wall carbon nanotubes (MWCNTs) for improving the processability of fluoro-ethylene-propylene (FEP). The thermally decomposed temperature of F-IL was higher than 350 °C measured by thermal gravimetric analysis (TGA) which indicated that the fluorinated ionic liquid could be suitable for melting blend with FEP (blending at 290 °C) by a twin-screw extruder. Through “cation-π” interaction between the imidazolium cation of F-IL and the graphene surface of MWCNTs, MWCNTs can be modified with F-IL and used as nanofillers to improve the dispersity of MWCNTs in fluorocopolymer FEP verifiedmore » by SEM images of the FEP nanocomposite. The structural characterization and mechanical property of FEP nanocomposite during the deformation were investigated by tensile experiments and simultaneous time-resolved wide-angle X-ray diffraction (WAXD) and small-angle X-ray scattering (SAXS) techniques.« less

Refractive index, molar refraction and comparative refractive index study of propylene carbonate binary liquid mixtures.

PubMed

Wankhede, Dnyaneshwar Shamrao

2012-06-01

Refractive indices (n) have been experimentally determined for the binary liquid-liquid mixtures of Propylene carbonate (PC) (1) with benzene, ethylbenzene, o-xylene and p-xylene (2) at 298.15, 303.15 and 308.15 K over the entire mole fraction range. The experimental values of n are utilised to calculate deviation in refractive index (Δn), molar refraction (R) and deviation in molar refraction (ΔR). A comparative study of Arago-Biot (A-B), Newton (NW), Eyring and John (E-J) equations for determining refractive index of a liquid has been carried out to test their validity for all the binary mixtures over the entire composition range at 298.15 K. Comparison of various mixing relations is represented in terms of average deviation (AVD). The Δn and ΔR values have been fitted to Redlich-Kister equation at 298.15 K and standard deviations have been calculated. The results are discussed in terms of intermolecular interactions present amongst the components.

Mechanical and thermal properties of eco-friendly poly(propylene carbonate)/cellulose acetate butyrate blends.

PubMed

Xing, Chenyang; Wang, Hengti; Hu, Qiaoqiao; Xu, Fenfen; Cao, Xiaojun; You, Jichun; Li, Yongjin

2013-02-15

The eco-friendly poly(propylene carbonate) (PPC)/cellulose acetate butyrate (CAB) blends were prepared by melt-blending in a batch mixer for the first time. PPC and CAB were partially miscible because of the drastically shifted glass transition temperatures of both PPC and CAB, which originated from the specific interactions between carbonyl groups and hydroxyl groups. The incorporation of CAB into PPC matrix enhanced not only tensile strength and modulus of PPC dramatically, but also improved heat resistance and thermal stability of PPC significantly. The tensile strength and the modulus of PPC/CAB=50/50 blend are 27.7 MPa and 1.24 GPa, which are 21 times and 28 times higher than those of the unmodified PPC, respectively. Moreover, the elongation at break of PPC/CAB=50/50 blend is as high as 117%. In addition, the obtained blends exhibited good transparency, which is very important for the package materials. The results in this work pave new possibility for the massive application of eco-friendly polymer materials. Copyright © 2012 Elsevier Ltd. All rights reserved.

Anaerobic treatability of wastewater contaminated with propylene glycol.

PubMed

Sezgin, Naim; Tonuk, Gulseven Ubay

2013-09-01

The purpose of this study was to investigate the biodegradability of propylene glycol in anaerobic conditions by using methanogenic culture. A master reactor was set up to develop a culture that would be acclimated to propylene glycol. After reaching steady-state, culture was transferred to serum bottles. Three reactors with same initial conditions were run for consistency. Propylene glycol was completely biodegradable under anaerobic methanogenic conditions. Semi-continuous reactors operated at a temperature of 35°C had consistently achieved a propylene glycol removal of higher than 95 % based on chemical oxygen demand (COD). It was found that in semi-continuous reactors, anaerobic treatment of propylene glycol at concentrations higher than 1,500 mg COD m(-3) day(-1) was not convenient due to instable effluent COD.

Modulating the protein content of complex proteomes using acetonitrile.

PubMed

Prates, João; Martins, Gonçalo; López-Fernández, Hugo; Lodeiro, Carlos; Capelo, J L; Santos, Hugo M

2018-05-15

In this work we present acetonitrile as a tool to modulate the dynamic range of the proteome of complex samples. Different concentrations of acetonitrile ranging from 15% v/v to 65% v/v were used to modulate the protein content of serum samples from healthy people and patients with lymphoma and myeloma. We show that the proteome above 70 kDa is pelleted as a function of the concentration of acetonitrile and that profiling with PCA or Clustering is only possible using the supernatants obtained for concentrations of acetonitrile higher than 45% v/v or the pellets for concentrations of acetonitrile of 35% and 45%. The differentiation and classification of the three groups of sera samples (healthy, lymphoma and myeloma) were possible using acetonitrile at 55% v/v concentration. This work opens new avenues for the application of acetonitrile as a cost-effective tool in proteomics applications. Copyright © 2018 Elsevier B.V. All rights reserved.

Propylene oxide

Integrated Risk Information System (IRIS)

Propylene oxide ; CASRN 75 - 56 - 9 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic Ef

Propylene glycol

Integrated Risk Information System (IRIS)

Propylene glycol ; CASRN 57 - 55 - 6 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic E

Interfacial characteristics of propylene carbonate and validation of simulation models for electrochemical applications

NASA Astrophysics Data System (ADS)

You, Xinli

Supercapacitors have occupy an indispensable role in today's energy storage systems due to their high power density and long life. The introduction of car- bon nanotube (CNT) forests as electrode offers the possibility of nano-scale design and high capacitance. We have performed molecular dynamics simulations on a CNT forest-based electrochemical double-layer capacitor (EDLC) and a widely used electrolyte solution (tetra-ethylammonium tetra-fluoroborate in propylene carbonate, TEABF4 /PC). We compare corresponding primitive model and atomically detailed model of TEABF4 /P, emphasizing the significance of ion clustering in electrolytes. The molecular dynamic simulation results suggests that the arrangement of closest neigh- bors leads to the formation of cation-anion chains or rings. Fuoss's discussion of ion-pairing model provides the approximation for a primitive model of 1-1 electrolyte is not broadly satisfactory for both primitive and atomically detailed cases. A more general Poisson statistical assumption is shown to be satisfactory when coordina- tion numbers are low, as is likely to be the case when ion-pairing initiates. We examined the Poisson-based model over a range of concentrations for both models of TEABF4 /P, and the atomically detailed model results identified solvent-separated nearest-neighbor ion-pairs. Large surface areas plays an essential role in nanomaterial properties, which calls for an accurate description of interfaces through modeling. We studied propylene carbonate, a widely used solvent in EDLC systems. PC wets graphite with a contact angle of 31°. The MD simulation model reproduced this contact angle after reduction 40% of the strength of graphite-C atom Lennard-Jones interactions with the solvent. The critical temperature of PC was accurately evaluated by extrapolating the PC liquid-vapor surface tensions. PC molecules tend to lie flat on the PC liquid-vapor surface, and project the propyl carbon toward the vapor phase. Liquid PC

Reaction Mechanism for Direct Propylene Epoxidation by Alumina-Supported Silver Aggregates. The Role of the Particle / Support Interface

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

Cheng, Lei; Yin, Chunrong; Mehmood, Faisal

2013-11-21

Sub-nanometer Ag aggregates on alumina supports have been found to be active toward direct propylene epoxidation to propylene oxide by molecular oxygen at low temperatures, with a negligible amount of carbon dioxide formation (Science 328, p. 224, 2010). In this work, we computationally and experimentally investigate the origin of the high reactivity of the sub-nanometer Ag aggregates. Computationally, we study O 2 dissociation and propylene epoxidation on unsupported Ag 19 and Ag 20 clusters, as well as alumina-supported Ag 19. The O 2 dissociation and propylene epoxidation apparent barriers at the interface between the Ag aggregate and the alumina supportmore » are calculated to be 0.2 and 0.2~0.4 eV, respectively. These barriers are somewhat lower than those on sites away from the interface. The mechanism at the interface is similar to what was previously found for the silver trimer on alumina and can account for the high activity observed for the direct oxidation of propylene on the Ag aggregates. The barriers for oxygen dissociation on these model systems both at the interface and on the surfaces are small compared to crystalline surfaces, indicating that availability of oxygen will not be a rate limiting step for the aggregates, as in the case of the crystalline surfaces. Experimentally, we investigate Ultrananocrystalline Diamond (UNCD)-supported silver aggregates under reactive conditions of propylene partial oxidation. The UNCD-supported Ag clusters are found to be not measurably active toward propylene oxidation, in contrast to the alumina supported Ag clusters. This suggests that the lack of metal-oxide interfacial sites of the Ag-UNCD catalyst, limits the epoxidation catalytic activity. This combined computational and experimental study shows the importance of the metal-oxide interface as well as the non-crystalline nature of the alumina-supported sub-nanometer Ag aggregate catalysts for propylene epoxidation.« less

An Artificial Lithium Protective Layer that Enables the Use of Acetonitrile-Based Electrolytes in Lithium Metal Batteries.

PubMed

Trinh, Ngoc Duc; Lepage, David; Aymé-Perrot, David; Badia, Antonella; Dollé, Mickael; Rochefort, Dominic

2018-04-23

The resurgence of the lithium metal battery requires innovations in technology, including the use of non-conventional liquid electrolytes. The inherent electrochemical potential of lithium metal (-3.04 V vs. SHE) inevitably limits its use in many solvents, such as acetonitrile, which could provide electrolytes with increased conductivity. The aim of this work is to produce an artificial passivation layer at the lithium metal/electrolyte interface that is electrochemically stable in acetonitrile-based electrolytes. To produce such a stable interface, the lithium metal was immersed in fluoroethylene carbonate (FEC) to generate a passivation layer via the spontaneous decomposition of the solvent. With this passivation layer, the chemical stability of lithium metal is shown for the first time in 1 m LiPF 6 in acetonitrile. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ab initio study of the structural properties of acetonitrile-water mixtures

NASA Astrophysics Data System (ADS)

Chen, Jinfan; Sit, Patrick H.-L.

2015-08-01

Structural properties of acetonitrile and acetonitrile-water mixtures are studied using Density Functional Theory (DFT) and ab initio molecular dynamics simulations. Stable molecular clusters consisted of several water and acetonitrile molecules are identified to provide microscopic understanding of the interaction among water and acetonitrile molecules. Ab initio molecular dynamics simulations are performed to study the liquid structure at the finite temperature. Three mixing compositions in which the mole fraction of acetonitrile equals 0.109, 0.5 and 0.891 are studied. These compositions correspond to three distinct structural regimes. At the 0.109 and 0.891 mole fraction of acetonitrile, the majority species are mostly connected among themselves and the minority species are either isolated or forming small clusters without disrupting the network of the majority species. At the 0.5 mole fraction of acetonitrile, large water and acetonitrile clusters persist throughout the simulation, exhibiting the microheterogeneous behavior in acetonitrile-water mixtures in the mid-range mixing ratio.

76 FR 38036 - Propylene Oxide; Pesticide Tolerances

Federal Register 2010, 2011, 2012, 2013, 2014

2011-06-29

... regulation amends the propylene oxide tolerance on ``nut, tree, group 14'' to ``nutmeat, processed, except... propylene oxide tolerance (40 CFR 180.491) on ``nut, tree, group 14'' to read ``nutmeat, processed, except...) on ``nut, tree, group 14'' to read ``nutmeat, processed, except peanuts.'' IV. Statutory and...

Inhalation developmental toxicology studies: Acetonitrile in rats. Final report

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

Mast, T.J.; Weigel, R.J.; Westerberg, R.B.

1994-02-01

The potential for acetonitrile to cause developmental toxicity was assessed in Sprague-Dawley rats exposed to 0, 100, 400, or 1200 ppM acetonitrile, 6 hours/day, 7 days/week. Exposure of rats to these concentrations of acetonitrile resulted in mortality in the 1200 ppM group (2/33 pregnant females; 1/10 non-pregnant females). However, there were no treatment-related effects upon body weights or reproduction indices at any exposure level, nor was there a significant increase in the incidence of fetal malformations or variations. The only effect observed in the fetuses was a slight, but not statiscally significant, exposure-correlated increase in the incidence of supernumerary ribs.more » Determination of acetonitrile and cyanide concentrations in maternal rat blood showed that acetonitrile concentration in the blood increased with exposure concentration for all exposed maternal rats. Detectable amounts of cyanide in the blood were found only in the rats exposed to 1200 ppM acetonitrile ({approximately}2 {mu}g cyanide/g of blood).« less

Propylene glycol accumulation in critically ill patients receiving continuous intravenous lorazepam infusions.

PubMed

Horinek, Erica L; Kiser, Tyree H; Fish, Douglas N; MacLaren, Robert

2009-12-01

Lorazepam is recommended by the Society of Critical Care Medicine as the preferred agent for sedation of critically ill patients. Intravenous lorazepam contains propylene glycol, which has been associated with toxicity when high doses of lorazepam are administered. To evaluate the accumulation of propylene glycol in critically ill patients receiving lorazepam by continuous infusion and determine factors associated with propylene glycol concentration. A 6-month, retrospective, safety assessment was conducted of adults admitted to the medical intensive care unit who were receiving lorazepam by continuous infusion for 12 hours or more. Propylene glycol serum concentrations were obtained 24-48 hours after continuous-infusion lorazepam was initiated and every 3-5 days thereafter. Propylene glycol accumulation was defined as concentrations of 25 mg/dL or more. Groups with and without propylene glycol accumulation were compared and factors associated with propylene glycol concentration were determined using multivariate correlation regression analyses. Forty-eight propylene glycol serum samples were obtained from 33 patients. Fourteen (42%) patients had propylene glycol accumulation, representing 23 (48%) serum samples. Univariate analyses showed the following factors were related to propylene glycol accumulation: baseline renal dysfunction, presence of alcohol withdrawal, sex, age, Acute Physiology and Chronic Health Evaluation (APACHE II) score, rate of lorazepam continuous infusion, and 24-hour lorazepam dose. Multivariate linear regression modeling demonstrated that propylene glycol concentration was strongly associated with the continuous infusion rate and 24-hour dose (adjusted r(2) > or = 0.77; p < 0.001). Independent correlation analyses showed that these 2 variables were so strongly associated with propylene glycol concentration (r(2) > or = 0.71; p < 0.001) that they alone predicted propylene glycol concentration. Seven (21%) patients developed renal dysfunction

X-ray absorption spectroscopy of LiBF 4 in propylene carbonate. A model lithium ion battery electrolyte

DOE PAGES

Smith, Jacob W.; Lam, Royce K.; Sheardy, Alex T.; ...

2014-08-20

Since their introduction into the commercial marketplace in 1991, lithium ion batteries have become increasingly ubiquitous in portable technology. Nevertheless, improvements to existing battery technology are necessary to expand their utility for larger-scale applications, such as electric vehicles. Advances may be realized from improvements to the liquid electrolyte; however, current understanding of the liquid structure and properties remains incomplete. X-ray absorption spectroscopy of solutions of LiBF 4 in propylene carbonate (PC), interpreted using first-principles electronic structure calculations within the eXcited electron and Core Hole (XCH) approximation, yields new insight into the solvation structure of the Li + ion in thismore » model electrolyte. By generating linear combinations of the computed spectra of Li +-associating and free PC molecules and comparing to the experimental spectrum, we find a Li +–solvent interaction number of 4.5. This result suggests that computational models of lithium ion battery electrolytes should move beyond tetrahedral coordination structures.« less

21 CFR 500.50 - Propylene glycol in or on cat food.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 6 2014-04-01 2014-04-01 false Propylene glycol in or on cat food. 500.50 Section... Propylene glycol in or on cat food. The Food and Drug Administration has determined that propylene glycol in... determined that this use of propylene glycol is not prior sanctioned. [61 FR 19544, May 2, 1996] ...

21 CFR 500.50 - Propylene glycol in or on cat food.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 21 Food and Drugs 6 2012-04-01 2012-04-01 false Propylene glycol in or on cat food. 500.50 Section... Propylene glycol in or on cat food. The Food and Drug Administration has determined that propylene glycol in... determined that this use of propylene glycol is not prior sanctioned. [61 FR 19544, May 2, 1996] ...

21 CFR 500.50 - Propylene glycol in or on cat food.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 21 Food and Drugs 6 2013-04-01 2013-04-01 false Propylene glycol in or on cat food. 500.50 Section... Propylene glycol in or on cat food. The Food and Drug Administration has determined that propylene glycol in... determined that this use of propylene glycol is not prior sanctioned. [61 FR 19544, May 2, 1996] ...

21 CFR 172.765 - Succistearin (stearoyl propylene glycol hydrogen succinate).

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Succistearin (stearoyl propylene glycol hydrogen... Other Specific Usage Additives § 172.765 Succistearin (stearoyl propylene glycol hydrogen succinate). The food additive succistearin (stearoyl propylene glycol hydrogen succinate) may be safely used in...

21 CFR 172.765 - Succistearin (stearoyl propylene glycol hydrogen succinate).

Code of Federal Regulations, 2012 CFR

2012-04-01

... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Succistearin (stearoyl propylene glycol hydrogen succinate). 172.765 Section 172.765 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND... propylene glycol hydrogen succinate). The food additive succistearin (stearoyl propylene glycol hydrogen...

21 CFR 172.765 - Succistearin (stearoyl propylene glycol hydrogen succinate).

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Succistearin (stearoyl propylene glycol hydrogen succinate). 172.765 Section 172.765 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND... propylene glycol hydrogen succinate). The food additive succistearin (stearoyl propylene glycol hydrogen...

21 CFR 172.765 - Succistearin (stearoyl propylene glycol hydrogen succinate).

Code of Federal Regulations, 2013 CFR

2013-04-01

... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Succistearin (stearoyl propylene glycol hydrogen succinate). 172.765 Section 172.765 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND... propylene glycol hydrogen succinate). The food additive succistearin (stearoyl propylene glycol hydrogen...

Characterization of un-plasticized and propylene carbonate plasticized carboxymethyl cellulose doped ammonium chloride solid biopolymer electrolytes.

PubMed

Ahmad, N H; Isa, M I N

2016-02-10

Two solid biopolymer electrolytes (SBEs) systems of carboxymethyl cellulose doped ammonium chloride (CMC-AC) and propylene carbonate plasticized (CMC-AC-PC) were prepared via solution casting technique. The ionic conductivity of SBEs were analyzed using electrical impedance spectroscopy (EIS) in the frequency range of 50 Hz-1 MHz at ambient temperature (303K). The highest ionic conductivity of CMC-AC SBE is 1.43 × 10(-3)S/cm for 16 wt.% of AC while the highest conductivity of plasticized SBE system is 1.01 × 10(-2)S/cm when added with 8 wt.% of PC. TGA/DSC showed that the addition of PC had increased the decomposition temperature compared of CMC-AC SBE. Fourier transform infrared (FTIR) spectra showed the occurrence of complexation between the SBE components and it is proved successfully executed by Gaussian software. X-ray diffraction (XRD) indicated that amorphous nature of SBEs. It is believed that the PC is one of the most promising plasticizer to enhance the ionic conductivity and performance for SBE system. Copyright © 2015 Elsevier Ltd. All rights reserved.

Intermolecular forces in acetonitrile + ethanol binary liquid mixtures

NASA Astrophysics Data System (ADS)

Elangovan, A.; Shanmugam, R.; Arivazhagan, G.; Mahendraprabu, A.; Karthick, N. K.

2015-10-01

FTIR spectral measurements have been carried out on the binary mixtures of acetonitrile with ethanol at 1:0 (acetonitrile:ethanol), 1:1, 1:2, 1:3 and 0:1 at room temperature. DFT and isosurface calculations have been performed. The acetonitrile + ethanol binary mixtures consist of 1:1, 1:2, 1:3 and 1:4 complexes formed through both the red and blue shifting H-bonds. Inter as well as intra molecular forces are found to exist in 1:3 and 1:4 complexes.

Mechanisms of propylene glycol and triacetin pyrolysis.

PubMed

Laino, Teodoro; Tuma, Christian; Moor, Philippe; Martin, Elyette; Stolz, Steffen; Curioni, Alessandro

2012-05-10

Propylene glycol and triacetin are chemical compounds, commonly used as food additives. Though the usage of the pure chemicals is not considered harmful when used as dietary supplements, little is known about the nature of their thermal degradation products and the impact they may have on human health. For these reasons, in this manuscript we investigate the thermal decomposition mechanisms of both neutral propylene glycol and triacetin in the gas phase by a novel simulation framework. This is based on a free energy sampling methodology followed by an accurate energy refinement. Structures, Gibbs free energy barriers, and rate constants at 800 K were computed for the different steps involved in the two pyrolytic processes. The thermal decomposition mechanisms found theoretically for propylene glycol and triacetin were validated by a qualitative experimental investigation using gas-phase chromatography-mass spectroscopy, with excellent agreement. The results provide a validation of the novel simulation framework and shed light on the potential hazard to the health that propylene glycol and triacetin may have when exposed to high temperatures.

Synthesis and characterization of amphiphilic block polymer poly(ethylene glycol)-poly(propylene carbonate)-poly(ethylene glycol) for drug delivery.

PubMed

Li, Hongchun; Niu, Yongsheng

2018-08-01

A novel amphiphilic block polymer poly(ethylene glycol)-poly(propylene carbonate)-poly(ethylene glycol) (PEG-PPC-PEG) was synthesized via the dicyclohexylcarbodiimide condensation reaction of double PEG-bis-amine and HOOC-PPC-COOH. The obtained copolymer was characterized by NMR to determine its structure. Using the PEG-PPC-PEG as the carrier and using doxorubicin (DOX) as a model drug, DOX-loaded nanoparticles with core shell structure were synthesized by self-assembly in water. The nanoparticles properties such as particle size, drug loading, encapsulation efficiency (EE) and drug release behavior were investigated as a function of the hydrophobic block length of PPC segments and compared with each other. The results showed that the EE was up to 88.8%. Nanoparticles were found to have a certain effect on the controlled release of DOX. Copyright © 2018 Elsevier B.V. All rights reserved.

NMR T1 relaxation time measurements and calculations with translational and rotational components for liquid electrolytes containing LiBF4 and propylene carbonate.

PubMed

Richardson, P M; Voice, A M; Ward, I M

2013-12-07

Longitudinal relaxation (T1) measurements of (19)F, (7)Li, and (1)H in propylene carbonate/LiBF4 liquid electrolytes are reported. Comparison of T1 values with those for the transverse relaxation time (T2) confirm that the measurements are in the high temperature (low correlation time) limit of the T1 minimum. Using data from pulsed field gradient measurements of self-diffusion coefficients and measurements of solution viscosity measured elsewhere, it is concluded that although in general there are contributions to T1 from both translational and rotational motions. For the lithium ions, this is mainly translational, and for the fluorine ions mainly rotational.

Evaluation of Municipal Wastewater Treatment Plant Activated Sludge for Biodegradation of Propylene Glycol as an Aircraft Deicing Fluid

DTIC Science & Technology

2012-03-01

Propylene Glycol Deicer Biodegredation Kinetics: Complete-Mix Stirred Tank Reactors , Filter, and Fluidized Bed . Journal of Environmental...scale sequencing batch reactor containing municipal waste water treatment facility activated sludge (AS) performing simultaneous organic carbon...Sequencing Batch Reactor Operation ..................................................................... 13 PG extraction from AS

Processes and systems for the production of propylene glycol from glycerol

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

Frye, John G; Oberg, Aaron A; Zacher, Alan H

2015-01-20

Processes and systems for converting glycerol to propylene glycol are disclosed. The glycerol feed is diluted with propylene glycol as the primary solvent, rather than water which is typically used. The diluted glycerol feed is sent to a reactor where the glycerol is converted to propylene glycol (as well as other byproducts) in the presence of a catalyst. The propylene glycol-containing product from the reactor is recycled as a solvent for the glycerol feed.

Simultaneous Saccharification and Fermentation of Sugar Beet Pulp with Mixed Bacterial Cultures for Lactic Acid and Propylene Glycol Production.

PubMed

Berlowska, Joanna; Cieciura, Weronika; Borowski, Sebastian; Dudkiewicz, Marta; Binczarski, Michal; Witonska, Izabela; Otlewska, Anna; Kregiel, Dorota

2016-10-17

Research into fermentative production of lactic acid from agricultural by-products has recently concentrated on the direct conversion of biomass, whereby pure sugars are replaced with inexpensive feedstock in the process of lactic acid production. In our studies, for the first time, the source of carbon used is sugar beet pulp, generated as a by-product of industrial sugar production. In this paper, we focus on the simultaneous saccharification of lignocellulosic biomass and fermentation of lactic acid, using mixed cultures with complementary assimilation profiles. Lactic acid is one of the primary platform chemicals, and can be used to synthesize a wide variety of useful products, including green propylene glycol. A series of controlled batch fermentations was conducted under various conditions, including pretreatment with enzymatic hydrolysis. Inoculation was performed in two sequential stages, to avoid carbon catabolite repression. Biologically-synthesized lactic acid was catalytically reduced to propylene glycol over 5% Ru/C. The highest lactic acid yield was obtained with mixed cultures. The yield of propylene glycol from the biological lactic acid was similar to that obtained with a water solution of pure lactic acid. Our results show that simultaneous saccharification and fermentation enables generation of lactic acid, suitable for further chemical transformations, from agricultural residues.

76 FR 17611 - Propylene Oxide; Proposed Pesticide Tolerance

Federal Register 2010, 2011, 2012, 2013, 2014

2011-03-30

...: This document proposes to amend the propylene oxide tolerance on ``nut, tree, group 14'' to ``nutmeat... ``nut, tree, group 14'' to read ``nutmeat, processed, except peanuts.'' A final rule published in the... the propylene oxide tolerance by replacing ``nutmeat, processed, except peanuts'' with ``nut, tree...

Propylene Glycol-Related Delirium After Esmolol Infusion.

PubMed

Kapitein, Berber S; Biesmans, Renee S C G; van der Sijs, Heleen S I; de Wildt, Saskia S N

2014-07-01

Excipients used in oral or intravenous preparations may cause serious adverse events. We present the case of a 15-year-old boy with hypertrophic cardiomyopathy. In the pediatric intensive care unit, he received high doses of continuous intravenous esmolol (range = 20-400 µg/kg/min) for cardiac rhythm control. After a few days he developed a delirium not responding to high doses of antipsychotics or discontinuation of benzodiazepines. We eventually realized that the IV esmolol formulation contained high doses of propylene glycol and ethanol, which may accumulate after prolonged infusion and cause intoxication. Intoxication with propylene glycolcan cause neuropsychiatric symptoms. The boy's propylene glycol plasma concentration was approximately 4 g/L, whereas clinical symptoms arise at concentrations above 1 to 1.44 g/L. Application of the Naranjo adverse drug reaction probability scale suggested a probable relationship (score 6) between the propylene glycol infusion and the delirium. After discontinuation of esmolol, the delirium disappeared spontaneously. This is the first case describing excipient toxicity of esmolol, with an objective causality assessment revealing a probable relationship for the adverse event-namely, delirium-and esmolol. Although excipient toxicity is a well-known adverse drug reaction, this case stresses the importance for easily available information for and education of physicians. © The Author(s) 2014.

21 CFR 589.1001 - Propylene glycol in or on cat food.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 21 Food and Drugs 6 2013-04-01 2013-04-01 false Propylene glycol in or on cat food. 589.1001... Listing of Specific Substances Prohibited From Use in Animal Food or Feed § 589.1001 Propylene glycol in or on cat food. The Food and Drug Administration has determined that propylene glycol in or on cat...

21 CFR 589.1001 - Propylene glycol in or on cat food.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 6 2014-04-01 2014-04-01 false Propylene glycol in or on cat food. 589.1001... Listing of Specific Substances Prohibited From Use in Animal Food or Feed § 589.1001 Propylene glycol in or on cat food. The Food and Drug Administration has determined that propylene glycol in or on cat...

21 CFR 589.1001 - Propylene glycol in or on cat food.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 21 Food and Drugs 6 2012-04-01 2012-04-01 false Propylene glycol in or on cat food. 589.1001... Listing of Specific Substances Prohibited From Use in Animal Food or Feed § 589.1001 Propylene glycol in or on cat food. The Food and Drug Administration has determined that propylene glycol in or on cat...

Measurement of diffusion coefficient of propylene glycol in skin tissue

NASA Astrophysics Data System (ADS)

Genin, Vadim D.; Bashkatov, Alexey N.; Genina, Elina A.; Tuchin, Valery V.

2015-03-01

Optical clearing of the rat skin under the action of propylene glycol was studied ex vivo. It was found that collimated transmittance of skin samples increased, whereas weight and thickness of the samples decreased during propylene glycol penetration in skin tissue. A mechanism of the optical clearing under the action of propylene glycol is discussed. Diffusion coefficient of propylene glycol in skin tissue ex vivo has been estimated as (1.35±0.95)×10-7 cm2/s with the taking into account of kinetics of both weight and thickness of skin samples. The presented results can be useful for enhancement of many methods of laser therapy and optical diagnostics of skin diseases and localization of subcutaneous neoplasms.

Acetonitrile Ion Suppression in Atmospheric Pressure Ionization Mass Spectrometry

NASA Astrophysics Data System (ADS)

Colizza, Kevin; Mahoney, Keira E.; Yevdokimov, Alexander V.; Smith, James L.; Oxley, Jimmie C.

2016-11-01

Efforts to analyze trace levels of cyclic peroxides by liquid chromatography/mass spectrometry gave evidence that acetonitrile suppressed ion formation. Further investigations extended this discovery to ketones, linear peroxides, esters, and possibly many other types of compounds, including triazole and menadione. Direct ionization suppression caused by acetonitrile was observed for multiple adduct types in both electrospray ionization and atmospheric pressure chemical ionization. The addition of only 2% acetonitrile significantly decreased the sensitivity of analyte response. Efforts to identify the mechanism were made using various nitriles. The ion suppression was reduced by substitution of an acetonitrile hydrogen with an electron-withdrawing group, but was exacerbated by electron-donating or steric groups adjacent to the nitrile. Although current theory does not explain this phenomenon, we propose that polar interactions between the various functionalities and the nitrile may be forming neutral aggregates that manifest as ionization suppression.

Designed synergetic effect of electrolyte additives to improve interfacial chemistry of MCMB electrode in propylene carbonate-based electrolyte for enhanced low and room temperature performance.

PubMed

Wotango, Aselefech Sorsa; Su, Wei-Nien; Haregewoin, Atetegeb Meazah; Chen, Hung-Ming; Cheng, Ju-Hsiang; Lin, Ming-Hsien; Wang, Chia-Hsin; Hwang, Bing-Joe

2018-05-09

The performance of lithium ion batteries rapidly falls at lower temperatures due to decreasing conductivity of electrolytes and Solid Electrolyte Interphase (SEI) on graphite anode. Hence, it limits the practical use of lithium ion batteries at sub-zero temperatures and also affects the development of lithium ion batteries for widespread applications. The SEI formed on the graphite surface is very influential in determining the performance of the battery. Herein, a new electrolyte additive, 4-Chloromethyl-1,3,2-dioxathiolane-2-oxide (CMDO), is prepared to improve the properties of commonly used electrolyte constituents - ethylene carbonate (EC), and fluoroethylene carbonate (FEC). The formation of an efficient passivation layer in propylene carbonate (PC) -based electrolyte for MCMB electrode was investigated. The addition of CMDO resulted in a much less irreversible capacity loss and induces thin SEI formation. However, the combination of the three additives played a key role to enhance reversible capacity of MCMB electrode at lower or ambient temperature. The electrochemical measurement analysis showed that the SEI formed from a mixture of the three additives gave better intercalation-deintercalation of lithium ions.

21 CFR 500.50 - Propylene glycol in or on cat food.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Propylene glycol in or on cat food. 500.50 Section... Propylene glycol in or on cat food. The Food and Drug Administration has determined that propylene glycol in or on cat food is not generally recognized as safe and is a food additive subject to section 409 of...

21 CFR 500.50 - Propylene glycol in or on cat food.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 6 2011-04-01 2011-04-01 false Propylene glycol in or on cat food. 500.50 Section... Propylene glycol in or on cat food. The Food and Drug Administration has determined that propylene glycol in or on cat food is not generally recognized as safe and is a food additive subject to section 409 of...

Interaction of monovalent cations with acetonitrile

NASA Astrophysics Data System (ADS)

Černušák, Ivan; Aranyosiová, Monika; Vollárová, Ol'ga; Velič, Dušan; Kirdajová, Ol'ga; Benko, Ján

Solvation of monovalent cations (Me+) of alkali metals=Na+, K+, Rb+, and Cs+, coinage metals=Cu+, Ag+, Au+, and p-block elements Ga+, In+, and Tl+ with acetonitrile was studied by means of ab initio calculations and time-of-flight secondary ion mass spectrometry (TOF-SIMS). The intermolecular interactions in the complexes Me+···CH3CN were investigated using the coupled clusters theory including single, double, and noniterative triple substitutions (CCSD(T)) in conjunction with the Pol and Pol-dk basis sets. The binding energies of these donor-acceptor complexes were estimated; taking into account the basis set superposition error, zero-point vibrations, correlation contribution, and scalar relativistic corrections. The theoretical ΔG0298 K values based on CCSD(T)/Pol and/or CCSD(T)/Pol-dk binding energies correlated well with experimental transfer Gibbs energies (from water to acetonitrile) for the series of cations. In the case of Au monocation, relativistic correction turned out to be extremely important. Composition of the complex of Ag+ and Na+ with acetonitrile was determined by using SIMS supporting both theoretical and experimental transfer Gibbs energies.

Single dose intratympanic mesna application inhibits propylene glycol induced cholesteatoma formation.

PubMed

Ismi, O; Karabulut, Y Y; Bal, K K; Vayisoglu, Y; Unal, M

2017-03-01

Mesna (i.e. sodium 2-mercaptoethanesulfonate; C2H5NaO3S2) has been used in otological surgery such as cholesteatoma dissection and tympanic membrane lateralisation in atelectatic ears. However, this study aimed to investigate its effect on cholesteatoma formation. A total of 20 Wistar rats were divided into two groups of 10 animals. The right and left ears of control animals were treated with saline (saline control group; n = 10 ears) and propylene glycol plus saline (propylene glycol control group; n = 10 ears), respectively. In the mesna group, both ears were treated with propylene glycol plus mesna (n = 20 ears). On days 1, 8 and 15, the saline control group had intratympanic injections of 0.2 ml saline and the propylene glycol control and mesna groups had intratympanic injections of 0.2 ml 100 per cent propylene glycol. On day 22, the propylene glycol control group had a single intratympanic injection of 0.2 ml saline and the mesna group had a single intratympanic injection of 10 per cent mesna. Animals were killed 12 weeks after the last injection and the temporal bones were sent for histopathological evaluation. The cholesteatoma formation rate was 88 per cent in the propylene glycol control group, but was significantly lower in the mesna group (p = 0.01). There were no significant differences in granulation tissue formation (p = 0.498), cyst formation in the bulla (p = 0.381), fibrosis (p = 0.072) and epithelial hyperplasia (p = 0.081) among experimental groups. Intratympanic propylene glycol administration is an effective method of promoting experimental cholesteatoma formation. Administration of a single dose of intratympanic mesna inhibited cholesteatoma formation in an animal model.

Synthesis of Poly(Propylene Fumarate)

PubMed Central

Kasper, F. Kurtis; Tanahashi, Kazuhiro; Fisher, John P.; Mikos, Antonios G.

2010-01-01

This protocol describes the synthesis of 500 – 4000 Da poly(propylene fumarate) by a two-step reaction of diethyl fumarate and propylene glycol through a bis(hydroxypropyl) fumarate diester intermediate. Purified PPF can be covalently crosslinked to form degradable polymer networks, which have been widely explored for biomedical applications. The properties of crosslinked PPF networks depend upon the molecular properties of the constituent polymer, such as the molecular weight. The purity of the reactants and the exclusion of water from the reaction system are of utmost importance in the generation of high-molecular-weight PPF products. Additionally, the reaction time and temperature influence the molecular weight of the PPF product. The expected time required to complete this protocol is 3 d. PMID:19325548

Propylene glycol monoethyl ether

Integrated Risk Information System (IRIS)

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

Preparation, melting behavior and thermal stability of poly(lactic acid)/poly(propylene carbonate) blends processed by vane extruder

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

Zou, Wei, E-mail: zw55624@163.com; Chen, Rongyuan; Zhang, Haichen

Poly (lactic acid) (PLA)/Poly (propylene carbonate) (PPC) blends were prepared by vane extruder which is a type of novel polymer processing extruder based on elongation force field. Scanning electron microscope (SEM), differential scanning calorimetry (DSC) and thermogravimetric (TG) were used respectively to analyze the compatibility, the melting behavior and thermal stability properties of PLA/PPC blends affected by the different content of PPC. The results showed that with the increase of the PPC content, the glass transition temperature of PLA was reduced, and the glass transition temperature of PPC was increased, which indicated that PLA and PPC had partial compatibility. Themore » cold crystallization temperature of PLA increased with the increase of the PPC content, which showed that PPC hindered the cold crystallization process of PLA. The addition of PPC had little impact on the melting process of PLA, and the melting temperature of PLA was almost kept the same value. Thermogravimetric analysis showed that the thermal stability of PPC was worse than that of PLA, the addition of PPC reduced the thermal stability of PLA.« less

Modeling random methyl branching in ethylene/ propylene copolymers using metathesis chemistry: synthesis and thermal behavior.

PubMed

Sworen, John C; Smith, Jason A; Wagener, Kenneth B; Baugh, Lisa S; Rucker, Steven P

2003-02-26

The structure of random ethylene/propylene (EP) copolymers has been modeled using step polymerization chemistry. Six ethylene/propylene model copolymers have been prepared via acyclic diene metathesis (ADMET) polymerization and characterized for primary and higher level structure using in-depth NMR, IR, DSC, WAXD, and GPC analysis. These copolymers possess 1.5, 7.1, 13.6, 25.0, 43.3, and 55.6 methyl branches per 1000 carbons. Examination of these macromolecules by IR and WAXD analysis has demonstrated the first hexagonal phase in EP copolymers containing high ethylene content (90%) without the influence of sample manipulation (temperature, pressure, or radiation). Thermal behavior studies have shown that the melting point and heat of fusion decrease as the branch content increases. Further, comparisons have been made between these random ADMET EP copolymers, random EP copolymers made by typical chain addition techniques, and precisely branched ADMET EP copolymers.

Stabilization of distearoylphosphatidylcholine lamellar phases in propylene glycol using cholesterol.

PubMed

Harvey, Richard D; Ara, Nargis; Heenan, Richard K; Barlow, David J; Quinn, Peter J; Lawrence, M Jayne

2013-12-02

Phospholipid vesicles (liposomes) formed in pharmaceutically acceptable nonaqueous polar solvents such as propylene glycol are of interest in drug delivery because of their ability to improve the bioavailability of drugs with poor aqueous solubility. We have demonstrated a stabilizing effect of cholesterol on lamellar phases formed by dispersion of distearoylphosphatidylcholine (DSPC) in water/propylene glycol (PG) solutions with glycol concentrations ranging from 0 to 100%. The stability of the dispersions was assessed by determining the effect of propylene glycol concentration on structural parameters of the lamellar phases using a complementary combination of X-ray and neutron scattering techniques at 25 °C and in the case of X-ray scattering at 65 °C. Significantly, although stable lamellar phases (and liposomes) were formed in all PG solutions at 25 °C, the association of the glycol with the liposomes' lamellar structures led to the formation of interdigitated phases, which were not thermostable at 65 °C. With the addition of equimolar quantities of cholesterol to the dispersions of DSPC, stable lamellar dispersions (and indeed liposomes) were formed in all propylene glycol solutions at 25 °C, with the significant lateral phase separation of the bilayer components only detectable in propylene glycol concentrations above 60% (w/w). We propose that the stability of lamellar phases of the cholesterol-containing liposomes formed in propylene glycol concentrations of up to 60% (w/w) represent potentially very valuable drug delivery vehicles for a variety of routes of administration.

Dewetting acrylic polymer films with water/propylene carbonate/surfactant mixtures - implications for cultural heritage conservation.

PubMed

Baglioni, M; Montis, C; Brandi, F; Guaragnone, T; Meazzini, I; Baglioni, P; Berti, D

2017-09-13

The removal of hydrophobic polymer films from surfaces is one of the top priorities of modern conservation science. Nanostructured fluids containing water, good solvents for polymers, either immiscible or partially miscible with water, and surfactants have been used in the last decade to achieve controlled removal. The dewetting of the polymer film is often an essential step to achieve efficient removal; however, the role of the surfactant throughout the process is yet to be fully understood. We report on the dewetting of a methacrylate/acrylate copolymer film induced by a ternary mixture of water, propylene carbonate (PC) and C 9-11 E 6 , a nonionic alcohol ethoxylate surfactant. The fluid microstructure was characterised through small angle X-ray scattering and the interactions between the film and water, water/PC and water/PC/C 9-11 E 6 , were monitored through confocal laser-scanning microscopy (CLSM) and analised both from a thermodynamic and a kinetic point of view. The presence of a surfactant is a prerequisite to induce dewetting of μm-thick films at room temperature, but it is not a thermodynamic driver. The amphiphile lowers the interfacial energy between the phases and favors the loss of adhesion of the polymer on glass, decreasing, in turn, the activation energy barrier, which can be overcome by the thermal fluctuations of polymer film stability, initiating the dewetting process.

21 CFR 172.765 - Succistearin (stearoyl propylene glycol hydrogen succinate).

Code of Federal Regulations, 2010 CFR

2010-04-01

... HUMAN SERVICES (CONTINUED) FOOD FOR HUMAN CONSUMPTION (CONTINUED) FOOD ADDITIVES PERMITTED FOR DIRECT ADDITION TO FOOD FOR HUMAN CONSUMPTION Other Specific Usage Additives § 172.765 Succistearin (stearoyl propylene glycol hydrogen succinate). The food additive succistearin (stearoyl propylene glycol hydrogen...

Green hydrophilic interaction chromatography using ethanol-water-carbon dioxide mixtures.

PubMed

Pereira, Alberto dos Santos; Girón, Ana Jiménez; Admasu, Engdawork; Sandra, Pat

2010-03-01

In hydrophilic interaction chromatography (HILIC), best results are obtained with high concentrations of acetonitrile. In the framework of green chromatography, different concentrations of carbon dioxide were added to the mobile phases acetonitrile-water and ethanol-water and the impact on retention and separation in HILIC using bare silica as stationary phase was explored. The features of HILIC using enhanced-fluidity mobile phases are illustrated with the analysis of the nucleobases and a mixture containing the nucleobases and cortisol, flurbiprofen, theophylline and caffeine. For both organic constituents, the elution window is widened in function of the carbon dioxide concentration and selectivity changes. At high concentrations of carbon dioxide in ethanol, separations were similar to those obtained with acetonitrile without carbon dioxide addition.

Severe lactic acidosis after an iatrogenic propylene glycol overdose.

PubMed

Zosel, Amy; Egelhoff, Elizabeth; Heard, Kennon

2010-02-01

Propylene glycol is a diluent found in many intravenous and oral drugs, including phenytoin, diazepam, and lorazepam. Propylene glycol is eliminated from the body by oxidation through alcohol dehydrogenase to form lactic acid. Under normal conditions, the body converts lactate to pyruvate and metabolizes pyruvate through the Krebs cycle. Lactic acidosis has occurred in patients, often those with renal dysfunction, who were receiving prolonged infusions of drugs that contain propylene glycol as a diluent. We describe a 50-year-old man who experienced severe lactic acidosis after receiving an accidental overdose of lorazepam, which contains propylene glycol. The patient was acutely intoxicated, with a serum ethanol concentration of 406 mg/dl. He had choked on a large piece of meat and subsequently experienced pulseless electrical activity with ventricular fibrillation cardiac arrest. He was brought to the emergency department; within 2 hours, he was admitted to the intensive care unit for initiation of the hypothermia protocol. The patient began to experience generalized tonic-clonic seizures 12 hours later, which resolved after several boluses of lorazepam. A lorazepam infusion was started; however, it was inadvertently administered at a rate of 2 mg/minute instead of the standard rate of 2 mg/hour. Ten hours later, the administration error was recognized and the infusion stopped. The patient's peak propylene glycol level was 659 mg/dl, pH 6.9, serum bicarbonate level 5 mEq/L, and lactate level 18.6 mmol/L. Fomepizole was started the next day and was continued until hospital day 3. Continuous renal replacement therapy was started and then replaced with continuous venovenous hemofiltration (CVVH) for the remainder of the hospital stay. The patient's acidosis resolved by day 3, when his propylene glycol level had decreased to 45 mg/dl. Fomepizole was discontinued, but the patient's prognosis was poor (anoxic brain injury); thus care was withdrawn and the patient died

Comparison of Thermal Performance Characteristics of Ammonia and Propylene Loop Heat Pipes

NASA Technical Reports Server (NTRS)

Kaya, Tarik; Baker, Charles; Ku, Jentung

2000-01-01

In this paper, experimental work performed on a breadboard Loop Heat Pipe (LHP) is presented. The test article was built by DCI for the Geoscience Laser Altimeter System (GLAS) instrument on the ICESat spacecraft. The thermal system requirements of GLAS have shown that ammonia cannot be used as the working fluid in this LHP because GLAS radiators could cool to well below the freezing point of ammonia. As a result, propylene was proposed as an alternative LHP working fluid since it has a lower freezing point than ammonia. Both working fluids were tested in the same LHP following a similar test plan in ambient conditions. The thermal performance characteristics of ammonia and propylene LHP's were then compared. In general, the propylene LHP required slightly less startup superheat 5nd less control heater power than the ammonia LHP, The thermal conductance values for the propylene LHP were also lower than the ammonia LHP. Later, the propylene LHP was tested in a thermal vacuum chamber. These tests demonstrated that propylene could meet the GLAS thermal design requirements. Design guidelines were proposed for the next flight-like Development Model (DM) LHP for thermal control of the GLAS instrument.

21 CFR 172.850 - Lactylated fatty acid esters of glycerol and propylene glycol.

Code of Federal Regulations, 2014 CFR

2014-04-01

... propylene glycol. 172.850 Section 172.850 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH... CONSUMPTION Multipurpose Additives § 172.850 Lactylated fatty acid esters of glycerol and propylene glycol. The food additive lactylated fatty acid esters of glycerol and propylene glycol may be safely used in...

Severe propylene glycol toxicity secondary to use of anti-epileptics.

PubMed

Pillai, Unnikrishnan; Hothi, Jatinder C; Bhat, Zeenat Y

2014-01-01

Propylene glycol toxicity presenting as high anion gap metabolic acidosis and osmolar gap has been extensively reported in literature, and most of them are secondary to intravenous lorazepam infusion. However, propylene glycol is used as a solvent in a number of medications that are frequently utilized in critical care setting, and hence one should be aware that the toxicity is possible from a variety of medication. Phenobarbital and phenytoin are one of those, and we hereby report a novel case of propylene glycol toxicity secondary to phenobarbital and phenytoin infusion in a patient with refractory status epilepticus. Furthermore, our patient had end-stage renal disease, which we think could have been an important precipitating factor for the toxicity. Because most of the symptoms from propylene glycol toxicity can mimic sepsis-which is very common in critical care unit patients-this life threatening scenario could be easily missed. Regular monitoring of osmolar gap is an easily available intervention in the at risk patients.

21 CFR 172.850 - Lactylated fatty acid esters of glycerol and propylene glycol.

Code of Federal Regulations, 2012 CFR

2012-04-01

... propylene glycol. 172.850 Section 172.850 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH... esters of glycerol and propylene glycol. The food additive lactylated fatty acid esters of glycerol and propylene glycol may be safely used in food in accordance with the following prescribed conditions: (a) The...

21 CFR 172.850 - Lactylated fatty acid esters of glycerol and propylene glycol.

Code of Federal Regulations, 2013 CFR

2013-04-01

... propylene glycol. 172.850 Section 172.850 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH... esters of glycerol and propylene glycol. The food additive lactylated fatty acid esters of glycerol and propylene glycol may be safely used in food in accordance with the following prescribed conditions: (a) The...

Enzymatic remediated biodegradation of propylene glycol 1,2-dinitrate

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

Meng, M.; Geelhaar, L.; Speedie, M.K.

1995-12-31

Two bacterial species, Enterobacter agglomerans and Bacillus thuringiensis/cereus, which were selected from nitroglycerin (GTN) contaminated soil, have previously been shown to have denitrating ability on nitroglycerin. This abstract presents the investigation of the cell free extracts from both microorganisms for the degradation of another nitrate ester contaminant; propylene glycol 1,2-dinitrate (PGDN). This compound has been previously considered resistant to the biodegradation. In order to probe the pathway, the whole process was monitored by using [1-{sup 14}C]-PGDN as substrate and the intermediates were identified by HPLC and TLC chromatography. Long term biodegradation experiments have shown that the enzymes in the cytoplasmmore » fraction of Bacillus thuringiensis/cereus and the membrane fraction of Enterobacter agglomerans convert PGDN successively into propylene glycol 1-mononitrate (1-PGMN) and propylene glycol 2-mononitrate (2-PGMN), and finally, propylene glycol. The capacity to achieve sequential and complete degradation of PGDN implies that it follows a similar mechanism to that observed in the GTN degradation. Cofactor requirements for PGDN breakdown have been studied, it was found that no dissociable, dialyzable cofactors are required.« less

Interaction of acetonitrile with the surfaces of amorphous and crystalline ice

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

Schaff, J.E.; Roberts, J.T.

1999-10-12

The adsorption of acetonitrile (CH{sub 3}CN) on ultrathin films of ice under ultrahigh vacuum was investigated with temperature-programmed desorption ass spectrometry (TPD) and Fourier transform infrared reflection absorption spectroscopy (FTIRAS). Two types of film were studied, amorphous and crystalline. On the amorphous films, two sates of adsorbed acetonitrile were observed by TPD and FTIRAS. One of the states is attributed to acetonitrile that is hydrogen bonded to agree OH group at the ice surface; the other state is assigned to acetonitrile that is purely physiorbed. Evidence for the hydrogen-bonded state is two-fold. First, there is a large kinetic isotope effectmore » for desorption from H{sub 2}O-and D{sub 2}O-ice: the desorption temperatures from ice-h{sub 2} and ice-d{sub 2} are {approximately}161 and {approximately}176 K, respectively. Second, the C{triple{underscore}bond}N stretching frequency (2,265 cm{sup {minus}1}) is 16 cm{sup {minus}1} is greater than that of physisorbed acetonitrile, and it is roughly equal to that of acetonitrile which is hydrogen bonded to an OH group at the air-liquid water interface. On the crystalline films, there is no evidence for a hydrogen-bonded state in the TPD spectra. The FTIRAS spectra do show that some hydrogen-bonded acetonitrile is present but at a maximum coverage that is roughly one-sixth of that on the amorphous surface. The difference between the amorphous and crystalline surfaces cannot be attributed to a difference n surface areas. Rather, this work provides additional evidence that the surface chemical properties of amorphous ice are different from those of crystalline ice.« less

Cometabolic degradation of chlorinated alkenes by alkene monooxygenase in a propylene-grown Xanthobacter strain.

PubMed Central

Ensign, S A; Hyman, M R; Arp, D J

1992-01-01

Propylene-grown Xanthobacter cells (strain Py2) degraded several chlorinated alkenes of environmental concern, including trichloroethylene, 1-chloroethylene (vinyl chloride), cis- and trans-1,2-dichloroethylene, 1,3-dichloropropylene, and 2,3-dichloropropylene. 1,1-Dichloroethylene was not degraded efficiently, while tetrachloroethylene was not degraded. The role of alkene monooxygenase in catalyzing chlorinated alkene degradations was established by demonstrating that glucose-grown cells which lack alkene monooxygenase and propylene-grown cells in which alkene monooxygenase was selectively inactivated by propyne were unable to degrade the compounds. C2 and C3 chlorinated alkanes were not oxidized by alkene monooxygenase, but a number of these compounds were inhibitors of propylene and ethylene oxidation, suggesting that they compete for binding to the enzyme. A number of metabolites enhanced the rate of degradation of chlorinated alkenes, including propylene oxide, propionaldehyde, and glucose. Propylene stimulated chlorinated alkene oxidation slightly when present at a low concentration but became inhibitory at higher concentrations. Toxic effects associated with chlorinated alkene oxidations were determined by measuring the propylene oxidation and propylene oxide-dependent O2 uptake rates of cells previously incubated with chlorinated alkenes. Compounds which were substrates for alkene monooxygenase exhibited various levels of toxicity, with 1,1-dichloroethylene and trichloroethylene being the most potent inactivators of propylene oxidation and 1,3- and 2,3-dichloropropylene being the most potent inactivators of propylene oxide-dependent O2 uptake. No toxic effects were seen when cells were incubated with chlorinated alkenes anaerobically, indicating that the product(s) of chlorinated alkene oxidation mediates toxicity. PMID:1444418

Propylene glycol monomethyl ether (PGME)

Integrated Risk Information System (IRIS)

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

A computational study of the catalytic aerobic epoxidation of propylene over the coordinatively unsaturated metal-organic framework Fe3(btc)2: formation of propylene oxide and competing reactions.

PubMed

Maihom, Thana; Sawangphruk, Montree; Probst, Michael; Limtrakul, Jumras

2018-02-28

The aerobic epoxidation of propylene over the metal-organic framework Fe 3 (btc) 2 (btc = 1,3,5-benzentricarboxylate) as catalyst has been investigated by means of density functional calculations. The mechanisms of the reaction towards propylene oxide, carbonylic products (acetone and propanal) and a pi-allyl radical were investigated to assess the efficiency of Fe 3 (btc) 2 for the selective formation of propylene oxide. Propylene oxide and carbonylic products are formed on Fe 3 (btc) 2 by proceeding via propyleneoxy intermediates in the first step. Subsequently, the intermediates can then either be transformed to propylene oxide by way of ring closure of the intermediate or to the carbonylic compounds of propanal and acetone via 1,2-hydride shift. The results show that the formation of propylene oxide is favored over the formation of carbonylic products mainly due to the activation barriers being 2-3 times smaller. The activation barriers for the formation of the propyleneoxy intermediates on the Fe 3 (btc) 2 catalyst for the first and second reaction cycle are also lower than the barriers obtained for the formation of the pi-allyl radical that acts as the precursor to combustion products. On the basis of these computational results, we therefore expect a high catalytic selectivity of the Fe 3 (btc) 2 catalyst with respect to the formation of propylene oxide. We also compared the catalytic activities of Fe 3 (btc) 2 and Cu 3 (btc) 2 . The activation energy of the rate-determining step is almost 2 times lower for Fe 3 (btc) 2 than that for Cu 3 (btc) 2 , due to a larger charge transfer from the catalytic site to the O 2 molecule in the case of Fe 3 (btc) 2 .

Propylene Glycol Poisoning From Excess Whiskey Ingestion: A Case of High Osmolal Gap Metabolic Acidosis.

PubMed

Cunningham, Courtney A; Ku, Kevin; Sue, Gloria R

2015-01-01

In this report, we describe a case of high anion gap metabolic acidosis with a significant osmolal gap attributed to the ingestion of liquor containing propylene glycol. Recently, several reports have characterized severe lactic acidosis occurring in the setting of iatrogenic unintentional overdosing of medications that use propylene glycol as a diluent, including lorazepam and diazepam. To date, no studies have explored potential effects of excess propylene glycol in the setting of alcohol intoxication. Our patient endorsed drinking large volumes of cinnamon flavored whiskey, which was likely Fireball Cinnamon Whisky. To our knowledge, this is the first case of propylene glycol toxicity from an intentional ingestion of liquor containing propylene glycol.

Effect of BaTiO3 nano-particles on breakdown performance of propylene carbonate.

PubMed

Hou, Yanpan; Zhang, Zicheng; Zhang, Jiande; Liu, Zhuofeng; Song, Zuyin

2015-05-01

As an alternative to water, propylene carbonate (PC) has a good application prospect in the compact pulsed power sources for its breakdown strength higher than that of water, resistivity bigger than 10(9) Ω m, and low freezing temperature (-49 °C). In this paper, the investigation into dielectric breakdown of PC and PC-based nano-fluids (NFs) subjected to high amplitude electric field is presented with microsecond pulses applied to a 1 mm gap full of PC or NFs between spherical electrodes. One kind of NF is composed of PC mixed with 0.5-1.4 vol. % BaTiO3 (BT) nano-particles of mean diameter ≈100 nm and another is mixed with 0.3-0.8 vol. % BT nano-particles of mean diameter ≈30 nm. The experimental results demonstrate the rise of permittivity and improvement of the breakdown strength of NFs compared with PC. Moreover, it is found that there exists an optimum fraction for these NFs corresponding to tremendous surface area in nano-composites with finite mesoscopic thickness. In concrete, the dielectric breakdown voltage of NFs is 33% higher than that of PC as the volume concentration of nano-particles with a 100 nm diameter is 0.9% and the breakdown voltage of NFs is 40% higher as the volume concentration of nano-particles with a 30 nm diameter is 0.6%. These phenomena are considered as the dielectric breakdown voltage of PC-based NFs is increased because the interfaces between nano-fillers and PC matrices provide myriad trap sites for charge carriers, which play a dominant role in the breakdown performance of NFs.

21 CFR 172.856 - Propylene glycol mono- and diesters of fats and fatty acids.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Propylene glycol mono- and diesters of fats and... CONSUMPTION Multipurpose Additives § 172.856 Propylene glycol mono- and diesters of fats and fatty acids. Propylene glycol mono- and diesters of fats and fatty acids may be safely used in food, subject to the...

Laser synthesis and spectroscopy of acetonitrile/silver nanoparticles

NASA Astrophysics Data System (ADS)

Akin, S. T.; Liu, X.; Duncan, M. A.

2015-11-01

Silver nanoparticles with acetonitrile ligands are produced in a laser ablation flow reactor. Excimer laser ablation produces gas phase metal clusters which are thermalized with helium or argon collisions in the flowtube, and reactions with acetonitrile vapor coordinate this ligand to the particle surface. The gaseous mixture is captured in a cryogenic trap; warming produces a solution of excess ligand and coated particles. TEM images reveal particle sizes of 10-30 nm diameter. UV-vis absorption and fluorescence spectra are compared to those of standard silver nanoparticles with surfactant coatings. Deep-UV ligand absorption is strongly enhanced by nanoparticle adsorption.

Synthesis of biocompatible poly(ɛ-caprolactone)- block-poly(propylene adipate) copolymers appropriate for drug nanoencapsulation in the form of core-shell nanoparticles

PubMed Central

Nanaki, Stavroula G; Pantopoulos, Kostas; Bikiaris, Dimitrios N

2011-01-01

Poly(propylene adipate)-block-poly(ɛ-caprolactone) copolymers were synthesized using a combination of polycondensation and ring-opening polymerization of ɛ-caprolactone in the presence of poly(propylene adipate). Gel permeation chromatography was used for molecular weight determination, whereas hydrogen-1 nuclear magnetic resonance and carbon-13 nuclear magnetic resonance spectroscopy were employed for copolymer characterization and composition evaluation. The copolymers were found to be block while their composition was similar to the feeding ratio. They formed semicrystalline structures, while only poly(ɛ-caprolactone) formed crystals, as shown by wide angle X-ray diffraction. Differential scanning calorimetry data suggest that the melting point and heat of fusion of copolymers decreased by increasing the poly(propylene adipate) amount. The synthesized polymers exhibited low cytotoxicity and were used to encapsulate desferrioxamine, an iron-chelating drug. The desferrioxamine nanoparticles were self-assembled into core shell structures, had mean particle size <250 nm, and the drug remained in crystalline form. Further studies revealed that the dissolution rate was mainly related to the melting temperature, as well as to the degree of crystallinity of copolymers. PMID:22162656

Synthesis of biocompatible poly(ɛ-caprolactone)- block-poly(propylene adipate) copolymers appropriate for drug nanoencapsulation in the form of core-shell nanoparticles.

PubMed

Nanaki, Stavroula G; Pantopoulos, Kostas; Bikiaris, Dimitrios N

2011-01-01

Poly(propylene adipate)-block-poly(ɛ-caprolactone) copolymers were synthesized using a combination of polycondensation and ring-opening polymerization of ɛ-caprolactone in the presence of poly(propylene adipate). Gel permeation chromatography was used for molecular weight determination, whereas hydrogen-1 nuclear magnetic resonance and carbon-13 nuclear magnetic resonance spectroscopy were employed for copolymer characterization and composition evaluation. The copolymers were found to be block while their composition was similar to the feeding ratio. They formed semicrystalline structures, while only poly(ɛ-caprolactone) formed crystals, as shown by wide angle X-ray diffraction. Differential scanning calorimetry data suggest that the melting point and heat of fusion of copolymers decreased by increasing the poly(propylene adipate) amount. The synthesized polymers exhibited low cytotoxicity and were used to encapsulate desferrioxamine, an iron-chelating drug. The desferrioxamine nanoparticles were self-assembled into core shell structures, had mean particle size <250 nm, and the drug remained in crystalline form. Further studies revealed that the dissolution rate was mainly related to the melting temperature, as well as to the degree of crystallinity of copolymers.

Electrochemical behavior of high performance on-chip porous carbon films for micro-supercapacitors applications in organic electrolytes

NASA Astrophysics Data System (ADS)

Brousse, K.; Huang, P.; Pinaud, S.; Respaud, M.; Daffos, B.; Chaudret, B.; Lethien, C.; Taberna, P. L.; Simon, P.

2016-10-01

Carbide derived carbons (CDCs) are promising materials for preparing integrated micro-supercapacitors, as on-chip CDC films are prepared via a process fully compatible with current silicon-based device technology. These films show good adherence on the substrate and high capacitance thanks to their unique nanoporous structure which can be fine-tuned by adjusting the synthesis parameters during chlorination of the metallic carbide precursor. The carbon porosity is mostly related to the synthesis temperature whereas the thickness of the films depends on the chlorination duration. Increasing the pore size allows the adsorption of large solvated ions from organic electrolytes and leads to higher energy densities. Here, we investigated the electrochemical behavior and performance of on-chip TiC-CDC in ionic liquid solvent mixtures of 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIBF4) diluted in either acetonitrile or propylene carbonate via cyclic voltammetry and electrochemical impedance spectroscopy. Thin CDC films exhibited typical capacitive signature and achieved 169 F cm-3 in both electrolytes; 65% of the capacitance was still delivered at 1 V s-1. While increasing the thickness of the films, EMI+ transport limitation was observed in more viscous PC-based electrolyte. Nevertheless, the energy density reached 90 μW h cm-2 in 2M EMIBF4/ACN, confirming the interest of these CDC films for micro-supercapacitors applications.

Correlation between the size and the magnetic properties of Ag2+ clusters loaded on ceria surface and their catalytic performance in the total oxidation of propylene. EPR study

NASA Astrophysics Data System (ADS)

Hany, Sara; Skaf, Mira; Aouad, Samer; Gennequin, Cédric; Labaki, Madona; Abi-Aad, Edmond; Aboukaïs, Antoine

2018-03-01

Three different types of Ag2+ ions ("a", "b", and "c") have been identified and examined by electron paramagnetic resonance (EPR) on 10% wt Ag/CeO2 prepared by impregnation method. One of them, Ag2+(b), behaves differently than the two others, Ag2+(a) and Ag2+(c), under redox atmospheres. The fact that, in reducing conditions (vacuum, propylene, hydrogen, and carbon black), Ag2+(a) and Ag2+(c) species were more easily reduced than Ag2+(b) ones, could not explain the catalytic performance and stability of this latter species compared to the first ones in the reaction of total oxidation of propylene. The EPR technique evidenced that Ag2+(b) species form, upon propene oxidation, a cluster. This cluster is composed of two parallel electron spins (dimer) and three nuclear spins (trimer). It seems that before propylene oxidation, Ag2+(b) clusters were ferromagnetic. This ferromagnetic character of Ag2+(b) species may explain their better catalytic performance, in propylene oxidation, than those of Ag2+(a) and Ag2+(c) ones.

Flexible interfaces between Si anodes and composite electrolytes consisting of poly(propylene carbonates) and garnets for solid-state batteries

NASA Astrophysics Data System (ADS)

Huo, Hanyu; Sun, Jiyang; chen, Cheng; Meng, Xianglu; He, Minghui; Zhao, Ning; Guo, Xiangxin

2018-04-01

Flexible interfaces between Si anodes and composite electrolytes consisting of poly(propylene carbonates) (PPCs) and garnets have been fabricated. The solid polymer electrolytes (SPEs) of PPC/garnet/LiTFSI show the conductivity of 4.2 × 10-4 S cm-1 at room temperature. Their combination with the Si layer anodes allows great alleviation of internal stress resulting from the large volume variation during lithiation and delithiation process of Si anodes. As a result, the Si/SPE/Li cells exhibit 2520 mAh g-1, 2260 mAh g-1, 1902 mAh g-1, 1342 mAh g-1 at 0.1 C, 0.2 C, 0.5 C, and 1 C, respectively. Furthermore, with such compatible and stable interfaces of Si/SPE and the LiFePO4 cathodes in solid-state batteries, the specific capacity of 2296 mAh g-1 in terms of Si is obtained, which remains 82.6% after 100 cycles at room temperature and 0.1 C. The results here indicate that constructing of flexible interfaces between Si anodes and SPEs is a promising strategy to develop high performance solid-state batteries.

Influence of nanoparticle concentration on thermo-physical properties of CuO-propylene glycol nanofluids.

PubMed

Suganthi, Kuppusamy Swaminathan; Radhakrishnan, Anju K; Anusha, Natarajan; Rajan, Kalpoondi Sekar

2014-06-01

Experiments were performed on the preparation and characterization of CuO-propylene glycol nanofluids. The influence of nanoparticle concentration and temperature on nanofluid viscosity reveals existence of a range of nanoparticle concentration and temperature in which the viscosity of nanofluid is lower than that of propylene glycol, possibly due to interactions between nanoparticles and propylene glycol. A temperature-independent, thermal conductivity enhancement of 38% was obtained for nanoparticle concentration of 1.5 vol% over a temperature range of 10-60 degrees C. We believe that particle clustering contributes to the thermal conductivity enhancement in CuO-propylene glycol nanofluids.

Stabilization of the Thermal Decomposition of Poly(Propylene Carbonate) Through Copper Ion Incorporation and Use in Self-Patterning

NASA Astrophysics Data System (ADS)

Spencer, Todd J.; Chen, Yu-Chun; Saha, Rajarshi; Kohl, Paul A.

2011-06-01

Incorporation of copper ions into poly(propylene carbonate) (PPC) films cast from γ-butyrolactone (GBL), trichloroethylene (TCE) or methylene chloride (MeCl) solutions containing a photo-acid generator is shown to stabilize the PPC from thermal decomposition. Copper ions were introduced into the PPC mixtures by bringing the polymer mixture into contact with copper metal. The metal was oxidized and dissolved into the PPC mixture. The dissolved copper interferes with the decomposition mechanism of PPC, raising its decomposition temperature. Thermogravimetric analysis shows that copper ions make PPC more stable by up to 50°C. Spectroscopic analysis indicates that copper ions may stabilize terminal carboxylic acid groups, inhibiting PPC decomposition. The change in thermal stability based on PPC exposure to patterned copper substrates was used to provide a self-aligned patterning method for PPC on copper traces without the need for an additional photopatterning registration step. Thermal decomposition of PPC is then used to create air isolation regions around the copper traces. The spatial resolution of the self-patterning PPC process is limited by the lateral diffusion of the copper ions within the PPC. The concentration profiles of copper within the PPC, patterning resolution, and temperature effects on the PPC decomposition have been studied.

Status Epilepticus due to Intraperitoneal Injection of Vehicle Containing Propylene Glycol in Sprague Dawley Rats

PubMed Central

Meade, Seth M.; Smith, Cara S.; Chen, Keying; Kleinman, Nanette; Capadona, Jeffrey R.

2017-01-01

Published reports of status epilepticus due to intraperitoneal injection containing propylene glycol in rats are sparse. In fact, there are no reports specifying a maximum safe dose of propylene glycol through intraperitoneal administration. We report here a case of unexpected seizures in Sprague Dawley rats after receiving an intraperitoneal injection containing propylene glycol. Nine-week-old, 225–250 gram male rats were reported to experience tremor progressing to seizures within minutes after given injections of resveratrol (30 mg/kg) dissolved in a 40 : 60 propylene glycol/corn oil vehicle solution by direct intraperitoneal (IP) slow bolus injection or via a preplaced intraperitoneal catheter. The World Health Organization suggests a maximum dose of 25 mg/kg/day of propylene glycol taken orally and no more than 25 mg/dL in blood serum, whereas the animals used in our study got a calculated maximum 0.52 g/kg (25 times lower dose). Blood tests from the seizing rat support a diagnosis of hemolysis and lactic acidosis which may have led to the seizures, all of which appeared to be a consequence of the propylene glycol administration. These findings are consistent with oral and intravenous administration of propylene glycol toxicity as previously reported in other species, including humans. To our knowledge, this report represents the first published case of status epilepticus due to an IP injection containing propylene glycol. PMID:28785508

Status Epilepticus due to Intraperitoneal Injection of Vehicle Containing Propylene Glycol in Sprague Dawley Rats.

PubMed

Ereifej, Evon S; Meade, Seth M; Smith, Cara S; Chen, Keying; Kleinman, Nanette; Capadona, Jeffrey R

2017-01-01

Published reports of status epilepticus due to intraperitoneal injection containing propylene glycol in rats are sparse. In fact, there are no reports specifying a maximum safe dose of propylene glycol through intraperitoneal administration. We report here a case of unexpected seizures in Sprague Dawley rats after receiving an intraperitoneal injection containing propylene glycol. Nine-week-old, 225-250 gram male rats were reported to experience tremor progressing to seizures within minutes after given injections of resveratrol (30 mg/kg) dissolved in a 40 : 60 propylene glycol/corn oil vehicle solution by direct intraperitoneal (IP) slow bolus injection or via a preplaced intraperitoneal catheter. The World Health Organization suggests a maximum dose of 25 mg/kg/day of propylene glycol taken orally and no more than 25 mg/dL in blood serum, whereas the animals used in our study got a calculated maximum 0.52 g/kg (25 times lower dose). Blood tests from the seizing rat support a diagnosis of hemolysis and lactic acidosis which may have led to the seizures, all of which appeared to be a consequence of the propylene glycol administration. These findings are consistent with oral and intravenous administration of propylene glycol toxicity as previously reported in other species, including humans. To our knowledge, this report represents the first published case of status epilepticus due to an IP injection containing propylene glycol.

Transport properties of nonelectrolyte mixtures. IX. Viscosity coefficients for acetonitrile and for three mixtures of toluene+acetonitrile from 25 to 100°c at pressures up to 500 MPa

NASA Astrophysics Data System (ADS)

Dymond, J. H.; Awan, M. A.; Glen, N. F.; Isdale, J. D.

1991-05-01

A two-coil self-centering falling-body viscometer has been used to measure viscosity coefficients for acetonitrile and three binary mixtures of toluene+ acetonitrile at 25, 50, 75, and 100°C and pressures up to 500 MPa. The results for acetonitrile can be interpreted by an approach based on hard-sphere theory, with a roughness factor of 1.46. The binary-mixture data are well represented by the Grunberg and Nissan equation with a mixing parameter which is pressure and temperature dependent but composition independent.

21 CFR 589.1001 - Propylene glycol in or on cat food.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Propylene glycol in or on cat food. 589.1001... or on cat food. The Food and Drug Administration has determined that propylene glycol in or on cat... on cat food causes the feed to be adulterated and in violation of the Federal Food, Drug, and...

21 CFR 589.1001 - Propylene glycol in or on cat food.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 6 2011-04-01 2011-04-01 false Propylene glycol in or on cat food. 589.1001... or on cat food. The Food and Drug Administration has determined that propylene glycol in or on cat... on cat food causes the feed to be adulterated and in violation of the Federal Food, Drug, and...

New Photochrome Probe Allows Simultaneous pH and Microviscosity Sensing.

PubMed

Wu, Yuanyuan; Papper, Vladislav; Pokholenko, Oleksandr; Kharlanov, Vladimir; Zhou, Yubin; Steele, Terry W J; Marks, Robert S

2015-07-01

4-N,N'-dimethylamino-4'-N'-stilbenemaleamic acid (DASMA), a unique molecular photochrome probe that exhibits solubility and retains trans-cis photoisomerisation in a wide range of organic solvents and aqueous pH environments, was prepared, purified and chemically characterised. Absorption, fluorescence excitation and emission spectra and constant-illumination fluorescence decay were measured in acetonitrile, dimethyl sulfoxide, ethanol, propylene carbonate, and aqueous glycerol mixtures. The pseudo-first-order fluorescence decay rates were found to be strongly dependent on the medium viscosity. In addition, the molecule exhibited the pH-dependent fluorescence and photoisomerisation kinetics.

The Human Exposure Potential from Propylene Releases to the Environment

PubMed Central

Morgott, David A.

2018-01-01

A detailed literature search was performed to assess the sources, magnitudes and extent of human inhalation exposure to propylene. Exposure evaluations were performed at both the community and occupational levels for those living or working in different environments. The results revealed a multitude of pyrogenic, biogenic and anthropogenic emission sources. Pyrogenic sources, including biomass burning and fossil fuel combustion, appear to be the primary contributors to atmospheric propylene. Despite a very short atmospheric lifetime, measurable levels could be detected in highly remote locations as a result of biogenic release. The indoor/outdoor ratio for propylene has been shown to range from about 2 to 3 in non-smoking homes, which indicates that residential sources may be the largest contributor to the overall exposure for those not occupationally exposed. In homes where smoking takes place, the levels may be up to thirty times higher than non-smoking residences. Atmospheric levels in most rural regions are typically below 2 ppbv, whereas the values in urban levels are much more variable ranging as high as 10 ppbv. Somewhat elevated propylene exposures may also occur in the workplace; especially for firefighters or refinery plant operators who may encounter levels up to about 10 ppmv. PMID:29300328

Summary Review of the Health Effects Associated with Propylene: Health Issue Assessment

EPA Science Inventory

Propylene's major use is as a starting material in the manufacture of polypropylene, acrylonitrile, propylene oxide, and as a component in fuel. Ambient concentrations in urban areas of the United States range from about 1 to 10 ppb, with rural air levels being an order of magnit...

A rapid analysis of plasma/serum ethylene and propylene glycol by headspace gas chromatography.

PubMed

Ehlers, Alexandra; Morris, Cory; Krasowski, Matthew D

2013-12-01

A rapid headspace-gas chromatography (HS-GC) method was developed for the analysis of ethylene glycol and propylene glycol in plasma and serum specimens using 1,3-propanediol as the internal standard. The method employed a single-step derivitization using phenylboronic acid, was linear to 200 mg/dL and had a lower limit of quantitation of 1 mg/dL suitable for clinical analyses. The analytical method described allows for laboratories with HS-GC instrumentation to analyze ethanol, methanol, isopropanol, ethylene glycol, and propylene glycol on a single instrument with rapid switch-over from alcohols to glycols analysis. In addition to the novel HS-GC method, a retrospective analysis of patient specimens containing ethylene glycol and propylene glycol was also described. A total of 36 patients ingested ethylene glycol, including 3 patients who presented with two separate admissions for ethylene glycol toxicity. Laboratory studies on presentation to hospital for these patients showed both osmolal and anion gap in 13 patients, osmolal but not anion gap in 13 patients, anion but not osmolal gap in 8 patients, and 1 patient with neither an osmolal nor anion gap. Acidosis on arterial blood gas was present in 13 cases. Only one fatality was seen; this was a patient with initial serum ethylene glycol concentration of 1282 mg/dL who died on third day of hospitalization. Propylene glycol was common in patients being managed for toxic ingestions, and was often attributed to iatrogenic administration of propylene glycol-containing medications such as activated charcoal and intravenous lorazepam. In six patients, propylene glycol contributed to an abnormally high osmolal gap. The common presence of propylene glycol in hospitalized patients emphasizes the importance of being able to identify both ethylene glycol and propylene glycol by chromatographic methods.

21 CFR 172.808 - Copolymer condensates of ethylene oxide and propylene oxide.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Copolymer condensates of ethylene oxide and... ethylene oxide and propylene oxide. Copolymer condensates of ethylene oxide and propylene oxide may be... percent aqueous solution. (2) α-Hydro-omega-hydroxy-poly (oxy-ethylene)poly(oxypropylene)-(53-59 moles...

[Effect of Acetonitrile and n-hexane on the Immunoassay of Environmental Representative Pollutants].

PubMed

Lou, Xue-ning; Zhou, Li-ping; Song, Dan; Yang, Rong; Long, Feng

2016-01-15

Based on indirect competitive immunoassay mechanism, bisphenol A (BPA) was detected by the evanescent wave all-fiber immunosensor previously developed with the detection limit of 0.2 microg x L(-1) and the linear detection range of 0.3-33.4 microg x L(-1). The effects of two commonly used organic solvents, including acetonitrile and n-hexane, on the immunosensing assay of BPA were investigated. The influence mechanism of organic solvents on immunosensing assay was discussed. The experimental results showed that the effect of n-hexane on immunosensing assay was negligible even at a high concentration of up to 10%, whereas the effect of acetonitrile on the immunosensing assay was relatively great. BPA could be detected in solutions containing a low concentration of acetonitrile. However, the specific binding reaction between antibody and antigen in homogeneous solution was completely inhibited by high concentrations of acetonitrile, and the quantitative analysis of BPA was not achieved. This might result from the changes of antibody conformation or binding capability between antibody and antigen because acetonitrile replaced a part of the water molecules on the antibody surface.

Federal Register notice: Propylene Oxide; Testing Requirements

EPA Pesticide Factsheets

This final rule promulgated under section 4(a) of the Toxic Substances Control Act (TSCA) requires manufacturers and processors of propylene oxide (CAS No. 75-58-9) to test this chemical for developmental toxicity.

21 CFR 184.1666 - Propylene glycol.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Propylene glycol. 184.1666 Section 184.1666 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR HUMAN CONSUMPTION (CONTINUED) DIRECT FOOD SUBSTANCES AFFIRMED AS GENERALLY RECOGNIZED AS SAFE Listing of...

21 CFR 184.1666 - Propylene glycol.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Propylene glycol. 184.1666 Section 184.1666 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR HUMAN CONSUMPTION (CONTINUED) DIRECT FOOD SUBSTANCES AFFIRMED AS GENERALLY RECOGNIZED AS SAFE Listing of...

Limitations of using Raman microscopy for the analysis of high-content-carbon-filled ethylene propylene diene monomer rubber.

PubMed

Ghanbari-Siahkali, Afshin; Almdal, Kristoffer; Kingshott, Peter

2003-12-01

The effects of laser irradiation on changes to the surface chemistry and structure of a commercially available ethylene propylene diene monomer (EPDM) rubber sample after Raman microscopy analysis was investigated. The Raman measurements were carried out with different levels of laser power on the sample, ranging from 4.55 mW to 0.09 mW. The surface of the EPDM was analyzed before and after laser exposure using X-ray photoelectron spectroscopy (XPS) and attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy. The techniques have surface probe depths of approximately < or = 10 nm and 1 microm, respectively. Both sets of analysis show that ingredients of the blended EPDM rubber "bloom" to the surface as a result of local heating that takes place due to the absorption of laser by carbon black during the Raman analysis. Scanning electron microscopy (SEM) analysis was also performed on the Raman analyzed areas to visually illustrate the effects created due to laser light exposure (i.e., burning marks). The change in surface chemistry also occurs in regions a few millimeters from the exposed sites, indicating that the effect is quite long range. However, this phenomenon has no major influence, as far as XPS or ATR-FTIR results disclose, on the backbone structure of the rubber sample. The results indicate that precautions should be taken when analyzing complex blended polymer samples using Raman spectroscopy.

21 CFR 582.1666 - Propylene glycol.

Code of Federal Regulations, 2010 CFR

2010-04-01

... is generally recognized as safe (except in cat food) when used in accordance with good manufacturing... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Propylene glycol. 582.1666 Section 582.1666 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL...

21 CFR 582.1666 - Propylene glycol.

Code of Federal Regulations, 2011 CFR

2011-04-01

... is generally recognized as safe (except in cat food) when used in accordance with good manufacturing... 21 Food and Drugs 6 2011-04-01 2011-04-01 false Propylene glycol. 582.1666 Section 582.1666 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL...

Aphids preserved in propylene glycol can be used for reverse transcription-polymerase chain reaction detection of Potato virus Y.

PubMed

Nie, Xianzhou; Pelletier, Yvan; Mason, Nicola; Dilworth, Andrea; Giguère, Marie-Andrée

2011-08-01

The effectiveness of propylene glycol on the retention of RNA target of Potato virus Y (PVY), an aphid stylet-borne virus, in Myzus persicae was investigated in comparison to ethanol and liquid nitrogen/-80°C. Reverse transcription-polymerase chain reaction (RT-PCR) was used to detect the PVY targets from the propylene glycol/ethanol/liquid nitrogen preserved single aphids after a 5min acquisition period from infected potato plants. In the liquid nitrogen/-80°C and 70% ethanol treatments, 55.6% and 38.8% aphids tested PVY-positive, respectively. In the 0-75% propylene glycol treatments, 12.2-44.7% aphids tested PVY-positive. The lowest detection rate was in the 0% (positive rate, 15.2%) and the 10% propylene glycol (positive rate, 12.2%). As the propylene glycol concentration increased to 25%, 29.8% aphids tested positive. A high PVY-positive rate was also found in 35-75% propylene glycol treatments at 44.7% (35% propylene glycol), 36.7% (50% propylene glycol) and 34.8% (75% propylene glycol), which is comparable to the rate shown in 70% ethanol. No significant difference in the positive detection rate was observed in aphids preserved in 50% propylene glycol at room temperature for 2, 4 and 10 days. These results demonstrate that propylene glycol at 25-75% can retain PVY targets effectively in aphids for an extended time period, and thus can be used in aphid traps to preserve viruliferous aphids for later RT-PCR detection of PVY. Crown Copyright © 2011. Published by Elsevier B.V. All rights reserved.

Isolation and Characterization of PHA-Producing Bacteria from Propylene Oxide Saponification Wastewater Residual Sludge.

PubMed

Li, Ruirui; Gu, Pengfei; Fan, Xiangyu; Shen, Junyu; Wu, Yulian; Huang, Lixuan; Li, Qiang

2018-03-21

A polyhydroxyalkanoate (PHA)-producing strain was isolated from propylene oxide (PO) saponification wastewater activated sludge and was identified as Brevundimonas vesicularis UJN1 through 16S rDNA sequencing and Biolog microbiological identification. Single-factor and response surface methodology experiments were used to optimize the culture medium and conditions. The optimal C/N ratio was 100/1.04, and the optimal carbon and nitrogen sources were sucrose (10 g/L) and NH 4 Cl (0.104 g/L) respectively. The optimal culture conditions consisted of initial pH of 6.7 and an incubation temperature of 33.4 °C for 48 h, with 15% inoculum and 100 mL medium at an agitation rate of 180 rpm. The PHA concentration reached 34.1% of the cell dry weight and increased three times compared with that before optimization. The only report of PHA-producing bacteria by Brevundimonas vesicularis showed that the conversion rate of PHAs using glucose as the optimal carbon source was 1.67%. In our research, the conversion rate of PHAs with sucrose as the optimal carbon source was 3.05%, and PHA production using sucrose as the carbon source was much cheaper than that using glucose as the carbon source.

Anaesthetic properties of carbon monoxide and other gases in relation to plants, insects, and centipedes

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

Zimmerman, P.W.

The anaesthetic effect of carbon monoxide, carbon dioxide, propylene, butylene, ethylene, and acetylene, when mixed with oxygen, was tested on ten different species of insects and centipedes. The lowest concentrations found to cause anaesthesia are given in per cent by volume as follows: propylene, for centipede, 30; katydid, 75; rose chafer, 60. Carbon monoxide, for centipede, 81.5; katydid, 89, rose chafer, 85. Butylene, for centipede, 5; katydid, 10; rose chafer, 40. Ethylene or acetylene, for centipede, katydid, and rose chafer, 100. Carbon dioxide, for rose chafer, 30. Ethylene was the most effective plant anaesthetic, 0.0005 per cent stopping growth movementsmore » of tomato and sunflower plants as shown by motion pictures; 0.001 per cent stopped elongation of sweet pea seedlings, while 0.00001 per cent retarded elongation nearly 50 per cent. The degree of retardation in growth from ethylene gas varied with the concentration and the plant species. Acetylene and propylene were about equally effective as plant anaesthetics. Both were approximately 10 times as effective as carbon monoxide. Mimosa pudica lost its capacity to respond to external stimuli while being exposed to 0.25 per cent of carbon monoxide, but became normal again upon being removed from the gas. 3 references, 4 tables.« less

Hexanuclear Fe(III) wheels functionalized by amino-acetonitrile derivatives

NASA Astrophysics Data System (ADS)

Kravtsov, Victor Ch.; Malaestean, Iurie; Stingach, Eugenia P.; Duca, Gheorghe G.; Macaev, Fliur Z.; van Leusen, Jan; Kögerler, Paul; Hauser, Jürg; Krämer, Karl; Decurtins, Silvio; Liu, Shi-Xia; Ghosh, Ashta C.; Garcia, Yann; Baca, Svetlana G.

2018-04-01

Three new hexanuclear Fe(III) coordination wheels [Fe6Cl6(L1)6]·5(MeCN) (1), [Na0.5Fe6Cl6(L1)6](N3)0.5·4.5(MeCN) (2), and [Fe6Cl6(L2)6]·2(MeCN) (3) have been synthesized with new prepared amino-acetonitrile derivatives 2-[bis(2-hydroxyethyl)amino]acetonitrile hydrochloride (H2L1) and 3-[bis(2-hydroxyethyl)amino]propanenitrile hydrochloride (H2L2). They were structurally characterized by single-crystal X-ray diffraction. Mößbauer spectroscopy and magnetic susceptibility measurements indicate dominant antiferromagnetic behavior between the Fe(III) centers.

Study of cellulase enzymes self-assembly in aqueous-acetonitrile solvent: Viscosity measurements

NASA Astrophysics Data System (ADS)

Ghaouar, N.; Aschi, A.; Belbahri, L.; Trabelsi, S.; Gharbi, A.

2009-11-01

The present study extends the viscosity measurements performed by Ghaouar et al. [Physica B, submitted for publication.] to study the conformational change of the cellulase enzymes in aqueous-acetonitrile mixture. We aim to investigate: (i) the denaturation process by measuring the specific viscosity for temperatures varying between 25 and 65 °C and acetonitrile concentrations between 0% and 50%, (ii) the enzyme-enzyme interaction by calculating the Huggins coefficient and (iii) the enzyme sizes by following the hydrodynamic radius for various temperatures. The precipitation of cellulases versus acetonitrile concentration is also considered. We show from all physical quantities measured in this work that the precipitation and the denaturation processes of cellulase enzymes exist together.

Developing synthesis techniques for zeolitic-imidazolate framework membranes for high resolution propylene/propane separation

NASA Astrophysics Data System (ADS)

Kwon, Hyuk Taek

Propylene/propane separation is one of the most challenging separations, currently achieved by energy-intensive cryogenic distillation. Despite the great potentials for energy-efficient membrane-based propylene/propane separation processes, no commercial membranes are available due to the limitations (i.e., low selectivity) of current polymeric materials. Zeolitic imidazolate frameworks (ZIFs) are promising membrane materials primarily due to their well-defined ultra-micropores with controllable surface chemistry along with their relatively high thermal/chemical stabilities. In particular, ZIF-8 with the effective aperture size of ~ 4.0 A has been shown very promising for propylene/propane separation. Despite the extensive research on ZIF-8 membranes, only a few of ZIF-8 membranes have displayed good propylene/propane separation performances presumably due to the challenges of controlling the microstructures of polycrystalline membranes. Since the membrane microstructures are greatly influenced by processing techniques, it is critically important to develop new techniques. In this dissertation, three state-of-the-art ZIF membrane synthesis techniques are developed. The first is a one-step in-situ synthesis technique based on the concept of counter diffusion. The technique enabled us to obtain highly propylene selective ZIF-8 membranes in less than a couple of hours with exceptional mechanical strength. Most importantly, due to the nature of the counter-diffusion concept, the new method offered unique opportunities such as healing defective membranes (i.e., poorly-intergrown) as well as significantly reducing the consumption of costly ligands and organic solvents. The second is a microwave-assisted seeding technique. Using this new seeding technique, we were able to prepare seeded supports with a high packing density in a couple of minutes, which subsequently grown into highly propylene-selective ZIF-8 membranes with an average propylene/propane selectivity of ~40

Standard reduction potentials for oxygen and carbon dioxide couples in acetonitrile and N, N -dimethylformamide

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

Pegis, Michael L.; Roberts, John A. S.; Wasylenko, Derek J.

A variety of next-generation energy processes utilize the electrochemical interconversions of dioxygen and water as the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER). Reported here are the first estimates of the standard reduction potential of the O 2 + 4e – + 4H + ⇌ 2H 2O couple in organic solvents. The values are +1.21 V in acetonitrile (MeCN) and +0.60 V in N,N-dimethylformamide (DMF), each versus the ferrocenium/ferrocene couple (Fc +/0) in the respective solvent (as are all of the potentials reported here). The potentials have been determined using a thermochemical cycle that combines the freemore » energy for transferring water from aqueous solution to organic solvent, –0.43 kcal mol –1 for MeCN and –1.47 kcal mol –1 for DMF, and the potential of the H +/H 2 couple, – 0.028 V in MeCN and –0.662 V in DMF. The H +/H 2 couple in DMF has been directly measured electrochemically using the previously reported procedure for the MeCN value. The thermochemical approach used for the O 2/H 2O couple has been extended to the CO 2/CO and CO 2/CH 4 couples to give values of –0.12 and +0.15 V in MeCN and –0.73 and –0.48 V in DMF, respectively. Here, extensions to other reduction potentials are discussed. Additionally, the free energy for transfer of protons from water to organic solvent is estimated as +14 kcal mol –1 for acetonitrile and +0.6 kcal mol –1 for DMF.« less

Standard reduction potentials for oxygen and carbon dioxide couples in acetonitrile and N, N -dimethylformamide

DOE PAGES

Pegis, Michael L.; Roberts, John A. S.; Wasylenko, Derek J.; ...

2015-12-07

A variety of next-generation energy processes utilize the electrochemical interconversions of dioxygen and water as the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER). Reported here are the first estimates of the standard reduction potential of the O 2 + 4e – + 4H + ⇌ 2H 2O couple in organic solvents. The values are +1.21 V in acetonitrile (MeCN) and +0.60 V in N,N-dimethylformamide (DMF), each versus the ferrocenium/ferrocene couple (Fc +/0) in the respective solvent (as are all of the potentials reported here). The potentials have been determined using a thermochemical cycle that combines the freemore » energy for transferring water from aqueous solution to organic solvent, –0.43 kcal mol –1 for MeCN and –1.47 kcal mol –1 for DMF, and the potential of the H +/H 2 couple, – 0.028 V in MeCN and –0.662 V in DMF. The H +/H 2 couple in DMF has been directly measured electrochemically using the previously reported procedure for the MeCN value. The thermochemical approach used for the O 2/H 2O couple has been extended to the CO 2/CO and CO 2/CH 4 couples to give values of –0.12 and +0.15 V in MeCN and –0.73 and –0.48 V in DMF, respectively. Here, extensions to other reduction potentials are discussed. Additionally, the free energy for transfer of protons from water to organic solvent is estimated as +14 kcal mol –1 for acetonitrile and +0.6 kcal mol –1 for DMF.« less

PNNL Provides Catalyst for Sustainable Propylene Glycol Production

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

Madison, Alison L.; Lund, Eric C.

2012-02-28

Submission for annual FLC magazine publication, Technology for Today, featuring technologies transferred by federal labs. Subject: PNNL transfer of Propylene Glycol from Renewable Sources catalytic process to Archer Daniels Midland Company.

Broadband terahertz dynamics of propylene glycol monomer and oligomers

NASA Astrophysics Data System (ADS)

Koda, Shota; Mori, Tatsuya; Kojima, Seiji

2016-12-01

We investigated the broadband terahertz spectra (0.1-5.0 THz) of glass-forming liquids, propylene glycol (PG), its oligomers poly (propylene glycol)s (PPGs), and poly (propylene glycol) diglycidyl ether (PPG-de) using broadband terahertz time-domain spectroscopy and low-frequency Raman scattering. The numerical value of the dielectric loss at around 1.5 THz, which is the peak position of broad peaks in all samples, decreased as the molecular weight increased. Furthermore, the peak at around 1.5 THz is insensitive to the molecular weight. For PPGs, the side chain effect of the oligomer was observed in the terahertz region. Based on the experimental and calculation results for the PPGs and PPG-de, whose end groups are epoxy groups, the beginnings of the increases in the observed dielectric loss above 3.5 THz of the PPGs are assigned to the OH bending vibration. The higher value of the dielectric loss in the terahertz region for the PPG-de can be the tail of a broad peak located in the MHz region. The difference between the Raman susceptibility and dielectric loss reflects the difference in the observable molecular dynamics between the infrared and Raman spectroscopies.

Detection of amino acetonitrile in Sgr B2(N)

NASA Astrophysics Data System (ADS)

Belloche, A.; Menten, K. M.; Comito, C.; Müller, H. S. P.; Schilke, P.; Ott, J.; Thorwirth, S.; Hieret, C.

2008-04-01

Context: Amino acids are building blocks of proteins and therefore key ingredients for the origin of life. The simplest amino acid, glycine (NH2CH2COOH), has long been searched for in the interstellar medium but has not been unambiguously detected so far. At the same time, more and more complex molecules have been newly found toward the prolific Galactic center source Sagittarius B2. Aims: Since the search for glycine has turned out to be extremely difficult, we aimed at detecting a chemically related species (possibly a direct precursor), amino acetonitrile (NH2CH2CN). Methods: With the IRAM 30 m telescope we carried out a complete line survey of the hot core regions Sgr B2(N) and (M) in the 3 mm range, plus partial surveys at 2 and 1.3 mm. We analyzed our 30 m line survey in the LTE approximation and modeled the emission of all known molecules simultaneously. We identified spectral features at the frequencies predicted for amino acetonitrile lines having intensities compatible with a unique rotation temperature. We also used the Very Large Array to look for cold, extended emission from amino acetonitrile. Results: We detected amino acetonitrile in Sgr B2(N) in our 30 m telescope line survey and conducted confirmatory observations of selected lines with the IRAM Plateau de Bure and the Australia Telescope Compact Array interferometers. The emission arises from a known hot core, the Large Molecule Heimat, and is compact with a source diameter of 2 arcsec (0.08 pc). We derived a column density of 2.8 × 1016 cm-2, a temperature of 100 K, and a linewidth of 7 km s-1. Based on the simultaneously observed continuum emission, we calculated a density of 1.7 × 108 cm-3, a mass of 2340 M_⊙, and an amino acetonitrile fractional abundance of 2.2 × 10-9. The high abundance and temperature may indicate that amino acetonitrile is formed by grain surface chemistry. We did not detect any hot, compact amino acetonitrile emission toward Sgr B2(M) or any cold, extended emission

Calculation of Vibrational Spectra for Coordinated Thiocyanate Ion in Acetonitrile

NASA Astrophysics Data System (ADS)

Mikhailov, G. P.

2016-07-01

The impact of the association of lithium cation with NCS- ion in acetonitrile on the vibrational spectrum was studied by the density-functional method in the B3LYP/6-31+G(d,p) approximation. The best agreement between experimental and calculated ionic association data was achieved taking into account the nonspecific solvation, oversolvation, and solubility of ionic complexes within the discrete-continuum model. The microstructures of the thiocyanate ion in a contact ion pair with lithium cation and ion-pair dimer and trimer in acetonitrile were established.

Influence of propylene glycol on aqueous silica dispersions and particle-stabilized emulsions.

PubMed

Binks, Bernard P; Fletcher, Paul D I; Thompson, Michael A; Elliott, Russell P

2013-05-14

We have studied the influence of adding propylene glycol to both aqueous dispersions of fumed silica nanoparticles and emulsions of paraffin liquid and water stabilized by the same particles. In the absence of oil, aerating mixtures of aqueous propylene glycol and particles yields either stable dispersions, aqueous foams, climbing particle films, or liquid marbles depending on the glycol content and particle hydrophobicity. The presence of glycol in water promotes particles to behave as if they are more hydrophilic. Calculations of their contact angle at the air-aqueous propylene glycol surface are in agreement with these findings. In the presence of oil, particle-stabilized emulsions invert from water-in-oil to oil-in-water upon increasing either the inherent hydrophilicity of the particles or the glycol content in the aqueous phase. Stable multiple emulsions occur around phase inversion in systems of low glycol content, and completely stable, waterless oil-in-propylene glycol emulsions can also be prepared. Accounting for the surface energies at the respective interfaces allows estimation of the contact angle at the oil-polar phase interface; reasonable agreement between measured and calculated phase inversion conditions is found assuming no glycol adsorption on particle surfaces.

New Force Field Model for Propylene Glycol: Insight to Local Structure and Dynamics.

PubMed

Ferreira, Elisabete S C; Voroshylova, Iuliia V; Koverga, Volodymyr A; Pereira, Carlos M; Cordeiro, M Natália D S

2017-12-07

In this work we developed a new force field model (FFM) for propylene glycol (PG) based on the OPLS all-atom potential. The OPLS potential was refined using quantum chemical calculations, taking into account the densities and self-diffusion coefficients. The validation of this new FFM was carried out based on a wide range of physicochemical properties, such as density, enthalpy of vaporization, self-diffusion coefficients, isothermal compressibility, surface tension, and shear viscosity. The molecular dynamics (MD) simulations were performed over a large range of temperatures (293.15-373.15 K). The comparison with other force field models, such as OPLS, CHARMM27, and GAFF, revealed a large improvement of the results, allowing a better agreement with experimental data. Specific structural properties (radial distribution functions, hydrogen bonding and spatial distribution functions) were then analyzed in order to support the adequacy of the proposed FFM. Pure propylene glycol forms a continuous phase, displaying no microstructures. It is shown that the developed FFM gives rise to suitable results not only for pure propylene glycol but also for mixtures by testing its behavior for a 50 mol % aqueous propylene glycol solution. Furthermore, it is demonstrated that the addition of water to the PG phase produces a homogeneous solution and that the hydration interactions prevail over the propylene glycol self-association interactions.

Evaluation in vitro and in vivo of dimethicone transdermal therapeutic systems. Influence of propylene glycol on drug release.

PubMed

Ritschel, W A; Nayak, P M

1987-03-01

Coumarin-containing transdermal drug delivery systems were studied in vitro for drug release and in vivo in rats for drug absorption. The matrix of the transdermal delivery system, dimethicone, was a commercially available silicone elastomer. The devices containing 1, 3 and 5% coumarin released in vitro 8.8 (87.4%), 23.4 (74.5%) and 31.6 mg (63.3%) of drug within 24 h. The device containing 5% coumarin was selected for further studies in which 5, 10, 20, 30, 50 and 70% propylene glycol was added. Up to 20% propylene glycol content did not change the amount released. The preparations with 30, 50 and 70% propylene glycol released 69.3, 73.6 and 87.9%, respectively. The 50 and 70% preparations were physically not acceptable. Only the preparations containing 5% coumarin without propylene glycol and 5% coumarin and 30% propylene glycol in the elastomer were evaluated in vivo. The area under the blood level-time curve of the propylene glycol-containing system was twice that of the device without propylene glycol. Blood levels were maintained between about 2 micrograms/ml and 5 micrograms/ml during the time the device was kept on the skin (24 h).

21 CFR 177.1980 - Vinyl chloride-propylene copolymers.

Code of Federal Regulations, 2014 CFR

2014-04-01

... grams of granular sodium peroxide, 0.1 gram of powdered starch, and 0.02 gram potassium nitrate; and the... provisions of this section are not applicable to vinyl chloride-propylene copolymers used in food-packaging...

Preparation and Thermo-Physical Properties of Fe2O3-Propylene Glycol Nanofluids.

PubMed

Shylaja, A; Manikandan, S; Suganthi, K S; Rajan, K S

2015-02-01

Iron oxide (Fe2O3) nanoparticles were prepared from ferric chloride and ferrous sulphate by precipitation reaction. Fe2O3-propylene glycol nanofluid was prepared by dispersing Fe2O3 nanoparticles in propylene glycol through stirred bead milling, shear homogenization and probe ultrasonication. The nanofluid was characterized through measurement of viscosity, particle size distribution and thermal conductivity. The interactions between Fe2O3 nanoparticles and propylene glycol on the nanoparticle surfaces lead to reduction in viscosity, the magnitude of which increases with nanoparticle concentration (0-2 vol%) at room temperature. The thermal conductivity enhancement for 2 vol% nanofluid was about 21% at room temperature, with liquid layering being the major contributor for thermal conductivity enhancement.

Molecular dynamics simulation of the ionic liquid N-octylpyridinium tetrafluoroborate and acetonitrile: Thermodynamic and structural properties

NASA Astrophysics Data System (ADS)

Zhou, Siwen; Zhu, Guanglai; Kang, Xianqu; Li, Qiang; Sha, Maolin; Cui, Zhifeng; Xu, Xinsheng

2018-06-01

Using molecular dynamics simulation, the research obtained the thermodynamic properties and microstructures of the mixture of N-octylpyridinium tetrafluoroborate and acetonitrile, including density, self-diffusion coefficients, excess properties, radial distribution functions (RDFs) and spatial distribution functions (SDFs). Both RDFs and SDFs indicate that the local microstructure of the polar region is different from the nonpolar region with different mole fraction of ionic liquids. Acetonitrile could increase the order of the polar regions. While with acetonitrile increasing, the orderliness of the nonpolar region increases firstly and then decreases. In relatively dilute solution, ionic liquids were dispersed to form small aggregates wrapped by acetonitrile.

A facile approach towards increasing the nitrogen-content in nitrogen-doped carbon nanotubes via halogenated catalysts

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

Ombaka, L.M.; Ndungu, P.G.; Department of Applied Chemistry, Doornfontein Campus, University of Johannesburg, P.O. Box 17011, Johannesburg 2028

Nitrogen-doped carbon nanotubes (N-CNTs) have been synthesized at 850 °C via a CVD deposition technique by use of three ferrocenyl derivative catalysts, i.e. para-CN, -CF{sub 3} and -Cl substituted-phenyl rings. The synthesized catalysts have been characterized by NMR, IR, HR-MS and XRD. The XRD analysis of the para-CF{sub 3} catalyst indicates that steric factors influence the X-ray structure of 1,1′-ferrocenylphenyldiacrylonitriles. Acetonitrile or pyridine was used as carbon and nitrogen sources to yield mixtures of N-CNTs and carbon spheres (CS). The N-CNTs obtained from the para-CF{sub 3} catalysts, in pyridine, have the highest nitrogen-doping level, show a helical morphology and aremore » less thermally stable compared with those synthesized by use of the para-CN and -Cl as catalyst. This suggests that fluorine heteroatoms enhance nitrogen-doping in N-CNTs and formation of helical-N-CNTs (H-N-CNTs). The para-CF{sub 3} and para-Cl catalysts in acetonitrile yielded iron-filled N-CNTs, indicating that halogens promote encapsulation of iron into the cavity of N-CNT. The use of acetonitrile, as carbon and nitrogen source, with the para-CN and -Cl as catalysts also yielded a mixture of N-CNTs and carbon nanofibres (CNFs), with less abundance of CNFs in the products obtained using para-Cl catalysts. However, para-CF{sub 3} catalyst in acetonitrile gave N-CNTs as the only shaped carbon nanomaterials. - Graphical abstract: Graphical abstract showing the synthesis of N-CNTs using halogenated-ferrocenyl derivatives as catalyst with pyridine or acetonitrile as nitrogen and carbon sources via the chemical vapour deposition technique. - Highlights: • N-CNTs were synthesized from halogenated ferrocenyl catalysts. • Halogenated catalysts promote nitrogen-doping and pyridinic nitrogen in N-CNTs. • Halogenated catalysts facilitate iron filling of N-CNTs.« less

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

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

Chen, Long; Li, Zhenjun; Smith, R. Scott

2014-10-09

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

21 CFR 177.1980 - Vinyl chloride-propylene copolymers.

Code of Federal Regulations, 2013 CFR

2013-04-01

... contents of the cup are added 3.5 grams of granular sodium peroxide, 0.1 gram of powdered starch, and 0.02... applicable to vinyl chloride-propylene copolymers used in food-packaging adhesives complying with § 175.105...

21 CFR 177.1980 - Vinyl chloride-propylene copolymers.

Code of Federal Regulations, 2012 CFR

2012-04-01

... contents of the cup are added 3.5 grams of granular sodium peroxide, 0.1 gram of powdered starch, and 0.02... applicable to vinyl chloride-propylene copolymers used in food-packaging adhesives complying with § 175.105...

Effect of the composition of a solution on the enthalpies of solvation of piperidine in methanol-acetonitrile and dimethylsulfoxide-acetonitrile mixed solvents

NASA Astrophysics Data System (ADS)

Kuz'mina, I. A.; Volkova, M. A.; Sitnikova, K. A.; Sharnin, V. A.

2014-01-01

Heat effects of dissolution of piperidine (ppd) are measured by calorimetry at 298.15 K over the range of composition of acetonitrile-methanol (AN-MeOH) mixed solvents. Based on the Δsol H ○(ppd)AN-MeOH values obtained using the literature data on Δsol H ○ (ppd) in acetonitrile-dimethylsulfoxide (AN-DMSO) mixed solvents and the vaporization enthalpy of ppd, the enthalpies of solvation of amine in AN-MeOH and AN-DMSO binary mixtures are calculated. A rise in the exothermicity of solvation of piperidine is observed upon the transition from AN to DMSO and MeOH, due mainly to the enhanced solvation of the amino group of ppd as a result of changes in the acid-base properties of the mixed solvent.

Smart poly(oligo(propylene glycol) methacrylate) hydrogel prepared by gamma radiation

NASA Astrophysics Data System (ADS)

Suljovrujic, E.; Micic, M.

2015-01-01

The synthesis of poly(oligo(propylene glycol) methacrylate) (POPGMA) from functionalised oligo(propylene glycol) methacrylate (OPGMA) monomers by gamma radiation-induced radical polymerisation is reported for the first time; POPGMA homopolymeric hydrogel with oligo(propylene glycol) (OPG) pendant chains, as a non-linear PPGMA-analogue, was synthesised from an monomer-solvent (OPGMA375-water/ethanol) mixture at different irradiation doses (5, 10, 25, and 40 kGy). Determination of the gel fraction was conducted after synthesis. The swelling properties of the POPGMA hydrogel were preliminarily investigated over wide pH (2.2-9.0) and temperature (4-70 °C) ranges. Additional characterisation of structure and properties was conducted by UV-vis and Fourier transform infrared (FTIR) spectroscopy as well as by differential scanning calorimetry (DSC). In order to evaluate the potential for biomedical applications, biocompatibility (cytocompatibility and haemolytic activity) studies were performed as well. Sol-gel conversion was relatively high for all irradiation doses, indicating radiation-induced synthesis as a good method for fabricating this hydrogel. Thermoresponsiveness and variations in swelling capacity as a result of thermosensitive OPG pendant chains with a lower critical solution temperature (LCST) were mainly observed below room temperature; thus, the volume phase transition temperature (VPTT) of POPGMA homopolymeric hydrogel is about 15 °C. Furthermore, POPGMA has satisfactory biocompatibility. The results indicate that the hydrogels with propylene glycol pendant chains can be easily prepared by gamma radiation and have potential for different applications as smart and biocompatible polymers.

40 CFR 180.1250 - C8, C10, and C12 fatty acid monoesters of glycerol and propylene glycol; exemption from the...

Code of Federal Regulations, 2012 CFR

2012-07-01

... of glycerol and propylene glycol; exemption from the requirement of a tolerance. 180.1250 Section 180..., C10, and C12 fatty acid monoesters of glycerol and propylene glycol; exemption from the requirement of... monocaprylate, glycerol monocaprate, and glycerol monolaurate) and propylene glycol (propylene glycol...

40 CFR 180.1250 - C8, C10, and C12 fatty acid monoesters of glycerol and propylene glycol; exemption from the...

Code of Federal Regulations, 2013 CFR

2013-07-01

... of glycerol and propylene glycol; exemption from the requirement of a tolerance. 180.1250 Section 180..., C10, and C12 fatty acid monoesters of glycerol and propylene glycol; exemption from the requirement of... monocaprylate, glycerol monocaprate, and glycerol monolaurate) and propylene glycol (propylene glycol...

40 CFR 180.1250 - C8, C10, and C12 fatty acid monoesters of glycerol and propylene glycol; exemption from the...

Code of Federal Regulations, 2014 CFR

2014-07-01

... of glycerol and propylene glycol; exemption from the requirement of a tolerance. 180.1250 Section 180..., C10, and C12 fatty acid monoesters of glycerol and propylene glycol; exemption from the requirement of... monocaprylate, glycerol monocaprate, and glycerol monolaurate) and propylene glycol (propylene glycol...

21 CFR 172.856 - Propylene glycol mono- and diesters of fats and fatty acids.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Propylene glycol mono- and diesters of fats and... diesters of fats and fatty acids. Propylene glycol mono- and diesters of fats and fatty acids may be safely used in food, subject to the following prescribed conditions: (a) They are produced from edible fats...

21 CFR 172.856 - Propylene glycol mono- and diesters of fats and fatty acids.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Propylene glycol mono- and diesters of fats and... diesters of fats and fatty acids. Propylene glycol mono- and diesters of fats and fatty acids may be safely used in food, subject to the following prescribed conditions: (a) They are produced from edible fats...

Antioxidant and antibacterial activities of acetonitrile and hexane extracts of Lentinus tigrinus and Pleurotus djamour

USDA-ARS?s Scientific Manuscript database

This paper highlighted the antioxidant and antibacterial activities of Lentinus tigrinus and Pleurotus djamour. Extracts of mushroom fruiting bodies were obtained using hexane and acetonitrile solvents. Acetonitrile extracts of both mushrooms exhibited higher biological activities than hexane extrac...

Analysis of sorption into single ODS-silica gel microparticles in acetonitrile-water.

PubMed

Nakatani, Kiyoharu; Kakizaki, Hiroshi

2003-08-01

Intraparticle mass transfer processes of Phenol Blue (PB) in single octadecylsilyl (ODS)-silica gel microparticles in acetonitrile-water were analyzed by microcapillary manipulation and microabsorption methods. An absorption maximum of PB, the sorption isotherm parameters, and the sorption rate in the microparticle system were highly dependent on the percentage of acetonitrile in solution. The results are discussed in terms of the microscopic polarity surrounding PB in the ODS phase and the relationship between the isotherm parameters and the sorption rate.

Hydride affinities of cumulated, isolated, and conjugated dienes in acetonitrile.

PubMed

Zhu, Xiao-Qing; Liang, Hao; Zhu, Yan; Cheng, Jin-Pei

2008-11-07

The hydride affinities (defined as the enthalpy changes in this work) of 15 polarized dienes [five phenyl sulfone substituted allenes (1a), the corresponding five isolated dienes (1b), and the corresponding five conjugated dienes (1c)] in acetonitrile solution were determined by titration calorimetry for the first time. The results display that the hydride affinity scales of the 15 dienes in acetonitrile range from -71.6 to -73.9 kcal/mol for 1a, from -46.2 to -49.7 kcal/mol for 1b, and from -45.0 to -46.5 kcal/mol for 1c, which indicates that the hydride-obtaining abilities of the cumulated dienes (1a) are not only much larger than those of the corresponding conjugated dienes (1c) but also much larger than those of the corresponding isolated dienes (1b). The hydrogen affinities of the 15 dienes as well as the hydrogen affinities and the proton affinities of the radical anions of the dienes (1(-*)) in acetonitrile were also evaluated by using relative thermodynamic cycles according to Hess's law. The results show that (i) the hydrogen affinities of the neutral dienes 1 cover a range from -44.5 to -45.6 kcal/mol for 1a, from -20.4 to -21.4 kcal/mol for 1b, and from -17.3 to -18.5 kcal/mol for 1c; (ii) the hydrogen affinities of the radical anions of the dienes (1(-*)) in acetonitrile cover a range from -40.6 to -47.2 kcal/mol for 1a(-*), from -21.6 to -29.6 kcal/mol for 1b(-*), and from -10.0 to -15.4 kcal/mol for 1c(-*); (iii) the proton affinities of the 15 1a(-*) in acetonitrile cover a range from -97.0 to -100.6 kcal/mol for 1a(-*), from -77.8 to -83.4 kcal/mol for 1b(-*), and from -66.2 to -68.9 kcal/mol for 1c(-*). The main reasons for the great difference between the cumulated dienes and the corresponding isolated and conjugated dienes in the hydride affinity, hydrogen affinity, and proton affinity have been examined. It is evident that these experimental results should be quite valuable to facilitate the elucidation of the origins of the especially high

A nitromethane-based HPLC system alternative to acetonitrile for carotenoid analysis of fruit and vegetables.

PubMed

Sandmann, Gerhard

2010-01-01

Acetonitrile-based HPLC systems are the most commonly used for carotenoid analysis from different plant tissues. Because of the acetonitrile shortage, an HPLC system for the separation of carotenoids on C(18) reversed-phase columns was developed in which an acetonitrile-alcohol-based mobile phase was replaced by nitromethane. This solvent comes closest to acetonitrile with respect to its elutrophic property. Our criterion was to obtain similar separation and retention times for a range of differently structured carotenoids. This was achieved by further increase in the lipophilicity with ethylacetate. For all the carotenoids which we tested, we found co-elution only of β-cryptoxanthin and lycopene. By addition of 1% of water, separation of this pair of carotenoids was also achieved. The final recommended mobile phase consisted of nitromethane : 2-propanol : ethyl acetate : water (79 : 10 : 10 : 1, by volume). On Nucleosil C(18) columns and related ones like Hypersil C(18), we obtained separation of carotenes, hydroxyl, epoxy and keto derivatives, which resembles the excellent separation properties of acetonitrile-based mobile phases on C(18) reversed phase columns. We successfully applied the newly developed HPLC system to the separation of carotenoids from different vegetables and fruit. Copyright © 2010 John Wiley & Sons, Ltd.

[Comparison of acetonitrile, ethanol and chromatographic column to eliminate high-abundance proteins in human serum].

PubMed

Li, Yin; Liao, Ming; He, Xiao; Zhou, Yi; Luo, Rong; Li, Hongtao; Wang, Yun; He, Min

2012-11-01

To compare the effects of acetonitrile precipitation, ethanol precipitation and multiple affinity chromatography column Human 14 removal to eliminate high-abundance proteins in human serum. Elimination of serum high-abundance proteins performed with acetonitrile precipitation, ethanol precipitation and multiple affinity chromatography column Human 14 removal. Bis-Tris Mini Gels electrophoresis and two-dimensional gel electrophoresis to detect the effect. Grey value analysis from 1-DE figure showed that after serum processed by acetonitrile method, multiple affinity chromatography column Human 14 removal method and ethanol method, the grey value of albumin changed into 157.2, 40.8 and 8.2 respectively from the original value of 19. 2-DE analysis results indicated that using multiple affinity chromatography column Human 14 method, the protein points noticeable increased by 137 compared to the original serum. After processed by acetonitrile method and ethanol method, the protein point reduced, but the low abundance protein point emerged. The acetonitrile precipitation could eliminate the vast majority of high abundance proteins in serum and gain more proteins of low molecular weight, ethanol precipitation could eliminate part of high abundance proteins in serum, but low abundance proteins less harvested, and multiple affinity chromatography column Human 14 method could effectively removed the high abundance proteins, and keep a large number of low abundance proteins.

Effects of Propylene Carbonate Content in CsPF6-Containing Electrolytes on the Enhanced Performances of Graphite Electrode for Lithium-Ion Batteries

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

Zheng, Jianming; Yan, Pengfei; Cao, Ruiguo

2016-02-10

Cesium salt has been demonstrated as an efficient electrolyte additive in suppressing the lithium (Li) dendrite formation and directing the formation of an ultrathin and stable solid electrolyte interphase (SEI) even in propylene carbonate (PC)-ethylene carbonate (EC)-based electrolytes. Here, we further investigate the effect of PC content in the presence of CsPF6 additive (0.05 M) on the performances of graphite electrode in Li||graphite half cells and in graphite||LiNi0.80Co0.15Al0.05O2 (NCA) full cells. It is found that the performance of graphite electrode is also affected by PC content even though CsPF6 additive is present in the electrolytes. An optimal PC content ofmore » 20% by weight in the solvent mixtures is identified. The enhanced electrochemical performance of graphite electrode is attributed to the synergistic effects of the Cs+ additive and the PC solvent. The formation of a robust, ultrathin and compact SEI layer containing lithium-enriched species on the graphite electrode, directed by Cs+, effectively suppresses the PC co-intercalation and thus prevents the graphite exfoliation. This SEI layer is only permeable for de-solvated Li+ ions and allows fast Li+ ion transport through it, which therefore largely alleviates the Li dendrite formation on graphite electrode during lithiation even at high current densities. The presence of low-melting-point PC solvent also enables the sustainable operation of the graphite||NCA full cells under a wide spectrum of temperatures. The fundamental findings of this work shed light on the importance of manipulating/maintaining the electrode/electrolyte interphasial stability in a variety of energy storage devices.« less

Solid-state drawing of post-consumer isotactic poly(propylene): Effect of melt filtration and carbon black on structural and mechanical properties.

PubMed

Luijsterburg, B J; Jobse, P S; Spoelstra, A B; Goossens, J G P

2016-08-01

Post-consumer plastic waste obtained via mechanical recycling is usually applied in thick-walled products, because of the low mechanical strength due to the presence of contaminants. In fact, sorted post-consumer isotactic poly(propylene) (i-PP) can be considered as a blend of 95% i-PP and 5% poly(ethylene), with traces of poly(ethylene terephthalate) (PET). By applying a treatment such as solid-state drawing (SSD) after melt extrusion, the polymer chains can be oriented in one direction, thereby improving the stiffness and tensile strength. In this research, molecular processes such as crystal break-up and chain orientation of these complex blends were monitored as a function of draw ratio. The melt filter mesh size - used to exclude rigid PET particles - and the addition of carbon black (CB) - often added for coloration in the recycling industry - were varied to investigate their influence on the SSD process. This research shows that despite the blend complexity, the molecular processes during SSD compare to virgin i-PP and that similar draw ratios can be obtained (λmax=20), albeit at reduced stiffness and strength as a result of the foreign polymers present in post-consumer i-PP. It is observed that the process stability improves with decreasing mesh size and that higher draw ratios can be obtained. The addition of carbon black, which resides in the dispersed PE phase, also stabilizes the SSD process. Compared to isotropic post-consumer i-PP, the stiffness can be improved by a factor 10 to over 11GPa, while the tensile strength can be improved by a factor 15-385MPa, which is approx. 70% of the maximum tensile strength achieved for virgin i-PP. Copyright © 2016 Elsevier Ltd. All rights reserved.

Determination of sulfonamides in swine muscle after salting-out assisted liquid extraction with acetonitrile coupled with back-extraction by a water/acetonitrile/dichloromethane ternary component system prior to high-performance liquid chromatography.

PubMed

Tsai, Wen-Hsien; Huang, Tzou-Chi; Chen, Ho-Hsien; Wu, Yuh-Wern; Huang, Joh-Jong; Chuang, Hung-Yi

2010-01-15

A salting-out assisted liquid extraction coupled with back-extraction by a water/acetonitrile/dichloromethane ternary component system combined with high-performance liquid chromatography with diode-array detection (HPLC-DAD) was developed for the extraction and determination of sulfonamides in solid tissue samples. After the homogenization of the swine muscle with acetonitrile and salt-promoted partitioning, an aliquot of 1 mL of the acetonitrile extract containing a small amount of dichloromethane (250-400 microL) was alkalinized with diethylamine. The clear organic extract obtained by centrifugation was used as a donor phase and then a small amount of water (40-55 microL) could be used as an acceptor phase to back-extract the analytes in the water/acetonitrile/dichloromethane ternary component system. In the back-extraction procedure, after mixing and centrifuging, the sedimented phase would be water and could be withdrawn easily into a microsyringe and directly injected into the HPLC system. Under the optimal conditions, recoveries were determined for swine muscle fortified at 10 ng/g and quantification was achieved by matrix-matched calibration. The calibration curves of five sulfonamides showed linearity with the coefficient of estimation above 0.998. Relative recoveries for the analytes were all from 96.5 to 109.2% with relative standard deviation of 2.7-4.0%. Preconcentration factors ranged from 16.8 to 30.6 for 1 mL of the acetonitrile extract. Limits of detection ranged from 0.2 to 1.0 ng/g. 2009 Elsevier B.V. All rights reserved.

Laboratory Investigations into the Spectra and Origin of Propylene Oxide: A Chiral Interstellar Molecule

NASA Technical Reports Server (NTRS)

Hudson, R. L.; Loeffler, M. J.; Yocum, K. M.

2017-01-01

Propylene oxide was recently identified in the interstellar medium, but few laboratory results are available for this molecule to guide current and future investigations. To address this situation, here we report infrared spectra, absorption coefficients, and band strengths of solid propylene oxide along with the first measurement of its refractive index and a calculation of its density, all for the amorphous solid form of the compound. We present the first experimental results showing a low-temperature formation pathway for propylene oxide near 10 K in interstellar ice analogs. Connections are drawn between our new results and the interstellar molecules propanal and acetone, and predictions are made about several as yet unobserved vinyl alcohols and methylketene. Comparisons are given to earlier laboratory work and a few applications to interstellar and solar system astrochemistry are described.

Laboratory Investigations into the Spectra and Origin of Propylene Oxide: A Chiral Interstellar Molecule

NASA Astrophysics Data System (ADS)

Hudson, R. L.; Loeffler, M. J.; Yocum, K. M.

2017-02-01

Propylene oxide was recently identified in the interstellar medium, but few laboratory results are available for this molecule to guide current and future investigations. To address this situation, here we report infrared spectra, absorption coefficients, and band strengths of solid propylene oxide along with the first measurement of its refractive index and a calculation of its density, all for the amorphous solid form of the compound. We present the first experimental results showing a low-temperature formation pathway for propylene oxide near 10 K in interstellar ice analogs. Connections are drawn between our new results and the interstellar molecules propanal and acetone, and predictions are made about several as yet unobserved vinyl alcohols and methylketene. Comparisons are given to earlier laboratory work and a few applications to interstellar and solar system astrochemistry are described.

Anaerobic biotransformation of explosives in aquifer slurries amended with ethanol and propylene glycol.

PubMed

Adrian, Neal R; Arnett, Clint M

2007-01-01

Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), and 2,4,6-trinitrotoluene (TNT) are explosives that are frequently found as environmental contaminants on military installations. Hydrogen has been shown to support the anaerobic transformation of these explosives. We investigated ethanol and propylene glycol as electron donors for providing syntrophically produced H2 for stimulating the anaerobic biodegradation of explosives in contaminated soil. The study was conducted using anoxic microcosms constructed with slurries of the contaminated soil and groundwater. The addition of 5mM ethanol and propylene glycol enhanced the biodegradation of RDX and HMX relative to the control bottles. Ethanol was depleted within about 20 days, resulting in the transient formation of hydrogen, acetate, and methane. The hydrogen headspace concentration increased from 8 ppm to 1838 ppm before decreasing to background concentrations. Propylene glycol was completely degraded after 15 days, forming hydrogen, propionate, and acetate as end-products. The hydrogen headspace concentrations increased from 56 ppm to 628 ppm before decreasing to background concentrations. No methane formation was observed during the incubation period of 48 days. Our findings indicate the addition of ethanol and propylene to the aquifer slurries increased the hydrogen concentrations and enhanced the biotransformation of RDX and HMX in the explosive-contaminated soil.

Comparison of biodegradation of poly(ethylene glycol)s and poly(propylene glycol)s.

PubMed

Zgoła-Grześkowiak, Agnieszka; Grześkowiak, Tomasz; Zembrzuska, Joanna; Łukaszewski, Zenon

2006-07-01

The biodegradation of poly(ethylene glycol)s (PEGs) and poly(propylene glycol)s (PPGs), both being major by-products of non-ionic surfactants biodegradation, was studied under the conditions of the River Water Die-Away Test. PEGs were isolated from a water matrix using solid-phase extraction with graphitized carbon black sorbent, then derivatized with phenyl isocyanate and determined by HPLC with UV detection. PPGs were isolated from a water matrix by liquid-liquid extraction with chloroform, then derivatized with naphthyl isocyanate and determined by HPLC with fluorescence detection. The primary biodegradation of both PEGs and PPGs reached approximately 99% during the test. The tests show different biodegradation pathways of PEG and PPG. During PEG biodegradation, their chains are shortened leading to the formation of ethylene glycol and diethylene glycol. During PPG biodegradation, no short-chained biodegradation products were found.

Impact of the propylene glycol-water-borax coolant on material recovery operations

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

Duerksen, W.K.; Taylor, P.A.

1983-05-01

The reaction of the propylene glycol-water-borax coolant with nitric acid has now been studied in some detail. This document is intended to provide a summary of the results. Findings are summarized under nine headings. Tests have also been conducted to determine if the new coolant would have any adverse effects on the uranium recycle systems. Experiments were scientifically designed after observation of the production operations so that accurate response to the immediate production concerns could be provided. Conclusions from these studies are: formation of glycol nitrates is very improbable; the reaction of concentrated (70%) nitric acid with pure propylene glycolmore » is very violent and hazardous; dilution of the nitric acid-glycol mixture causes a drastic decrease in the rate and intensity of the reaction; the mechanism of the nitric acid propylene glycol reaction is autocatalytic in nitrous acid; no reaction is observed between coolant and 30% nitric acid unless the solution is heated; the coolant reacts fairly vigorously with 55% nitric acid after a concentration-dependent induction time; experiments showed that the dissolution of uranium chips that had been soaked in coolant proceeded at about the same rate as if the chips had not previously contacted glycol; thermodynamic calculations show that the enthalpy change (heat liberated) by the reaction of nitric acid (30%) with propylene glycol is smaller than if the same amount of nitric acid reacted with uranium. Each of these conclusions is briefly discussed. The effect of new coolant on uranium recycle operations is then briefly discussed.« less

Safety assessment of propylene glycol, tripropylene glycol, and PPGs as used in cosmetics.

PubMed

Fiume, Monice M; Bergfeld, Wilma F; Belsito, Donald V; Hill, Ronald A; Klaassen, Curtis D; Liebler, Daniel; Marks, James G; Shank, Ronald C; Slaga, Thomas J; Snyder, Paul W; Andersen, F Alan

2012-01-01

Propylene glycol is an aliphatic alcohol that functions as a skin conditioning agent, viscosity decreasing agent, solvent, and fragrance ingredient in cosmetics. Tripropylene glycol functions as a humectant, antioxidant, and emulsion stabilizer. Polypropylene glycols (PPGs), including PPG-3, PPG-7, PPG-9, PPG-12, PPG-13, PPG-15, PPG-16, PPG-17, PPG-20, PPG-26, PPG-30, PPG-33, PPG-34, PPG-51, PPG-52, and PPG-69, function primarily as skin conditioning agents, with some solvent use. The majority of the safety and toxicity information presented is for propylene glycol (PG). Propylene glycol is generally nontoxic and is noncarcinogenic. Clinical studies demonstrated an absence of dermal sensitization at use concentrations, although concerns about irritation remained. The CIR Expert Panel determined that the available information support the safety of tripropylene glycol as well as all the PPGs. The Expert Panel concluded that PG, tripropylene glycol, and PPGs ≥3 are safe as used in cosmetic formulations when formulated to be nonirritating.

Laboratory Investigations into the Spectra and Origin of Propylene Oxide: A Chiral Interstellar Molecule

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

Hudson, R. L.; Loeffler, M. J.; Yocum, K. M., E-mail: Reggie.Hudson@nasa.gov

Propylene oxide was recently identified in the interstellar medium, but few laboratory results are available for this molecule to guide current and future investigations. To address this situation, here we report infrared spectra, absorption coefficients, and band strengths of solid propylene oxide along with the first measurement of its refractive index and a calculation of its density, all for the amorphous solid form of the compound. We present the first experimental results showing a low-temperature formation pathway for propylene oxide near 10 K in interstellar ice analogs. Connections are drawn between our new results and the interstellar molecules propanal andmore » acetone, and predictions are made about several as yet unobserved vinyl alcohols and methylketene. Comparisons are given to earlier laboratory work and a few applications to interstellar and solar system astrochemistry are described.« less

Detection of Carbon Monoxide Using Polymer-Carbon Composite Films

NASA Technical Reports Server (NTRS)

Homer, Margie L.; Ryan, Margaret A.; Lara, Liana M.

2011-01-01

A carbon monoxide (CO) sensor was developed that can be incorporated into an existing sensing array architecture. The CO sensor is a low-power chemiresistor that operates at room temperature, and the sensor fabrication techniques are compatible with ceramic substrates. Sensors made from four different polymers were tested: poly (4-vinylpryridine), ethylene-propylene-diene-terpolymer, polyepichlorohydrin, and polyethylene oxide (PEO). The carbon black used for the composite films was Black Pearls 2000, a furnace black made by the Cabot Corporation. Polymers and carbon black were used as received. In fact, only two of these sensors showed a good response to CO. The poly (4-vinylpryridine) sensor is noisy, but it does respond to the CO above 200 ppm. The polyepichlorohydrin sensor is less noisy and shows good response down to 100 ppm.

Propylene glycol liposomes as a topical delivery system for miconazole nitrate: comparison with conventional liposomes.

PubMed

Elmoslemany, Riham M; Abdallah, Ossama Y; El-Khordagui, Labiba K; Khalafallah, Nawal M

2012-06-01

Propylene glycol (PG)-phospholipid vesicles have been advocated as flexible lipid vesicles for enhanced skin delivery of drugs. To further characterize the performance of these vesicles and to address some relevant pharmaceutical issues, miconazole nitrate(MN)-loaded PG nanoliposomes were prepared and characterized for vesicle size, entrapment efficiency, in vitro release, and vesicle stability. An issue of pharmaceutical importance is the time-dependent, dilution-driven diffusion of propylene glycol out of the vesicles. This was addressed by assessing propylene glycol using gas chromatography in the separated vesicles and monitoring its buildup in the medium after repeated dispersion of separated vesicles in fresh medium. Further, the antifungal activity of liposomal formulations under study was assessed using Candida albicans, and their in vitro skin permeation and retention were studied using human skin. At all instances, blank and drug-loaded conventional liposomes were included for comparison. The results provided evidence of controlled MN delivery, constant percent PG uptake in the vesicles (≈45.5%) in the PG concentration range 2.5 to 10%, improved vesicle stability, and enhanced skin deposition of MN with minimum skin permeation. These are key issues for different formulation and performance aspects of propylene glycol-phospholipid vesicles.

FORMATION OF POLYKETONES IN IRRADIATED TOLUENE/PROPYLENE/NOX/AIR MIXTURES

EPA Science Inventory

A laboratory study was carried out to investigate the formation of polyketones in secondary organic aerosol from photooxidation of the aromatic hydrocarbon toluene, a major constituent of automobile exhaust. The laboratory experiments consisted of irradiating toluene/propylene...

Solution stability of Captisol-stabilized melphalan (Evomela) versus Propylene glycol-based melphalan hydrochloride injection.

PubMed

Singh, Ramsharan; Chen, Jin; Miller, Teresa; Bergren, Michael; Mallik, Rangan

2016-12-14

The objective of this study was to compare the stability of recently approved Captisol-stabilized propylene glycol-free melphalan injection (Evomela™) against currently marketed propylene glycol-based melphalan injection. The products were compared as reconstituted solutions in vials as well as admixture solutions prepared from normal saline in infusion bags. Evomela and propylene glycol-based melphalan injection were reconstituted in normal saline and organic custom diluent, respectively, according to their package insert instructions. The reconstituted solutions were diluted in normal saline to obtain drug admixture solutions at specific drug concentrations. Stability of the solutions was studied at room temperature by assay of melphalan and determination of melphalan-related impurities. Results show that based on the increase in total impurities in propylene glycol-based melphalan injection at 0.45 mg/mL, Evomela admixture solutions are about 5, 9, 15 and 29 times more stable at concentrations of 0.45, 1.0, 2.0 and 5.0 mg/mL, respectively. Results confirmed that reconstituted Evomela solution can be stored in the vial for up to 1 h at RT or for up to 24 h at refrigerated temperature (2-8 °C) with no significant degradation. After storage in the vial, it remains stable for an additional 3-29 h after preparation of admixture solution in infusion bags at concentrations of 0.25-5.0 mg/mL, respectively. In addition, Evomela solution in saline, at concentration of 5.0 mg/mL melphalan was bacteriostatic through 72 h storage at 2-8 °C. Formulation of melphalan with Captisol technology significantly improved stability compared to melphalan hydrochloride reconstituted with propylene-glycol based diluents.

The influence of pore size and surface area of activated carbons on the performance of ionic liquid based supercapacitors.

PubMed

Pohlmann, Sebastian; Lobato, Belén; Centeno, Teresa A; Balducci, Andrea

2013-10-28

This study analyses and compares the behaviour of 5 commercial porous carbons in the ionic liquid N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR14TFSI) and its mixture with propylene carbonate (PC) as electrolytes. The results of this investigation show that the existence of a distribution of pore sizes and/or constrictions at the entrance of the pores leads to significant changes in the specific capacitance of the investigated materials. The use of PYR14TFSI as an electrolyte has a positive effect on the EDLC energy storage, but its high viscosity limits the power density. The mixture 50 : 50 wt% propylene carbonate-PYR14TFSI provides high operative voltage as well as low viscosity and thus notably enhances EDLC operation.

Phosphonate Pendant Armed Propylene Cross-Bridged Cyclam: Synthesis and Evaluation as a Chelator for Cu-64

PubMed Central

2015-01-01

A propylene cross-bridged macrocyclic chelator with two phosphonate pendant arms (PCB-TE2P) was synthesized from cyclam. Various properties of the synthesized chelator, including Cu-complexation, Cu-complex stability, 64Cu-radiolabeling, and in vivo behavior, were studied and compared with those of a previously reported propylene cross-bridged chelator (PCB-TE2A). PMID:26617972

Synthesis of ethylene-propylene rubber graft copolymers by borane approach

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

Chung, T.C.; Janvikul, W.; Bernard, R.

1994-01-01

This paper describes a new method to prepare graft copolymers which have an EP rubber backbone and several free radical polymerized polymers grafted thereto. The process involves hydroboration of commercial EPDM rubbers, such as poly(ethylene-co-propylene-co-1,4-hexadiene) and poly(ethylene-co-propylene-co-5-ethylidene-2-norbornene), with 9-borabicyclononane (9-BBN). The resulting secondary alkyl-9-BBN moieties in the EPDM copolymer were then exposed to oxygen in the presence of free radical polymerizable monomers. Under certain conditions, the selective autoxidation reaction of secondary alkyl-9-BBN took place to create desirable polymeric radicals which can in situ initiate free radical polymerization. High graft efficiency was observed with controllable copolymer compositions. The graft copolymer ofmore » EP-g-PMMA is used to show the chemistry as well as some of the physical properties.« less

Direct Epoxidation of Propylene over Stabilized Cu + Surface Sites on Ti Modified Cu 2O

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

Yang, X.; Kattel, S.; Xiong, K.

2015-07-17

Direct propylene epoxidation by O 2 is a challenging reaction because of the strong tendency for complete combustion. Results from the current study demonstrate the feasibility to tune the epoxidation selectivity by generating highly dispersed and stabilized Cu + active sites in a TiCuO x mixed oxide. The TiCuO x surface anchors the key surface intermediate, oxametallacycle, leading to higher selectivity for epoxidation of propylene.

Decay dynamics of nascent acetonitrile and nitromethane dipole-bound anions produced by intracluster charge-transfer

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

Yandell, Margaret A.; King, Sarah B.; Neumark, Daniel M., E-mail: dneumark@berkeley.edu

2014-05-14

Decay dynamics of nascent dipole bound states of acetonitrile and nitromethane are examined using time-resolved photoelectron imaging of iodide-acetonitrile (I{sup −}·CH{sub 3}CN) and iodide-nitromethane (I{sup −}·CH{sub 3}NO{sub 2}) complexes. Dipole-bound anions are created by UV-initiated electron transfer to the molecule of interest from the associated iodide ion at energies just below the vertical detachment energy of the halide-molecule complex. The acetonitrile anion is observed to decay biexponentially with time constants in the range of 4–900 ps. In contrast, the dipole bound state of nitromethane decays rapidly over 400 fs to form the valence bound anion. The nitromethane valence anion speciesmore » then decays biexponentially with time constants of 2 ps and 1200 ps. The biexponential decay dynamics in acetonitrile are interpreted as iodine atom loss and autodetachment from the excited dipole-bound anion, followed by slower autodetachment of the relaxed metastable ion, while the dynamics of the nitromethane system suggest that a dipole-bound anion to valence anion transition proceeds via intramolecular vibrational energy redistribution to nitro group modes in the vicinity of the iodine atom.« less

Decay dynamics of nascent acetonitrile and nitromethane dipole-bound anions produced by intracluster charge-transfer.

PubMed

Yandell, Margaret A; King, Sarah B; Neumark, Daniel M

2014-05-14

Decay dynamics of nascent dipole bound states of acetonitrile and nitromethane are examined using time-resolved photoelectron imaging of iodide-acetonitrile (I(-)·CH3CN) and iodide-nitromethane (I(-)·CH3NO2) complexes. Dipole-bound anions are created by UV-initiated electron transfer to the molecule of interest from the associated iodide ion at energies just below the vertical detachment energy of the halide-molecule complex. The acetonitrile anion is observed to decay biexponentially with time constants in the range of 4-900 ps. In contrast, the dipole bound state of nitromethane decays rapidly over 400 fs to form the valence bound anion. The nitromethane valence anion species then decays biexponentially with time constants of 2 ps and 1200 ps. The biexponential decay dynamics in acetonitrile are interpreted as iodine atom loss and autodetachment from the excited dipole-bound anion, followed by slower autodetachment of the relaxed metastable ion, while the dynamics of the nitromethane system suggest that a dipole-bound anion to valence anion transition proceeds via intramolecular vibrational energy redistribution to nitro group modes in the vicinity of the iodine atom.

Effects of Propylene Carbonate Content in CsPF 6 -Containing Electrolytes on the Enhanced Performances of Graphite Electrode for Lithium-Ion Batteries

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

Zheng, Jianming; Yan, Pengfei; Cao, Ruiguo

2016-02-15

The effects Of propylene carbonate (PC) content in CsPF6-containing electrolytes on the performances of graphite electrode in lithium half cells and in graphite parallel to LiNi0.80Co0.15Al0.05O2 (NCA) full cells are investigated. It is found that the performance of graphite electrode is significantly-affected by PC content in the CsPF6-containing electrolytes. An optimal PC content of 20% by weight in the solvent mixtures is identified. The enhanced electrochemical performance of graphite electrode can be attributed to the synergistic effects of the PC solvent and the Cs+ additive. The synergistic effects of Cs+ additive and appropriate amount of PC enable the formation ofmore » a robust, ultrathin, and compact solid electrolyte interphase (SEI) layer on the surface of graphite electrode, which is only permeable for desolvated Li+ ions and allows fast Li+ ion transport through it. Therefore, this SEI layer effectively suppresses the PC cointercalation and largely alleviates the Li dendrite formation on graphite electrode during lithiation even at relatively high current densities. The presence of low-melting-point PC solvent improves the sustainable operation of graphite parallel to NCA full cells under a wide temperature range. The fundamental findings also shed light On the importance of manipulating/maintaining the electrode/electrolyte interphasial stability in various energy-storage devices.« less

Ceo2 Based Catalysts for the Treatment of Propylene in Motorcycle’s Exhaust Gases

PubMed Central

Pham, Phuong Thi Mai; Le Minh, Thang; Nguyen, Tien The; Van Driessche, Isabel

2014-01-01

In this work, the catalytic activities of several single metallic oxides were studied for the treatment of propylene, a component in motorcycles’ exhaust gases, under oxygen deficient conditions. Amongst them, CeO2 is one of the materials that exhibit the highest activity for the oxidation of C3H6. Therefore, several mixtures of CeO2 with other oxides (SnO2, ZrO2, Co3O4) were tested to investigate the changes in catalytic activity (both propylene conversion and CO2 selectivity). Ce0.9Zr0.1O2, Ce0.8Zr0.2O2 solid solutions and the mixtures of CeO2 and Co3O4 was shown to exhibit the highest propylene conversion and CO2 selectivity. They also exhibited good activities when tested under oxygen sufficient and excess conditions and with the presence of co-existing gases (CO, H2O). PMID:28788253

Influence of Mixed Solvent on the Electrochemical Property of Hybrid Capacitor.

PubMed

Lee, Byunggwan; Yoon, J R

2015-11-01

The hybrid capacitors (2245 size, cylindrical type) were prepared by using activated carbon cathode and Li4Ti5O12 anode. In order to improve the cell operation at high temperature range, propylene carbonate (PC) was used in combination with acetonitrile (AN) with volume ratio of 7:3, 5:5, and 3:7, respectively. We investigated the electrochemical behavior of the hybrid capacitors that enabled cell operation with stability at high temperature. The organic electrolyte of hybrid capacitor containing PC and AN with a volume ratio 7:3 intended to exhibit highly reversible cycle performance with good capacity retention at 60 degrees C after 2200 cycles. From this study, it has been found that the very strong influence of the solvent nature on the characteristics of hybrid capacitor, and the difference in performance associated with the two solvents.

Immobilization of Rhodococcus rhodochrous BX2 (an acetonitrile-degrading bacterium) with biofilm-forming bacteria for wastewater treatment.

PubMed

Li, Chunyan; Li, Yue; Cheng, Xiaosong; Feng, Liping; Xi, Chuanwu; Zhang, Ying

2013-03-01

In this study, a unique biofilm consisting of three bacterial strains with high biofilm-forming capability (Bacillus subtilis E2, E3, and N4) and an acetonitrile-degrading bacterium (Rhodococcus rhodochrous BX2) was established for acetonitrile-containing wastewater treatment. The results indicated that this biofilm exhibited strong resistance to acetonitrile loading shock and displayed a typical spatial and structural heterogeneity and completely depleted the initial concentration of acetonitrile (800mgL(-1)) within 24h in a moving-bed-biofilm reactor (MBBR) after operation for 30days. The immobilization of BX2 cells in the biofilm was confirmed by PCR-DGGE. It has been demonstrated that biofilm-forming bacteria can promote the immobilization of contaminant-degrading bacteria in the biofilms and can subsequently improve the degradation of contaminants in wastewater. This approach offers a novel strategy for enhancing biological oxidation of toxic pollutants in wastewater. Copyright © 2012 Elsevier Ltd. All rights reserved.

Hydrogenolysis of Glycerol to Propylene Glycol on Nanosized Cu-Zn-Al Catalysts Prepared Using Microwave Process.

PubMed

Kim, Dong Won; Ha, Sang Ho; Moon, Myung Jun; Lim, Kwon Taek; Ryu, Young Bok; Lee, Sun Do; Lee, Man Sig; Hong, Seong-Soo

2015-01-01

Cu-Zn-Al catalysts were prepared using microwave-assisted process and co-precipitation methods. The prepared catalysts were characterized by XRD, BET, XPS and TPD of ammonia and their catalytic activity for the hydrogenolysis of glycerol to propylene glycol was also examined. The XRD patterns of Cu/Zn/Al mixed catalysts show CuO and ZnO crystalline phase regardless of preparation method. The highest glycerol hydrogenolysis conversion is obtained with the catalyst having a Cu/Zn/Al ratio of 2:2:1. Hydrogen pre-reduction of catalysts significantly enhanced both glycerol conversions and selectivity to propylene glycol. The glycerol conversion increased with an increase of reaction temperature. However, the selectivity to propylene glycol increased with an increase of temperature, and then declined to 30.5% at 523 K.

Electrosynthesis and characterization of oligophenylene deriving from 4-(methoxyphenyl)acetonitrile

NASA Astrophysics Data System (ADS)

Amor, Sarra Ben; Said, Ayoub Haj; Chemek, Mourad; Ayachi, Sahbi; Massuyeau, Florian; Wéry, Jany; Alimi, Kamel; Roudesli, Sadok

2013-01-01

An oligophenylene deriving from the 4-(methoxyphenyl)acetonitrile (MPA), was electrosynthesized by direct anodic oxidation at a constant potential in acetonitrile on a platinium electrode. This oligomer (OMPA) showed a good solubility in common organic solvents. The results of osmometry and gel permeation chromatography analyzes indicated that the average chain length for OMPA was about 5 units. Its chemical structure was elucidated by 1H and 13C NMR, FTIR and UV spectroscopy. A thermal study carried out by thermogravimetric analysis and Differential Scanning Calorimetry showed that the oligomer was stable up to 268 °C. In addition, the photoluminescent properties of OMPA were investigated. In solution, an emission was recorded in the indigo-blue region, however, in solid state this emission was shifted to the orange-red zone. Finally a mechanism for the electro-oligomerization was evoked in the light of the electronic structures of the MPA and its radical cation obtained by DFT calculation.

Origin of electrochemical, structural and transport properties in non-aqueous zinc electrolytes

DOE PAGES

Han, Sang -Don; Rajput, Nav Nidhi; Qu, Xiaohui; ...

2016-01-14

Through coupled experimental analysis and computational techniques, we uncover the origin of anodic stability for a range of nonaqueous zinc electrolytes. By examination of electrochemical, structural, and transport properties of nonaqueous zinc electrolytes with varying concentrations, it is demonstrated that the acetonitrile Zn(TFSI) 2, acetonitrile Zn(CF 3SO 3) 2, and propylene carbonate Zn(TFSI) 2 electrolytes can not only support highly reversible Zn deposition behavior on a Zn metal anode (≥99% of Coulombic efficiency), but also provide high anodic stability (up to ~3.8 V). The predicted anodic stability from DFT calculations is well in accordance with experimental results, and elucidates thatmore » the solvents play an important role in anodic stability of most electrolytes. Molecular dynamics (MD) simulations were used to understand the solvation structure (e.g., ion solvation and ionic association) and its effect on dynamics and transport properties (e.g., diffusion coefficient and ionic conductivity) of the electrolytes. Lastly, the combination of these techniques provides unprecedented insight into the origin of the electrochemical, structural, and transport properties in nonaqueous zinc electrolytes« less

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

Han, Sang -Don; Rajput, Nav Nidhi; Qu, Xiaohui

Through coupled experimental analysis and computational techniques, we uncover the origin of anodic stability for a range of nonaqueous zinc electrolytes. By examination of electrochemical, structural, and transport properties of nonaqueous zinc electrolytes with varying concentrations, it is demonstrated that the acetonitrile Zn(TFSI) 2, acetonitrile Zn(CF 3SO 3) 2, and propylene carbonate Zn(TFSI) 2 electrolytes can not only support highly reversible Zn deposition behavior on a Zn metal anode (≥99% of Coulombic efficiency), but also provide high anodic stability (up to ~3.8 V). The predicted anodic stability from DFT calculations is well in accordance with experimental results, and elucidates thatmore » the solvents play an important role in anodic stability of most electrolytes. Molecular dynamics (MD) simulations were used to understand the solvation structure (e.g., ion solvation and ionic association) and its effect on dynamics and transport properties (e.g., diffusion coefficient and ionic conductivity) of the electrolytes. Lastly, the combination of these techniques provides unprecedented insight into the origin of the electrochemical, structural, and transport properties in nonaqueous zinc electrolytes« less

Theoretical and experimental examination of SFG polarization analysis at acetonitrile-water solution surfaces.

PubMed

Saito, Kengo; Peng, Qiling; Qiao, Lin; Wang, Lin; Joutsuka, Tatsuya; Ishiyama, Tatsuya; Ye, Shen; Morita, Akihiro

2017-03-29

Sum frequency generation (SFG) spectroscopy is widely used to observe molecular orientation at interfaces through a combination of various types of polarization. The present work thoroughly examines the relation between the polarization dependence of SFG signals and the molecular orientation, by comparing SFG measurements and molecular dynamics (MD) simulations of acetonitrile/water solutions. The present SFG experiment and MD simulations yield quite consistent results on the ratios of χ (2) elements, supporting the reliability of both means. However, the subsequent polarization analysis tends to derive more upright tilt angles of acetonitrile than the direct MD calculations. The reasons for discrepancy are examined in terms of three issues; (i) anisotropy of the Raman tensor, (ii) cross-correlation, and (iii) orientational distribution. The analysis revealed that the issues (i) and (iii) are the main causes of errors in the conventional polarization analysis of SFG spectra. In methyl CH stretching, the anisotropy of Raman tensor cannot be estimated from the simple bond polarizability model. The neglect of the orientational distribution is shown to systematically underestimate the tilt angle of acetonitrile. Further refined use of polarization analysis in collaboration with MD simulations should be proposed.

Evidence of three-body correlation functions in Rb+ and Sr2+ acetonitrile solutions

NASA Astrophysics Data System (ADS)

D'Angelo, P.; Pavel, N. V.

1999-09-01

The local structure of Sr2+ and Rb+ ions in acetonitrile has been investigated by x-ray absorption spectroscopy (XAS) and molecular dynamics simulations. The extended x-ray absorption fine structure above the Sr and Rb K edges has been interpreted in the framework of multiple scattering (MS) formalism and, for the first time, clear evidence of MS contributions has been found in noncomplexing ion solutions. Molecular dynamics has been used to generate the partial pair and triangular distribution functions from which model χ(k) signals have been constructed. The Sr2+ and Rb+ acetonitrile pair distribution functions show very sharp and well-defined first peaks indicating the presence of a well organized first solvation shell. Most of the linear acetonitrile molecules have been found to be distributed like hedgehog spines around the Sr2+ and Rb+ ions. The presence of three-body correlations has been singled out by the existence of well-defined peaks in the triangular configurations. Excellent agreement has been found between the theoretical and experimental data enforcing the reliability of the interatomic potentials used in the simulations. These results demonstrate the ability of the XAS technique in probing the higher-order correlation functions in solution.

Identification of Furosemide Photodegradation Products in Water-Acetonitrile Mixture.

PubMed

Katsura, Shinji; Yamada, Nobuo; Nakashima, Atsushi; Shiraishi, Sumihiro; Furuishi, Takayuki; Ueda, Haruhisa

2015-01-01

The aim of this study was to identify the chemical structure of the photodegradation products of furosemide in a water-acetonitrile mixture (1 : 1). Furosemide solution was irradiated with a D65 fluorescent lamp and the products were isolated by preparative HPLC. The fractions were evaporated to dryness in vacuo. The purity of the photodegradation products was measured by HPLC. The purity of products 1, 3, and 4 was greater than 90%, whereas that of product 2 was 13%, therefore, photodegradation product 2 was unstable. We identified photodegradation products 1 and 3 as 4-chloro-5-sulfamoylanthranilic acid and 4-hydroxy-N-furfuryl-5-sulfamoylanthranilic acid, respectively, by LC/MS and NMR. Additionally, we assumed that photodegradation product 4 was methyl 2-((furan-2-ylmethyl)amino)-4-hydroxy-3-(methyleneamino)-5-sulfamoylbenzoate by LC/MS and NMR. This showed that furosemide underwent hydrolysis and substitution, and reacted with the acetonitrile under the light of a D65 fluorescent lamp. We were furthermore able to determine the elution times of the photodegradation products of furosemide by applying the Japanese Pharmacopoeia chromatographic method for related substances to the isolated products.

A combined experimental and theoretical study on ethanol conversion to propylene over Y/ZrO2 catalyst

NASA Astrophysics Data System (ADS)

Wang, Fangfang; Xia, Wei; Mu, Xichuan; Chen, Kun; Si, Huimin; Li, Zhihao

2018-05-01

ZrO2-based catalysts doped with Y were prepared by co-precipitation method. The effect of yttrium modification on the selective conversion of bio-ethanol to propylene over ZrO2 catalysts was investigated. The physical and chemical properties of the catalysts were characterized by N2 adsorption-desorption method, temperature programmed desorption and X-ray diffraction. The maximum yield of propylene reached 44.0% over 0.03Y/ZrO2 catalyst. A coordination of acid-base properties accounts for the remarkable improvement of reaction activities over Y-doped ZrO2 catalysts in this investigation. On the basis of calculation results, it can be concluded that significant charge transfer occurs as a result of introduction of Y or O-vacancy. The adsorption of ethanol and propylene on perfect t-ZrO2 (1 0 1), defect t-ZrO2 (1 0 1) and Y/ZrO2 (1 0 1) surfaces were investigated with density functional theory (DFT). The adsorption for ethanol on Y/ZrO2 (1 0 1) and defect t-ZrO2 (1 0 1) surfaces are more stable than that on perfect t-ZrO2 (1 0 1). On the defect t-ZrO2 (1 0 1) surface, ethanol dominantly absorbs at the O-vacancy site, indicating that O-vacancy becomes the favorable adsorption site. On the Y/ZrO2 (1 0 1) and defect t-ZrO2 (1 0 1) surfaces, the adsorption energy of propylene decreases, which makes propylene desorb quickly after formation.

Bactericidal activity of propylene glycol, glycerine, polyethylene glycol 400, and polyethylene glycol 1000 against selected microorganisms

PubMed Central

Nalawade, Triveni Mohan; Bhat, Kishore; Sogi, Suma H. P.

2015-01-01

Aim: The aim of the present study was to evaluate the bactericidal activity of propylene glycol, glycerine, polyethylene glycol 400 (PEG 400), and polyethylene glycol 1000 (PEG 1000) against selected microorganisms in vitro. Materials and Methods: Five vehicles, namely propylene glycol, glycerine, PEG 400, PEG 1000, and combination of propylene glycol with PEG 400, were tested for their bactericidal activity. The minimum bactericidal concentration was noted against four standard strains of organisms, i.e. Streptococcus mutans American Type Culture Collection (ATCC) 25175, Streptococcus mutans ATCC 12598, Enterococcus faecalis ATCC 35550, and Escherichia coli ATCC 25922, using broth dilution assay. Successful endodontic therapy depends upon thorough disinfection of root canals. In some refractory cases, routine endodontic therapy is not sufficient, so intracanal medicaments are used for proper disinfection of canals. Intracanal medicaments are dispensed with vehicles which aid in increased diffusion through the dentinal tubules and improve their efficacy. Among the various vehicles used, glycerine is easily available, whereas others like propylene glycol and polyethylene glycol have to be procured from appropriate sources. Also, these vehicles, being viscous, aid in sustained release of the medicaments and improve their handling properties. The most commonly used intracanal medicaments like calcium hydroxide are ineffective on many microorganisms, while most of the other medicaments like MTAD (Mixture of Tetracycline, an Acid, and a Detergent) and Triple Antibiotic Paste (TAP) consist of antibiotics which can lead to development of antibiotic resistance among microorganisms. Thus, in order to use safer and equally effective intracanal medicaments, newer alternatives like chlorhexidine gluconate, ozonized water, etc., are being explored. Similarly, the five vehicles mentioned above are being tested for their antimicrobial activity in this study. Results: All vehicles

Bactericidal activity of propylene glycol, glycerine, polyethylene glycol 400, and polyethylene glycol 1000 against selected microorganisms.

PubMed

Nalawade, Triveni Mohan; Bhat, Kishore; Sogi, Suma H P

2015-01-01

The aim of the present study was to evaluate the bactericidal activity of propylene glycol, glycerine, polyethylene glycol 400 (PEG 400), and polyethylene glycol 1000 (PEG 1000) against selected microorganisms in vitro. Five vehicles, namely propylene glycol, glycerine, PEG 400, PEG 1000, and combination of propylene glycol with PEG 400, were tested for their bactericidal activity. The minimum bactericidal concentration was noted against four standard strains of organisms, i.e. Streptococcus mutans American Type Culture Collection (ATCC) 25175, Streptococcus mutans ATCC 12598, Enterococcus faecalis ATCC 35550, and Escherichia coli ATCC 25922, using broth dilution assay. Successful endodontic therapy depends upon thorough disinfection of root canals. In some refractory cases, routine endodontic therapy is not sufficient, so intracanal medicaments are used for proper disinfection of canals. Intracanal medicaments are dispensed with vehicles which aid in increased diffusion through the dentinal tubules and improve their efficacy. Among the various vehicles used, glycerine is easily available, whereas others like propylene glycol and polyethylene glycol have to be procured from appropriate sources. Also, these vehicles, being viscous, aid in sustained release of the medicaments and improve their handling properties. The most commonly used intracanal medicaments like calcium hydroxide are ineffective on many microorganisms, while most of the other medicaments like MTAD (Mixture of Tetracycline, an Acid, and a Detergent) and Triple Antibiotic Paste (TAP) consist of antibiotics which can lead to development of antibiotic resistance among microorganisms. Thus, in order to use safer and equally effective intracanal medicaments, newer alternatives like chlorhexidine gluconate, ozonized water, etc., are being explored. Similarly, the five vehicles mentioned above are being tested for their antimicrobial activity in this study. All vehicles exhibited bactericidal activity at

Advances of two-stage riser catalytic cracking of heavy oil for maximizing propylene yield (TMP) process.

PubMed

Chaohe, Yang; Xiaobo, Chen; Jinhong, Zhang; Chunyi, Li; Honghong, Shan

Two-stage riser catalytic cracking of heavy oil for maximizing propylene yield (TMP) process proposed by State Key Laboratory of Heavy oil Processing, China University of Petroleum, can remarkably enhance the propylene yield and minimize the dry gas and coke yields, and obtain high-quality light oils (gasoline and diesel). It has been commercialized since 2006. Up to now, three TMP commercial units have been put into production and other four commercial units are under design and construction. The commercial data showed that taking paraffinic based Daqing (China) atmospheric residue as the feedstock, the propylene yield reached 20.31 wt%, the liquid products yield (the total yield of liquefied petroleum gas, gasoline, and diesel) was 82.66 wt%, and the total yield of dry gas and coke was 14.28 wt%. Moreover, the research octane number of gasoline could be up to 96.

The History of Current State of the Art of Propylene Polymerization Catalysts.

ERIC Educational Resources Information Center

Goodall, Brian L.

1986-01-01

Outlines the development of the modern catalysts for propylene polymerization, considering the historical background; structure of titanium chloride catalysts; first-generation catalysts; cocatalysts; second-generation catalysts; catalysts morphology; and third-generation (supported catalysts). (JN)

A novel derivatization-free method of formaldehyde and propylene glycol determination in hydrogels by liquid chromatography with refractometric detection.

PubMed

Isakau, Henadz; Robert, Marielle; Shingel, Kirill I

2009-04-05

The paper describes the development and validation of a new derivatization-free liquid chromatography method for simultaneous determination of propylene glycol and formaldehyde in the formulations containing formaldehyde-releasing preservative. Highly swollen hydrogel made of poly(ethylene glycol)-protein conjugates was taken as a model formulation for integration of the propylene glycol and the diazolydinyl urea as formaldehyde releaser. The method is shown to be simple and selective and, more importantly, allows determining an existing level of formaldehyde at the moment of analysis instead of all available formaldehyde that might be released during chemical derivatization. After liquid extraction the propylene glycol (PG) and formaldehyde (FA) amounts are determined chromatographically on a Shodex SH 1011 ligand-exchange column using 0.01 M sulfuric acid mobile phase, a flow rate of 1.0 ml/min and RI detection. The assay is validated showing good linearity, precision, and accuracy. The limits of detection of formaldehyde and propylene glycol in the analyzed solutions were estimated to be 25 ng and 87 ng, respectively. This analytical assay is considered useful for product stability studies and in developing new formaldehyde releaser-containing formulations where the concentration of formaldehyde is a presumable subject of labeling requirements. This method can also provide a rapid and convenient alternative to gas chromatography method of propylene glycol quantification.

The effect of glycerol, propylene glycol and polyethylene glycol 400 on the partition coefficient of benzophenone-3 (oxybenzone).

PubMed

Mbah, C J

2007-01-01

Sunscreen products are widely used to protect the skin from sun-related deleterious effects. The objective of the study was to investigate the potential effect of glycerol, propylene glycol and polyethylene glycol 400 on dermal absorption of oxybenzone by studying their effects on its partition coefficient. The partition coefficient was evaluated in a chloroform-water system at room temperature. It was found that glycerol and propylene glycol decreased the partition coefficient of oxybenzone, while an increase in partition coefficient was observed with polyethylene glycol 400. The findings suggest that polyethylene glycol 400 in contrast to glycerol and propylene glycol has the potential of increasing the vehicle-skin partition coefficient of oxybenzone when cosmetic products containing such an UV absorber are topically applied to the skin.

A positive chemical ionization GC/MS method for the determination of airborne ethylene glycol and propylene glycols in non-occupational environments.

PubMed

Zhu, Jiping; Feng, Yong-Lai; Aikawa, Bio

2004-11-01

An analytical method for ethylene glycol and propylene glycols has been developed for measuring airborne levels of these chemicals in non-occupational environments such as residences and office buildings. The analytes were collected on charcoal tubes, solvent extracted, and analyzed by gas chromatography-mass spectrometry using a positive chemical ionization technique. The method had a method detection limit of 0.07 microg m(-3) for ethylene glycol and 0.03 microg m(-3) for 1,2- and 1,3-propylene glycols, respectively, based on a 1.44 m3 sampling volume. Indoor air samples of several residential homes and other indoor environments have been analyzed. The median concentrations of ethylene glycol and 1,2-propylene glycol in nine residential indoor air samples were 53 microg m(-3) and 13 microg m(-3) respectively with maximum values of 223 microg m(-3) and 25 microg m(-3) detected for ethylene glycol and 1,2-propylene glycol respectively. The concentrations of these two chemicals in one office and two laboratories were at low microg m(-3) levels. The maximum concentration of 1,3-propylene glycol detected in indoor air was 0.1 microg m(-3).

Inert Reassessment Document for Propylene glycol alginate - CAS No. 9005-37-2

EPA Pesticide Factsheets

As an inert pesticide ingredient, propylene glycol alginate is exempt from the requirement for a tolerance when used as a deforming agent in pesticide formulations applies to growing crops, or to raw agricultural commodities after harvest.

Structure-function relationship of reduced cytochrome c probed by complete solution structure determination in 30% acetonitrile/water solution.

PubMed

Sivakolundu, Sivashankar G; Mabrouk, Patricia Ann

2003-05-01

The complete solution structure of ferrocytochrome c in 30% acetonitrile/70% water has been determined using high-field 1D and 2D (1)H NMR methods and deposited in the Protein Data Bank with codes 1LC1 and 1LC2. This is the first time a complete solution protein structure has been determined for a protein in nonaqueous media. Ferrocyt c retains a native protein secondary structure (five alpha-helices and two omega loops) in 30% acetonitrile. H18 and M80 residues are the axial heme ligands, as in aqueous solution. Residues believed to be axial heme ligands in the alkaline-like conformers of ferricyt c, specifically H33 and K72, are positioned close to the heme iron. The orientations of both heme propionates are markedly different in 30% acetonitrile/70% water. Comparative structural analysis of reduced cyt c in 30% acetonitrile/70% water solution with cyt c in different environments has given new insight into the cyt c folding mechanism, the electron transfer pathway, and cell apoptosis.

Singlet versus Triplet Excited State Mediated Photoinduced Dehalogenation Reactions of Itraconazole in Acetonitrile and Aqueous Solutions.

PubMed

Zhu, Ruixue; Li, Ming-de; Du, Lili; Phillips, David Lee

2017-04-06

Photoinduced dehalogenation of the antifungal drug itraconazole (ITR) in acetonitrile (ACN) and ACN/water mixed solutions was investigated using femtosecond and nanosecond time-resolved transient absorption (fs-TA and ns-TA, respectively) and nanosecond time-resolved resonance Raman spectroscopy (ns-TR 3 ) experiments. An excited resonance energy transfer is found to take place from the 4-phenyl-4,5-dihydro-3H-1,2,4-triazol-3-one part of the molecule to the 1,3-dichlorobenzene part of the molecule when ITR is excited by ultraviolet light. This photoexcitation is followed by a fast carbon-halogen bond cleavage that leads to the generation of radical intermediates via either triplet and/or singlet excited states. It is found that the singlet excited state-mediated carbon-halogen cleavage is the predominant dehalogenation process in ACN solvent, whereas a triplet state-mediated carbon-halogen cleavage prefers to occur in the ACN/water mixed solutions. The singlet-to-triplet energy gap is decreased in the ACN/water mixed solvents and this helps facilitate an intersystem crossing process, and thus, the carbon-halogen bond cleavage happens mostly through an excited triplet state in the aqueous solutions examined. The ns-TA and ns-TR 3 results also provide some evidence that radical intermediates are generated through a homolytic carbon-halogen bond cleavage via predominantly the singlet excited state pathway in ACN but via mainly the triplet state pathway in the aqueous solutions. In strong acidic solutions, protonation at the oxygen and/or nitrogen atoms of the 1,2,4-triazole-3-one group appears to hinder the dehalogenation reactions. This may offer the possibility that the phototoxicity of ITR due to the generation of aryl or halogen radicals can be reduced by protonation of certain moieties in suitably designed ITR halogen-containing derivatives.

Several novel N-donor tridentate ligands formed in chemical studies of new fac-Re(CO)3 complexes relevant to fac-99mTc(CO)3 radiopharmaceuticals: attack of a terminal amine on coordinated acetonitrile.

PubMed

Perera, Theshini; Marzilli, Patricia A; Fronczek, Frank R; Marzilli, Luigi G

2010-03-01

To evaluate syntheses of fac-[Re(CO)(3)L](+) complexes in organic solvents, we treated fac-[Re(CO)(3)(CH(3)CN)(3)]PF(6)/BF(4) in acetonitrile with triamine ligands (L). When L had two primary or two tertiary terminal amine groups, the expected fac-[Re(CO)(3)L](+) complexes formed. In contrast, N,N-dimethyldiethylenetriamine (N,N-Me(2)dien) formed an unusual compound, fac-[Re(CO)(3)(DAE)]BF(4) {DAE = (Z)-N'-(2-(2-(dimethylamino)ethylamino)ethyl)acetimidamide = (Me(2)NCH(2)CH(2))NH(CH(2)CH(2)N=C(NH(2))Me)}. DAE is formed by addition of acetonitrile to the N,N-Me(2)dien terminal primary amine, converting this sp(3) nitrogen to an sp(2) nitrogen with a double bond to the original acetonitrile sp carbon. The three Ns bound to Re derive from N,N-Me(2)dien. The pathway to fac-[Re(CO)(3)(DAE)]BF(4) is suggested by a second unusual compound, fac-[Re(CO)(3)(MAE)]PF(6) {MAE = N-methyl-N-(2-(methyl-(2-(methylamino)ethyl)amino)ethyl)acetimidamide = MeN(H)-CH(2)CH(2)-N(Me)-CH(2)CH(2)-N(Me)-C(Me)=NH}, isolated after treating fac-[Re(CO)(3)(CH(3)CN)(3)]PF(6) with N,N',N''-trimethyldiethylenetriamine (N,N',N''-Me(3)dien). MAE chelates via a terminal and a central sp(3) N from N,N',N''-Me(3)dien and via one sp(2) NH in a C(Me)=NH group. This group is derived from acetonitrile by addition of the other N,N',N''-Me(3)dien terminal amine to the nitrile carbon. This addition creates an endocyclic NMe group within a seven-membered chelate ring. The structure and other properties of fac-[Re(CO)(3)(MAE)]PF(6) allow us to propose a reaction scheme for the formation of the unprecedented DAE ligand. The new compounds advance our understanding of the spectral and structural properties of Re analogues of (99m)Tc radiopharmaceuticals.

Photo-assisted cyanation of transition metal nitrates coupled with room temperature C-C bond cleavage of acetonitrile.

PubMed

Zou, Shihui; Li, Renhong; Kobayashi, Hisayoshi; Liu, Juanjuan; Fan, Jie

2013-03-07

It is a challenge to use acetonitrile as a cyanating agent because of the difficulty in cleaving its C-CN bond. Herein, we report a mild photo-assisted route to conduct the cyanation of transition metal nitrates using acetonitrile as the cyanating agent coupled with room-temperature C-C bond cleavage. DFT calculations and experimental observations suggest a radical-involved reaction mechanism, which excludes toxicity from free cyanide ions.

Acetonitrile cluster solvation in a cryogenic ethane-methane-propane liquid: Implications for Titan lake chemistry.

PubMed

Corrales, L René; Yi, Thomas D; Trumbo, Samantha K; Shalloway, David; Lunine, Jonathan I; Usher, David A

2017-03-14

The atmosphere of Titan, Saturn's largest moon, exhibits interesting UV- and radiation-driven chemistry between nitrogen and methane, resulting in dipolar, nitrile-containing molecules. The assembly and subsequent solvation of such molecules in the alkane lakes and seas found on the moon's surface are of particular interest for investigating the possibility of prebiotic chemistry in Titan's hydrophobic seas. Here we characterize the solvation of acetonitrile, a product of Titan's atmospheric radiation chemistry tentatively detected on Titan's surface [H. B. Niemann et al., Nature 438, 779-784 (2005)], in an alkane mixture estimated to match a postulated composition of the smaller lakes during cycles of active drying and rewetting. Molecular dynamics simulations are employed to determine the potential of mean force of acetonitrile (CH 3 CN) clusters moving from the alkane vapor into the bulk liquid. We find that the clusters prefer the alkane liquid to the vapor and do not dissociate in the bulk liquid. This opens up the possibility that acetonitrile-based microscopic polar chemistry may be possible in the otherwise nonpolar Titan lakes.

Quantifying Residues from Postharvest Propylene Oxide Fumigation of Almonds and Walnuts.

PubMed

Jimenez, Leonel R; Hall, Wiley A; Rodriquez, Matthew S; Cooper, William J; Muhareb, Jeanette; Jones, Tom; Walse, Spencer S

2015-01-01

A novel analytical approach involving solvent extraction with methyl tert-butyl ether (MTBE) followed by GC was developed to quantify residues that result from the postharvest fumigation of almonds and walnuts with propylene oxide (PPO). Verification and quantification of PPO, propylene chlorohydrin (PCH) [1-chloropropan-2-ol (PCH-1) and 2-chloropropan-1-ol (PCH-2)], and propylene bromohydrin (PBH) [1-bromopropan-2-ol (PBH-1) and 2-bromopropan-1-ol (PBH-2)] was accomplished with a combination of electron impact ionization MS (EIMS), negative ion chemical ionization MS (NCIMS), and electron capture detection (ECD). Respective GC/EIMS LOQs for PPO, PCH-1, PCH-2, PBH-1, and PBH-2 in MTBE extracts were [ppm (μg/g nut)] 0.9, 2.1, 2.5, 30.3, and 50.0 for almonds and 0.8, 2.2, 2.02, 41.6, and 45.7 for walnuts. Relative to GC/EIMS, GC-ECD analyses resulted in no detection of PPO, similar detector responses for PCH isomers, and >100-fold more sensitive detection of PBH isomers. NCIMS did not enhance detection of PBH isomers relative to EIMS and was, respectively, approximately 20-, 5-, and 10-fold less sensitive to PPO, PCH-1, and PCH-2. MTBE extraction efficiencies were >90% for all analytes. The 10-fold concentration of MTBE extracts yielded recoveries of 85-105% for the PBH isomers and a concomitant decrease in LODs and LOQs across detector types. The recoveries of PCH isomers and PPO in the MTBE concentrate were relatively low (approximately 50 to 75%), which confound improvements in LODs and LOQs regardless of detector type.

Microwave dielectric relaxation spectroscopy study of propylene glycol/ethanol binary mixtures: Temperature dependence

NASA Astrophysics Data System (ADS)

Vishwam, T.; Shihab, Suriya; Murthy, V. R. K.; Tiong, Ha Sie; Sreehari Sastry, S.

2017-05-01

Complex dielectric permittivity measurements of propylene glycol (PG) in ethanol at various mole fractions were measured by using open-ended coaxial probe technique at different temperatures in the frequency range 0.02 < ν/GHz < 20. The dipole moment (μ), excess dipole moment (Δμ),excess permittivity (εE), excess inverse relaxation time(1/τ)E, Bruggeman parameter (fB), excess Helmholtz energy (ΔFE) are determined using experimental data. From the minimum energy based geometry optimization, dipole moments of individual monomers of propylene glycol and ethanol and their binary system have been evaluated theoretically at gaseous state as well as alcoholic medium by using PCM and IEFPCM solvation models from the Hatree-Fock (HF) and Density Functional Theory (DFT-B3LYP) methods with 6-311G* and 6-311G** basis sets. The obtained results have been interpreted in terms of the short and long range ordering of the dipoles, Kirkwood correlation factor (geff), thermodynamic parameters, mean molecular polarizability (αM) and interaction in the mixture through hydrogen bonding. Dielectric relaxation study of propylene glycol in ethanol medium Determination of excess dielectric and thermodynamic parameters Comparison of experimental dipole moment with theoretical calculations Interpretation of the molecular interactions in the liquid through H-bonding Correlation between the evaluated dielectric parameters and theoretical results

Quantifying residues from postharvest fumigation of almonds and walnuts with propylene oxide

USDA-ARS?s Scientific Manuscript database

A novel analytical approach, involving solvent extraction with methyl tert-butyl ether (MTBE) followed by gas chromatography (GC), was developed to quantify residues that result from the postharvest fumigation of almonds and walnuts with propylene oxide (PPO). Verification and quantification of PPO,...

Change in the Gibbs energy of 18-crown-6 ether transfer from methanol to methanol-acetonitrile mixtures at 298 K

NASA Astrophysics Data System (ADS)

Kuz'mina, I. A.; Usacheva, T. R.; Kuz'mina, K. I.; Volkova, M. A.; Sharnin, V. A.

2015-01-01

The Gibbs energies of the transfer of 18-crown-6 ether from methanol to its mixtures with acetonitrile (χAN = 0.0-1.0 mole fraction) are determined by means of interphase distribution at 298 K. The effect the solvent composition has on the thermodynamic characteristics of the solvation of 18-crown-6 ether is analyzed. An increase in the content of acetonitrile in the mixed solvent enhances the solvation of crown ether due to changes in the energy of the solution. Resolvation of the macrocycle is assumed to be complete at acetonitrile concentrations higher than 0.6 mole fraction.

Strategies for the Hyperpolarization of Acetonitrile and Related Ligands by SABRE

PubMed Central

2014-01-01

We report on a strategy for using SABRE (signal amplification by reversible exchange) for polarizing 1H and 13C nuclei of weakly interacting ligands which possess biologically relevant and nonaromatic motifs. We first demonstrate this via the polarization of acetonitrile, using Ir(IMes)(COD)Cl as the catalyst precursor, and confirm that the route to hyperpolarization transfer is via the J-coupling network. We extend this work to the polarization of propionitrile, benzylnitrile, benzonitrile, and trans-3-hexenedinitrile in order to assess its generality. In the 1H NMR spectrum, the signal for acetonitrile is enhanced 8-fold over its thermal counterpart when [Ir(H)2(IMes)(MeCN)3]+ is the catalyst. Upon addition of pyridine or pyridine-d5, the active catalyst changes to [Ir(H)2(IMes)(py)2(MeCN)]+ and the resulting acetonitrile 1H signal enhancement increases to 20- and 60-fold, respectively. In 13C NMR studies, polarization transfers optimally to the quaternary 13C nucleus of MeCN while the methyl 13C is hardly polarized. Transfer to 13C is shown to occur first via the 1H–1H coupling between the hydrides and the methyl protons and then via either the 2J or 1J couplings to the respective 13Cs, of which the 2J route is more efficient. These experimental results are rationalized through a theoretical treatment which shows excellent agreement with experiment. In the case of MeCN, longitudinal two-spin orders between pairs of 1H nuclei in the three-spin methyl group are created. Two-spin order states, between the 1H and 13C nuclei, are also created, and their existence is confirmed for Me13CN in both the 1H and 13C NMR spectra using the Only Parahydrogen Spectroscopy protocol. PMID:25539423

Strategies for the hyperpolarization of acetonitrile and related ligands by SABRE.

PubMed

Mewis, Ryan E; Green, Richard A; Cockett, Martin C R; Cowley, Michael J; Duckett, Simon B; Green, Gary G R; John, Richard O; Rayner, Peter J; Williamson, David C

2015-01-29

We report on a strategy for using SABRE (signal amplification by reversible exchange) for polarizing (1)H and (13)C nuclei of weakly interacting ligands which possess biologically relevant and nonaromatic motifs. We first demonstrate this via the polarization of acetonitrile, using Ir(IMes)(COD)Cl as the catalyst precursor, and confirm that the route to hyperpolarization transfer is via the J-coupling network. We extend this work to the polarization of propionitrile, benzylnitrile, benzonitrile, and trans-3-hexenedinitrile in order to assess its generality. In the (1)H NMR spectrum, the signal for acetonitrile is enhanced 8-fold over its thermal counterpart when [Ir(H)2(IMes)(MeCN)3](+) is the catalyst. Upon addition of pyridine or pyridine-d5, the active catalyst changes to [Ir(H)2(IMes)(py)2(MeCN)](+) and the resulting acetonitrile (1)H signal enhancement increases to 20- and 60-fold, respectively. In (13)C NMR studies, polarization transfers optimally to the quaternary (13)C nucleus of MeCN while the methyl (13)C is hardly polarized. Transfer to (13)C is shown to occur first via the (1)H-(1)H coupling between the hydrides and the methyl protons and then via either the (2)J or (1)J couplings to the respective (13)Cs, of which the (2)J route is more efficient. These experimental results are rationalized through a theoretical treatment which shows excellent agreement with experiment. In the case of MeCN, longitudinal two-spin orders between pairs of (1)H nuclei in the three-spin methyl group are created. Two-spin order states, between the (1)H and (13)C nuclei, are also created, and their existence is confirmed for Me(13)CN in both the (1)H and (13)C NMR spectra using the Only Parahydrogen Spectroscopy protocol.

Effect of biogenic fermentation impurities on lactic acid hydrogenation to propylene glycol.

PubMed

Zhang, Zhigang; Jackson, James E; Miller, Dennis J

2008-09-01

The effect of residual impurities from glucose fermentation to lactic acid (LA) on subsequent ruthenium-catalyzed hydrogenation of LA to propylene glycol (PG) is examined. Whereas refined LA feed exhibits stable conversion to PG over carbon-supported ruthenium catalyst in a trickle bed reactor, partially refined LA from fermentation shows a steep decline in PG production over short (<40 h) reaction times followed by a further slow decay in performance. Addition of model impurities to refined LA has varying effects: organic acids, sugars, or inorganic salts have little effect on conversion; alanine, a model amino acid, results in a strong but reversible decline in conversion via competitive adsorption between alanine and LA on the Ru surface. The sulfur-containing amino acids cysteine and methionine irreversibly poison the catalyst for LA conversion. Addition of 0.1 wt% albumin as a model protein leads to slow decline in rate, consistent with pore plugging or combined pore plugging and poisoning of the Ru surface. This study points to the need for integrated design and operation of biological processes and chemical processes in the biorefinery in order to make efficient conversion schemes viable.

Low-Temperature Fluorination of Soft-Templated Mesoporous Carbons for a High-Power Lithium/Carbon Fluoride Battery

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

Fulvio, Pasquale F.; Brown, Suree S.; Adcock, Jamie

Soft-templated mesoporous carbons and activated mesoporous carbons were fluorinated using elemental fluorine between room temperature and 235 °C. The mesoporous carbons were prepared via self-assembly synthesis of phloroglucinol–formaldehyde as a carbon precursor in the presence of triblock ethylene oxide–propylene oxide–ethylene oxide copolymer BASF Pluronic F127 as the template. The F/C ratios ranged from ~0.15 to 0.75 according to gravimetric, energy dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy analysis. Materials have mesopore diameters up to 11 nm and specific surface areas as high as 850 m² g⁻¹ after fluorination as calculated from nitrogen adsorption isotherms at -196 °C. Furthermore, the materialsmore » exhibit higher discharge potentials and energy and power densities as well as faster reaction kinetics under high current densities than commercial carbon fluorides with similar fluorine contents when tested as cathodes for Li/CF x batteries.« less

Low-Temperature Fluorination of Soft-Templated Mesoporous Carbons for a High-Power Lithium/Carbon Fluoride Battery

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

Fulvio, Pasquale F; Dai, Sheng; Guo, Bingkun

Soft-templated mesoporous carbons and activated mesoporous carbons were fluorinated using elemental fluorine between room temperature and 235 C. The mesoporous carbons were prepared via self-assembly synthesis of phloroglucinol formaldehyde as a carbon precursor in the presence of triblock ethylene oxide propylene oxide ethylene oxide copolymer BASF Pluronic F127 as the template. The F/C ratios ranged from 0.15 to 0.75 according to gravimetric, energy dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy analysis. Materials have mesopore diameters up to 11 nm and specific surface areas as high as 850 m2 g 1 after fluorination as calculated from nitrogen adsorption isotherms at 196more » C. Furthermore, the materials exhibit higher discharge potentials and energy and power densities as well as faster reaction kinetics under high current densities than commercial carbon fluorides with similar fluorine contents when tested as cathodes for Li/CFx batteries.« less

Comparison of single-ion molecular dynamics in common solvents

NASA Astrophysics Data System (ADS)

Muralidharan, A.; Pratt, L. R.; Chaudhari, M. I.; Rempe, S. B.

2018-06-01

Laying a basis for molecularly specific theory for the mobilities of ions in solutions of practical interest, we report a broad survey of velocity autocorrelation functions (VACFs) of Li+ and PF6- ions in water, ethylene carbonate, propylene carbonate, and acetonitrile solutions. We extract the memory function, γ(t), which characterizes the random forces governing the mobilities of ions. We provide comparisons controlling for the effects of electrolyte concentration and ion-pairing, van der Waals attractive interactions, and solvent molecular characteristics. For the heavier ion (PF6-), velocity relaxations are all similar: negative tail relaxations for the VACF and a clear second relaxation for γ (t ), observed previously also for other molecular ions and with n-pentanol as the solvent. For the light Li+ ion, short time-scale oscillatory behavior masks simple, longer time-scale relaxation of γ (t ). But the corresponding analysis of the solventberg Li+(H2O)4 does conform to the standard picture set by all the PF6- results.

Determination of hydride affinities of various aldehydes and ketones in acetonitrile.

PubMed

Zhu, Xiao-Qing; Chen, Xi; Mei, Lian-Rui

2011-05-06

The hydride affinities of 21 typical aldehydes and ketones in acetonitrile were determined by using an experimental method, which is valuable for chemists choosing suitable reducing agents to reduce them. The focus of this paper is to introduce a very facile experimental method, which can be used to determine the hydride affinities of various carbonyl compounds in solution.

Thermometric titrations of amines with nitrosyl perchlorate in acetonitrile solvent.

PubMed

Gündüz, T; Kiliç, E; Cakirer, O

1996-05-01

Thirteen aliphatic and four aromatic amines, namely diethylamine, triethylamine, n-propylamine, di-n-propylamine, tri-n-butylamine, isopropylamine, di-isopropylamine, n-butylamine, di-n-butylamine, tri-n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, aniline, N,N-dimethylaniline, 2-nitroaniline and 4-nitroaniline were titrated thermometrically with nitrosyl perchlorate in acetonitrile solvent. All the aliphatic amines gave very well-shaped thermometric titration curves. The calculated recovery values of the amines were very good. In comparison, the aromatic amines, aniline and N,N-dimethylaniline gave rather well-shaped titration curves, but the recovery values were fairly low. 2-Nitro- and 4-nitro anilines gave no thermometric response at all. The heats of reaction of the amines with nitrosyl perchlorate are rather high. However, the average heat of reaction of the aromatic amines is approximately two-thirds that of the average heat of the aliphatic amines. To support this method all the amines were also titrated potentiometrically and very similar results to those obtained with the thermometric method are seen. The nitrosyl ion is a Lewis acid, strong enough to titrate quantitatively aliphatic amines in acetonitrile solvent, but not strong enough to titrate aromatic amines at the required level in the same solvent.

Contribution of mesopores in MgO-templated mesoporous carbons to capacitance in non-aqueous electrolytes

NASA Astrophysics Data System (ADS)

Kado, Yuya; Soneda, Yasushi; Yoshizawa, Noriko

2015-02-01

MgO-templated mesoporous carbons were fabricated by annealing trimagnesium dicitrate nonahydrate at various temperatures from 700 to 1000 °C with subsequent acid leaching of MgO. The obtained carbons contained a large amount of mesopores. Performances of electric double-layer capacitors using these carbons were examined for propylene carbonate electrolyte containing 1 M tetraethylammonium tetrafluoroborate. The mesoporous carbons synthesized at higher temperatures showed better rate capabilities. AC impedance measurements indicated that high-temperature annealing of the carbon precursors and the presence of mesopores were important for high rate performance. In addition, the contribution of mesopores to capacitance was more significant at higher current densities of 30 A g-1.

Long Duration Life Test of Propylene Glycol Water Based Thermal Fluid Within Thermal Control Loop

NASA Technical Reports Server (NTRS)

Le, Hung; Hill, Charles; Stephan, Ryan A.

2010-01-01

Evaluations of thermal properties and resistance to microbial growth concluded that 50% Propylene Glycol (PG)-based fluid and 50% de-ionized water mixture was desirable for use as a fluid within a vehicle s thermal control loop. However, previous testing with a commercial mixture of PG and water containing phosphate corrosion inhibitors resulted in corrosion of aluminum within the test system and instability of the test fluid. This paper describes a follow-on long duration testing and analysis of 50% Propylene Glycol (PG)-based fluid and 50% de-ionized water mixture with inorganic corrosion inhibitors used in place of phosphates. The test evaluates the long-term fluid stability and resistance to microbial and chemical changes

Bis(tetraphenylarsonium) hexachloridozirconate(IV) acetonitrile tetrasolvate

DOE PAGES

Borjas, Rosendo; Mariappan Balasekaran, Samundeeswari; Poineau, Frederic

2018-04-06

The bis(tetraphenylarsonium) hexachloridozirconate(IV) salt, (AsPh 4 ) 2 [ZrCl 6 ] (Ph = C 6 H 5 ), was prepared more than 25 years ago [Esmadi & Sutcliffe (1991). Indian J. Chem. 30 A , 99–101], but its crystal structure was never reported. By following a similar experimental procedure, the compound was synthesized and its crystal structure was investigated as a acetonitrile tetrasolvate, (As(C 6 H 5 ) 4 ) 2 [ZrCl 6 ]·4CH 3 CN, by single-crystal X –ray diffraction. The [ZrCl 6 ] 2− anion adopts a slightly distorted octahedral coordination sphere, with Zr—Cl bond lengths of 2.4586 (6), 2.4723 (6),more » and 2.4818 (5) Å, and Cl—Zr—Cl angles ranging from 89.602 (19) to 90.397 (19)°.« less

Bis(tetraphenylarsonium) hexachloridozirconate(IV) acetonitrile tetrasolvate

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

Borjas, Rosendo; Mariappan Balasekaran, Samundeeswari; Poineau, Frederic

The bis(tetraphenylarsonium) hexachloridozirconate(IV) salt, (AsPh 4 ) 2 [ZrCl 6 ] (Ph = C 6 H 5 ), was prepared more than 25 years ago [Esmadi & Sutcliffe (1991). Indian J. Chem. 30 A , 99–101], but its crystal structure was never reported. By following a similar experimental procedure, the compound was synthesized and its crystal structure was investigated as a acetonitrile tetrasolvate, (As(C 6 H 5 ) 4 ) 2 [ZrCl 6 ]·4CH 3 CN, by single-crystal X –ray diffraction. The [ZrCl 6 ] 2− anion adopts a slightly distorted octahedral coordination sphere, with Zr—Cl bond lengths of 2.4586 (6), 2.4723 (6),more » and 2.4818 (5) Å, and Cl—Zr—Cl angles ranging from 89.602 (19) to 90.397 (19)°.« less

Complexes of Small Chiral Molecules: Propylene Oxide and 3-BUTYN-2OL

NASA Astrophysics Data System (ADS)

Evangelisti, Luca; West, Channing; Coles, Ellie; Pate, Brooks

2017-06-01

Complexes of propylene oxide with 3-butyn-2-ol were observed in the molecular rotational spectra, and isotopologue analysis allowed for structural determination of the complexes. Using a gas mixture of 0.1% propylene oxide and 0.1% 3-butyn-2-ol in neon, the broadband rotational spectrum was measured in the 2-8 GHz frequency range using a chirped-pulse Fourier transform microwave spectrometer. Four isomers of each diastereomer pair, formed by a hydrogen bond between the two monomers, are identified in quantum chemistry study of the complex using B3LYP-D3BJ with the def2TZVP basis set. The initial measurement used racemic samples of both molecules in order to obtain all possible isomers of the complex in the pulsed jet expansion. A total of six distinct spectra were assigned in the racemic measurement - three for both the homochiral and heterochiral complex. Substitution structures for the most intense homochiral and heterochiral complexes were obtained. These complexes use the two lowest energy conformations of butynol despite conformational cooling of the monomer, resulting in a single identified isomer. This result shows that a wide range monomer conformational geometries need to be examined when performing searches for the lowest energy geometry. Analysis of the diastereomer spectra was used to develop a method for determining the enantiomeric excess of 3-butyn-2-ol and propylene oxide for use as a chiral tag, which could be used in subsequent measurements to determine enantiomeric excess. The sensitivity limits for enantiomeric excess determination and the linearity of the rotational spectroscopy signals as a function of sample enantiomeric excess will be presented.

A novel liquid/liquid extraction process composed of surfactant and acetonitrile for purification of polygalacturonase enzyme from Durio zibethinus.

PubMed

Amid, Mehrnoush; Manap, Yazid; Azmira, Farhana; Hussin, Muhaini; Sarker, Zaidul Islam

2015-07-01

Polygalacturonase is one of the important enzymes used in various industries such as food, detergent, pharmaceutical, textile, pulp and paper. A novel liquid/liquid extraction process composed of surfactant and acetonitrile was employed for the first time to purify polygalacturonase from Durio zibethinus. The influences of different parameters such as type and concentration of surfactants, concentrations of acetonitrile and composition of surfactant/acetonitrile on partitioning behavior and recovery of polygalacturonase was investigated. Moreover, the effect of pH of system and crude load on purification fold and yield of purified polygalacturonase were studied. The results of the experiment indicated the polygalacturonase was partitioned into surfactant top rich phase with impurities being partitioned into acetonitrile bottom rich phase in the novel method of liquid/liquid process composed of 23% (w/w) Triton X-100 and 19% (w/w) acetonitrile, at 55.6% of TLL (tie line length) crude load of 25% (w/w) at pH 6.0. Recovery and recycling of components also was measured in each successive step of liquid/liquid extraction process. The enzyme was successfully recovered by the method with a high purification factor of 14.3 and yield of 97.3% while phase components were also recovered and recycled above 95%. This study demonstrated that the novel method of liquid/liquid extraction process can be used as an efficient and economical extraction method rather than the traditional methods of extraction for the purification and recovery of the valuable enzyme. Copyright © 2015 Elsevier B.V. All rights reserved.

INORGANIC ELECTROLYTES IN ANHYDROUS ACETONITRILE. Technical Report No. 5

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

Janz, G.J.; Marcinkowsky, A.E.

Research concerned with the properties of inorganic electrolytes in anhydrous acetonitrile is reported. Infor mation related to ionic interactions, solute-solvent interactions and solute-solute interactions is emphasized. The work is differentiated into phases including that pertaining to the region of dilute concentration in which Kl was studied, the region of high concentration in which. AgNO/sub 3/ was studied, and systems which exhibit pronounced complexion behavior for which the cobaltous halide salts were investigated. Discussions of procedures, and result interpretation are included with data. (J.R.D.)

Tris(acetonitrile)chloropalladium tetrafluoroborate synthesis, application and structural analysis

NASA Astrophysics Data System (ADS)

Dybała, Izabela; Demchuk, Oleg M.

2016-10-01

Results of the single crystal X-ray diffraction analysis of tris(acetonitrile)chloropalladium tetrafluoroborate [PdCl(CH3CN)3]BF4 are presented in details. It was found that the title compound crystallises in the monoclinic system, in the space group C2/c. The role of charge-assisted C-HṡṡṡF-B interactions in crystal architecture was investigated. Due to its untypical properties the prepared [PdCl(CH3CN)3]BF4 has proved to be an excellent palladium source in the synthesis of phosphine-palladium complexes.

Physicochemical properties of valsartan and the effect of ethyl alcohol, propylene glycol and pH on its solubility.

PubMed

Mbah, C J

2005-11-01

The aqueous solubility and partition coefficient of valsartan were determined at room temperature. The effect of ethyl alcohol, propylene glycol and pH on its solubility was also investigated. It was found that both solvents increased the solubility of the drug in water. The solubilizing power of ethyl alcohol was found to be higher than that of propylene glycol. Valsartan solubility was also observed to increase at high pH values and its lipophilicity wasdemonstrated by the high positive value of the logarithm of partition coefficient.

Biodegradability relationships among propylene glycol substances in the Organization for Economic Cooperation and Development ready- and seawater biodegradability tests.

PubMed

West, Robert J; Davis, John W; Pottenger, Lynn H; Banton, Marcy I; Graham, Cynthia

2007-05-01

Eight propylene glycol substances, ranging from 1,2-propanediol to a poly(propylene glycol) (PPG) having number-average molecular weight (M(n)) of 2,700 (i.e., PPG 2700), were evaluated in the Organization for Economic Cooperation and Development (OECD) ready- and seawater biodegradability tests. Uniformity in test parameters, such as inoculum source/density and test substance concentrations, combined with frequent measurements of O2 consumption and CO2 evolution, revealed unexpected biodegradability trends across this family of substances. Biodegradability in both tests decreased with increased number of oxy-propylene repeating units (n = 1, 2, 3, 4) of the oligomeric propylene glycols (PGs). However, this trend was reversed for the PPG polymers, and increased biodegradability was observed with increases of average n to seven, 17, and 34 (M(n) = 425, 1,000, and 2,000, respectively). This relationship between molecular weight and biodegradability was reversed again when average n was incremented from 34 (PPG 2000) to 46 (PPG 2700). Six of the tested substances (n = 1, 2, 3, 7, 17, and 34) met the OECD-specified criteria for "ready biodegradability," whereas the tetrapropylene glycol (n = 4) and PPG 2700 substances failed to meet these criteria. Biodegradation half-lives for these eight substances ranged from 3.8 d (PPG 2000) to 33.2 d (PPG 2700) in the ready test, and from 13.6 (PG) to 410 d (PPG 2700) in seawater. Biodegradation half-lives in seawater were significantly correlated with half-lives determined in the ready test. However, half-lives in both tests were correlated poorly with molecular weight, water solubility, and log K(ow). It is speculated that the molecular conformation of these substances, perhaps more so than these other physicochemical properties, has an important role in influencing biodegradability of the propylene glycol substances.

Effects of propylene glycol drenching before and after luteolysis on blood glucose, ovarian steroids and follicular dynamics in heifers.

PubMed

Umeki, A; Tanaka, T; Kamomae, H

2012-02-01

The effect of propylene glycol drenching on ovarian and hormonal dynamics was studied in heifers. Five cycling heifers were used twice (as control and treatment) with crossover design. After the confirmation of ovulation (day 0), the heifers in the treatment group received propylene glycol on days 6, 7 and 8 as an oral drench (250 ml of 90% propylene glycol). On day 10, prostaglandin F2α (PGF2α), 15 mg per head of dinoprost, was administered intramuscularly to induce luteal regression followed by the follicular phase and then propylene glycol was again administered twice daily (500 ml/day) on days 10, 11 and 12. Palpation per rectum and ovarian ultrasonography were performed every other day from days 0 to 10, and daily after PGF2α administration until the subsequent ovulation (second ovulation) for analysis of follicular and luteal dynamics. Blood samples were also collected every other day from days 0 to 10, and then at 6 h intervals after PGF2α administration until the second ovulation. For the samples taken at 6-h intervals after PGF2α administration, the concentrations of glucose showed clear daily fluctuations in both groups. Changes in the plasma concentration of glucose in the treatment group were significantly (P < 0.05) higher than those of the control groups during the period between 0 and 72 h after PGF2α administration. No significant difference was detected in the growth of dominant follicles, maximum diameter of the ovulatory follicles and the changes in oestradiol and progesterone during the follicular phase between treatment and control groups. This study showed the clear daily fluctuations and stimulatory changes in the blood glucose concentrations at 24-h intervals during the short-term treatment of propylene glycol drenching in heifers. However, no significant changes in ovarian and hormonal dynamics were found under such metabolic conditions.

Evaluation of the effect of green tea extract on mouth bacterial activity in the presence of propylene glycol.

PubMed

Moghbel, Abdolhossein; Farjzadeh, Ahmad; Aghel, Nasrin; Agheli, Homaun; Raisi, Nafiseh

2012-01-01

Compounds present in green tea have proved to inhibit the growth and activity of bacteria associated with infections. To assess the effects of green tea leaves extract in presence of propylene glycol on the aerobic mouth bacteria load. Saliva of 25 volunteer girl students aging 20-25 years were selected and evaluated by a mouthwash sample containing 1% tannin, as the most effective antibacterial complex in green tea. Comparative studies were also conducted between green tea mouthwashes containing 1% tannin and a similar sample with 10% propylene glycol added during extraction. This comparison was applied for a chlorhexidine 0.2% sample as a chemical mouthwash brand, too. There was a meaningful difference between the green tea mouthwashes containing 10% propylene glycol and the simple green tea extract (P < 0.05). Significant difference was also seen between the herbal and chemical mouthwashes (P < 0.05). The extract 1% tannin containing 10% propylene glycol reduced the aerobic mouth bacterial load of the student salvia about 64 percent. The pH monotonousness in different days and temperatures approved the stability of tannin in liquid water medium. Using green tea extract as a herbal mouthwash is safe and harmless specially for children and pregnant women. This result led us to suppose that green tea may prevent plaque formation on teeth, coming over halitosis due to mouth infection, too. These effects need to be approved in an in vivo trial as a second study.

Photoinduced electron transfer and solvation in iodide-doped acetonitrile clusters.

PubMed

Ehrler, Oli T; Griffin, Graham B; Young, Ryan M; Neumark, Daniel M

2009-04-02

We have used ultrafast time-resolved photoelectron imaging to measure charge transfer dynamics in iodide-doped acetonitrile clusters I(-)(CH(3)CN)(n) with n = 5-10. Strong modulations of vertical detachment energies were observed following charge transfer from the halide, allowing interpretation of the ongoing dynamics. We observe a sharp drop in the vertical detachment energy (VDE) within 300-400 fs, followed by a biexponential increase that is complete by approximately 10 ps. Comparison to theory suggests that the iodide is internally solvated and that photodetachment results in formation of a diffuse electron cloud in a confined cavity. We interpret the initial drop in VDE as a combination of expansion of the cavity and localization of the excess electron on one or two solvent molecules. The subsequent increase in VDE is attributed to a combination of the I atom leaving the cavity and rearrangement of the acetonitrile molecules to solvate the electron. The n = 5-8 clusters then show a drop in VDE of around 50 meV on a much longer time scale. The long-time VDEs are consistent with those of (CH(3)CN)(n)(-) clusters with internally solvated electrons. Although the excited-state created by the pump pulse decays by emission of a slow electron, no such decay is seen by 200 ps.

Synthesis and Small-Angle X-Ray Scattering Investigations of Ureido-Pyrimidone Hydrogen Bonding Star and Linear Poly(ethylene-co-propylene)s

DTIC Science & Technology

2006-02-01

Synthesis and Small-Angle X-ray Scattering Investigations of Ureido- Pyrimidone Hydrogen Bonding Star and Linear Poly(ethylene-co-propylene)s...Scattering Investigations of Ureido- Pyrimidone Hydrogen Bonding Star and Linear Poly(ethylene-co-propylene)s Frederick L. Beyer Weapons and...control number. PLEASE DO NOT RETURN YOUR FORM TO THE ABOVE ADDRESS. 1. REPORT DATE (DD-MM-YYYY) February 2006 2 . REPORT TYPE Interim 3. DATES

Automatized sspKa measurements of dihydrogen phosphate and Tris(hydroxymethyl) aminomethane in acetonitrile/water mixtures from 20 to 60°C.

PubMed

Acquaviva, A; Tascon, M; Padró, J M; Gagliardi, L G; Castells, C B

2014-09-01

We measured pKa values of Tris(hydroxymethyl)aminomethane and dihydrogen phosphate; both are commonly used to prepare buffers for reverse-phase liquid chromatography (RPLC), in acetonitrile/water mixtures from 0% to 70% (v/v) (64.6% (w/w)) acetonitrile and at 20, 30, 40, 50, and 60°C. The procedure is based on potentiometric measurements of pH of buffer solutions of variable solvent compositions using a glass electrode and a novel automated system. The method consists in the controlled additions of small volumes of a thermostated solution from an automatic buret into another isothermal solution containing exactly the same buffer-component concentrations, but a different solvent composition. The continuous changes in the solvent composition induce changes in the potentials. Thus, only two sequences of additions are needed: increasing the amount of acetonitrile from pure water and decreasing the content of acetonitrile from 70% (v/v) (64.6% (w/w)). In the procedure with homemade apparatus, times for additions, stirring, homogenization, and data acquisition are entirely controlled by software programmed for this specific routine. This rapid, fully automated method was applied to acquire more than 40 potential data covering the whole composition range (at each temperature) in about two hours and allowed a systematic study of the effect of temperature and acetonitrile composition on acid-base equilibria of two widely used substances to control pH close to 7. The experimental pKa results were fitted to empirical functions between pKa and temperature and acetonitrile composition. These equations allowed predictions of pKa to estimate the pH of mixtures at any composition and temperature, which would be very useful, for instance, during chromatographic method development. Copyright © 2014 Elsevier B.V. All rights reserved.

Solid-State Characterization of Novel Propylene Glycol Ester Solvates Isolated from Lipid Formulations.

PubMed

Chakravarty, Paroma; Kothari, Sanjeev; Deese, Alan; Lubach, Joseph W

2015-07-06

The purpose of this study was to identify and characterize precipitates obtained from a liquid formulation of GNE068.HCl, a Genentech developmental compound, and lipophilic excipients, such as propylene glycol monocaprylate, and monolaurate. Precipitates were characterized using powder X-ray diffractometry (PXRD), differential scanning calorimetry, thermogravimetry, microscopy, nuclear magnetic resonance spectroscopy (NMR; solution and solid-state) and water sorption analysis. PXRD and NMR revealed the precipitates to be crystalline solvates of propylene glycol esters. The solvates (capryolate and lauroglycolate) were isomorphic and stable up to 70 °C, beyond which melting of the lattice occurred with subsequent dissolution of the active ingredient in the melt (microscopy and variable temperature PXRD). They were found to be mechanically stable (no change in PXRD pattern upon compression) and were nonhygroscopic up to ∼70% RH (25 °C). Our results highlight the outcome of inadvertent drug-excipient interactions in two separate lipid solution formulations with good solid-state properties and, thus, potential for further development.

Red/blue shifting hydrogen bonds in acetonitrile-dimethyl sulphoxide solutions: FTIR and theoretical studies

NASA Astrophysics Data System (ADS)

Kannan, P. P.; Karthick, N. K.; Mahendraprabu, A.; Shanmugam, R.; Elangovan, A.; Arivazhagan, G.

2017-07-01

FTIR spectra of neat acetonitrile (AN), dimethyl sulphoxide (DMSO) and their binary solutions at various mole fractions have been recorded at room temperature. Theoretical calculations have also been carried out on acetonitrile (monomer, dimer), dimethyl sulphoxide (monomer, dimer) and AN - DMSO complex molecules. 1:2 (AN:DMSO) and 2:1 complexation through the red shifting (AN) C - H ⋯ O = S(DMSO) and blue shifting (DMSO) C - H ⋯ N ≡ C(AN) hydrogen bonds has been identified. The experimental and theoretical studies favour the presence of both the monomer and dimer in liquid AN, but only closed dimers in DMSO. The dipole-dipole interactions existed in AN and DMSO dimers disappear in the complex molecules. Partial π bond between S and O atoms, and three lone pair of electrons on oxygen atom of DMSO have been noticed theoretically.

Natural and enhanced biodegradation of propylene glycol in airport soil.

PubMed

Toscano, Giuseppe; Colarieti, M Letizia; Anton, Attila; Greco, Guido; Biró, Borbála

2014-01-01

Aircraft de-icing fluids (ADF) are a source of water and soil pollution in airport sites. Propylene glycol (PG) is a main component in several commercial formulations of ADFs. Even though PG is biodegradable in soil, seasonal overloads may result in occasional groundwater contamination. Feasibility studies for the biostimulation of PG degradation in soil have been carried out in soil slurries, soil microcosms and enrichment cultures with and without the addition of nutrients (N and P sources, oligoelements), alternative electron acceptors (nitrate, oxygen releasing compounds) and adsorbents (activated carbon). Soil samples have been taken from the contaminated area of Gardermoen Airport Oslo. Under aerobic conditions and in the absence of added nutrients, no or scarce biomass growth is observed and PG degradation occurs by maintenance metabolism at constant removal rate by the original population of PG degraders. With the addition of nutrient, biomass exponential growth enhances aerobic PG degradation also at low temperatures (4 ° C) that occur at the high season of snowmelt. Anaerobic PG degradation without added nutrients still proceeds at constant rate (i.e. no biomass growth) and gives rise to reduced fermentation product (propionic acid, reduced Fe and Mn, methane). The addition of nitrate does not promote biomass growth but allows full PG mineralization without reduced by-products. Further exploitation on the field is necessary to fully evaluate the effect of oxygen releasing compounds and adsorbents.

Differential substrate behaviours of ethylene oxide and propylene oxide towards human glutathione transferase theta hGSTT1-1.

PubMed

Thier, R; Wiebel, F A; Bolt, H M

1999-11-01

The transformation of ethylene oxide (EO), propylene oxide (PO) and 1-butylene oxide (1-BuO) by human glutathione transferase theta (hGSTT1-1) was studied comparatively using 'conjugator' (GSTT1 + individuals) erythrocyte lysates. The relative sequence of velocity of enzymic transformation was PO > EO > 1-BuO. The faster transformation of PO compared to EO was corroborated in studies with human and rat GSTT1-1 (hGSTT1-1 and rGSTT1-1, respectively) expressed by Salmonella typhimurium TA1535. This sequence of reactivities of homologous epoxides towards GSTT1-1 contrasts to the sequence observed in homologous alkyl halides (methyl bromide, MBr; ethyl bromide, EtBr; n-propyl bromide, PrBr) where the relative sequence MeBr > EtBr > PrBr is observed. The higher reactivity towards GSTT1-1 of propylene oxide compared to ethylene oxide is consistent with a higher chemical reactivity. This is corroborated by experimental data of acid-catalysed hydrolysis of a number of aliphatic epoxides, including ethylene oxide and propylene oxide and consistent with semi-empirical molecular orbital modelings.

Artificial sunlight and ultraviolet light induced photo-epoxidation of propylene over V-Ti/MCM-41 photocatalyst

PubMed Central

Nguyen, Van-Huy; Bai, Hsunling

2014-01-01

Summary The light irradiation parameters, including the wavelength spectrum and intensity of light source, can significantly influence a photocatalytic reaction. This study examines the propylene photo-epoxidation over V-Ti/MCM-41 photocatalyst by using artificial sunlight (Xe lamp with/without an Air Mass 1.5 Global Filter at 1.6/18.5 mW·cm−2) and ultraviolet light (Mercury Arc lamp with different filters in the range of 0.1–0.8 mW·cm−2). This is the first report of using artificial sunlight to drive the photo-epoxidation of propylene. Over V-Ti/MCM-41 photocatalyst, the propylene oxide (PO) formation rate is 193.0 and 112.1 µmol·gcat −1·h−1 with a PO selectivity of 35.0 and 53.7% under UV light and artificial sunlight, respectively. A normalized light utilization (NLU) index is defined and found to correlate well with the rate of both PO formation and C3H6 consumption in log–log scale. The light utilization with a mercury arc lamp is better than with a xenon lamp. The selectivity to PO remains practically unchanged with respect to NLU, suggesting that the photo-epoxidation occurs through the same mechanism under the conditions tested in this study. PMID:24991493

Theoretical analysis of co-solvent effect on the proton transfer reaction of glycine in a water-acetonitrile mixture

NASA Astrophysics Data System (ADS)

Kasai, Yukako; Yoshida, Norio; Nakano, Haruyuki

2015-05-01

The co-solvent effect on the proton transfer reaction of glycine in a water-acetonitrile mixture was examined using the reference interaction-site model self-consistent field theory. The free energy profiles of the proton transfer reaction of glycine between the carboxyl oxygen and amino nitrogen were computed in a water-acetonitrile mixture solvent at various molar fractions. Two types of reactions, the intramolecular proton transfer and water-mediated proton transfer, were considered. In both types of the reactions, a similar tendency was observed. In the pure water solvent, the zwitterionic form, where the carboxyl oxygen is deprotonated while the amino nitrogen is protonated, is more stable than the neutral form. The reaction free energy is -10.6 kcal mol-1. On the other hand, in the pure acetonitrile solvent, glycine takes only the neutral form. The reaction free energy from the neutral to zwitterionic form gradually increases with increasing acetonitrile concentration, and in an equally mixed solvent, the zwitterionic and neutral forms are almost isoenergetic, with a difference of only 0.3 kcal mol-1. The free energy component analysis based on the thermodynamic cycle of the reaction also revealed that the free energy change of the neutral form is insensitive to the change of solvent environment but the zwitterionic form shows drastic changes. In particular, the excess chemical potential, one of the components of the solvation free energy, is dominant and contributes to the stabilization of the zwitterionic form.

Polymerization of Acetonitrile via a Hydrogen Transfer Reaction from CH3 to CN under Extreme Conditions.

PubMed

Zheng, Haiyan; Li, Kuo; Cody, George D; Tulk, Christopher A; Dong, Xiao; Gao, Guoying; Molaison, Jamie J; Liu, Zhenxian; Feygenson, Mikhail; Yang, Wenge; Ivanov, Ilia N; Basile, Leonardo; Idrobo, Juan-Carlos; Guthrie, Malcolm; Mao, Ho-Kwang

2016-09-19

Acetonitrile (CH3 CN) is the simplest and one of the most stable nitriles. Reactions usually occur on the C≡N triple bond, while the C-H bond is very inert and can only be activated by a very strong base or a metal catalyst. It is demonstrated that C-H bonds can be activated by the cyano group under high pressure, but at room temperature. The hydrogen atom transfers from the CH3 to CN along the CH⋅⋅⋅N hydrogen bond, which produces an amino group and initiates polymerization to form a dimer, 1D chain, and 2D nanoribbon with mixed sp(2) and sp(3) bonded carbon. Finally, it transforms into a graphitic polymer by eliminating ammonia. This study shows that applying pressure can induce a distinctive reaction which is guided by the structure of the molecular crystal. It highlights the fact that very inert C-H can be activated by high pressure, even at room temperature and without a catalyst. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Polymerization of Acetonitrile via a Hydrogen Transfer Reaction from CH 3 to CN under Extreme Conditions

DOE PAGES

Zheng, Haiyan; Li, Kuo; Cody, George D.; ...

2016-08-25

Acetonitrile (CH 3CN) is the simplest and one of the most stable nitriles. Reactions usually occur on the C≡N triple bond, while the C-H bond is very inert and can only be activated by a very strong base or a metal catalyst. In this study, it is demonstrated that C-H bonds can be activated by the cyano group under high pressure, but at room temperature. The hydrogen atom transfers from the CH 3 to CN along the CH···N hydrogen bond, which produces an amino group and initiates polymerization to form a dimer, 1D chain, and 2D nanoribbon with mixed spmore » 2 and sp 3 bonded carbon. Lastly, it transforms into a graphitic polymer by eliminating ammonia. This study shows that applying pressure can induce a distinctive reaction which is guided by the structure of the molecular crystal. It highlights the fact that very inert C-H can be activated by high pressure, even at room temperature and without a catalyst.« less

Evaluation of the Effect of Green Tea Extract on Mouth Bacterial Activity in the Presence of Propylene Glycol

PubMed Central

Moghbel, Abdolhossein; Farjzadeh, Ahmad; Aghel, Nasrin; Agheli, Homaun; Raisi, Nafiseh

2012-01-01

Background Compounds present in green tea have proved to inhibit the growth and activity of bacteria associated with infections. Objectives To assess the effects of green tea leaves extract in presence of propylene glycol on the aerobic mouth bacteria load. Materials and Methods Saliva of 25 volunteer girl students aging 20-25 years were selected and evaluated by a mouthwash sample containing 1% tannin, as the most effective antibacterial complex in green tea. Comparative studies were also conducted between green tea mouthwashes containing 1% tannin and a similar sample with 10% propylene glycol added during extraction. This comparison was applied for a chlorhexidine 0.2% sample as a chemical mouthwash brand, too. Results There was a meaningful difference between the green tea mouthwashes containing 10% propylene glycol and the simple green tea extract (P < 0.05). Significant difference was also seen between the herbal and chemical mouthwashes (P < 0.05). The extract 1% tannin containing 10% propylene glycol reduced the aerobic mouth bacterial load of the student salvia about 64 percent. The pH monotonousness in different days and temperatures approved the stability of tannin in liquid water medium. Conclusions Using green tea extract as a herbal mouthwash is safe and harmless specially for children and pregnant women. This result led us to suppose that green tea may prevent plaque formation on teeth, coming over halitosis due to mouth infection, too. These effects need to be approved in an in vivo trial as a second study. PMID:24624155

Hydrogenolysis of 6-carbon sugars and other organic compounds

DOEpatents

Werpy, Todd A.; Frye, Jr., John G.; Zacher, Alan H.; Miller, Dennis J.

2005-01-11

Methods for hydrogenolysis are described which use a Re-containing multimetallic catalyst for hydrogenolysis of both C--O and C--C bonds. Methods and compositions for reactions of hydrogen over a Re-containing catalyst with compositions containing a 6-carbon sugar, sugar alcohol, or glycerol are described. It has been surprisingly discovered that reaction with hydrogen over a Re-containing multimetallic catalyst resulted in superior conversion and selectivity to desired products such as propylene glycol.

78 FR 14241 - Acetonitrile; Community Right-to-Know Toxic Chemical Release Reporting

Federal Register 2010, 2011, 2012, 2013, 2014

2013-03-05

... 50 values (i.e., the dose of a chemical that is lethal to 50 percent of the test organisms) have been...., the concentration of a chemical that is lethal to 50 percent of the test organisms) of 12,000, 16,000... estimate for acetonitrile in mice was reported to be 2,693 ppm (Ref. 6). A recent study (Ref. 12) reported...

21 CFR 172.850 - Lactylated fatty acid esters of glycerol and propylene glycol.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Lactylated fatty acid esters of glycerol and... DIRECT ADDITION TO FOOD FOR HUMAN CONSUMPTION Multipurpose Additives § 172.850 Lactylated fatty acid esters of glycerol and propylene glycol. The food additive lactylated fatty acid esters of glycerol and...

21 CFR 172.850 - Lactylated fatty acid esters of glycerol and propylene glycol.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Lactylated fatty acid esters of glycerol and... DIRECT ADDITION TO FOOD FOR HUMAN CONSUMPTION Multipurpose Additives § 172.850 Lactylated fatty acid esters of glycerol and propylene glycol. The food additive lactylated fatty acid esters of glycerol and...

Substantially isotactic, linear, alternating copolymers of carbon monoxide and an olefin

DOEpatents

Sen, Ayusman; Jiang, Zhaozhong

1996-01-01

The compound, [Pd(Me-DUPHOS)(MeCN).sub.2 ](BF.sub.4).sub.2, [Me-DUPHOS: 1,2-bis(2,5-dimethylphospholano)benzene] is an effective catalyst for the highly enantioselective, alternating copolymerization of olefins, such as aliphatic .alpha.-olefins, with carbon monoxide to form optically active, isotactic polymers which can serve as excellent starting materials for the synthesis of other classes of chiral polymers. For example, the complete reduction of a propylene-carbon monoxide copolymer resulted in the formation of a novel, optically active poly(1,4-alcohol). Also, the previously described catalyst is a catalyst for the novel alternating isomerization cooligomerization of 2-butene with carbon monoxide to form optically active, isotactic poly(1,5-ketone)

Substantially isotactic, linear, alternating copolymers of carbon monoxide and an olefin

DOEpatents

Sen, A.; Jiang, Z.

1996-05-28

The compound, [Pd(Me-DUPHOS)(MeCN){sub 2}](BF{sub 4}){sub 2}, [Me-DUPHOS: 1,2-bis(2,5-dimethylphospholano)benzene] is an effective catalyst for the highly enantioselective, alternating copolymerization of olefins, such as aliphatic {alpha}-olefins, with carbon monoxide to form optically active, isotactic polymers which can serve as excellent starting materials for the synthesis of other classes of chiral polymers. For example, the complete reduction of a propylene-carbon monoxide copolymer resulted in the formation of a novel, optically active poly(1,4-alcohol). Also, the previously described catalyst is a catalyst for the novel alternating isomerization cooligomerization of 2-butene with carbon monoxide to form optically active, isotactic poly(1,5-ketone).

Heat transfer nanofluid based on curly ultra-long multi-wall carbon nanotubes

NASA Astrophysics Data System (ADS)

Boncel, Sławomir; Zniszczoł, Aurelia; Pawlyta, Mirosława; Labisz, Krzysztof; Dzido, Grzegorz

2018-02-01

The main challenge in the use of multi-wall carbon nanotube (MWCNT) as key components of nanofluids is to transfer excellent thermal properties from individual nanotubes into the bulk systems. We present studies on the performance of heat transfer nanofluids based on ultra-long ( 2 mm), curly MWCNTs - in the background of various other nanoC-sp2, i.e. oxidized MWCNTs, commercially available Nanocyl™ MWCNTs and spherical carbon nanoparticles (SCNs). The nanofluids prepared via ultrasonication from water and propylene glycol were studied in terms of heat conductivity and heat transfer in a scaled up thermal circuit containing a copper helical heat exchanger. Ultra-long curly MWCNT (1 wt.%) nanofluids (stabilized with Gum Arabic in water) emerged as the most thermally conducting ones with a 23-30%- and 39%-enhancement as compared to the base-fluids for water and propylene glycol, respectively. For turbulent flows ( Re = 8000-11,000), the increase of heat transfer coefficient for the over-months stable 1 wt.% ultra-long MWCNT nanofluid was found as high as >100%. The findings allow to confirm that longer MWCNTs are promising solid components in nanofluids and hence to predict their broader application in heat transfer media.

Performance of the SMD and SM8 models for predicting solvation free energy of neutral solutes in methanol, dimethyl sulfoxide and acetonitrile.

PubMed

Zanith, Caroline C; Pliego, Josefredo R

2015-03-01

The continuum solvation models SMD and SM8 were developed using 2,346 solvation free energy values for 318 neutral molecules in 91 solvents as reference. However, no solvation data of neutral solutes in methanol was used in the parametrization, while only few solvation free energy values of solutes in dimethyl sulfoxide and acetonitrile were used. In this report, we have tested the performance of the models for these important solvents. Taking data from literature, we have generated solvation free energy, enthalpy and entropy values for 37 solutes in methanol, 21 solutes in dimethyl sulfoxide and 19 solutes in acetonitrile. Both SMD and SM8 models have presented a good performance in methanol and acetonitrile, with mean unsigned error equal or less than 0.66 and 0.55 kcal mol(-1) in methanol and acetonitrile, respectively. However, the correlation is worse in dimethyl sulfoxide, where the SMD and SM8 methods present mean unsigned error of 1.02 and 0.95 kcal mol(-1), respectively. Our results point out the SMx family of models need be improved for dimethyl sulfoxide solvent.

Performance of the SMD and SM8 models for predicting solvation free energy of neutral solutes in methanol, dimethyl sulfoxide and acetonitrile

NASA Astrophysics Data System (ADS)

Zanith, Caroline C.; Pliego, Josefredo R.

2015-03-01

The continuum solvation models SMD and SM8 were developed using 2,346 solvation free energy values for 318 neutral molecules in 91 solvents as reference. However, no solvation data of neutral solutes in methanol was used in the parametrization, while only few solvation free energy values of solutes in dimethyl sulfoxide and acetonitrile were used. In this report, we have tested the performance of the models for these important solvents. Taking data from literature, we have generated solvation free energy, enthalpy and entropy values for 37 solutes in methanol, 21 solutes in dimethyl sulfoxide and 19 solutes in acetonitrile. Both SMD and SM8 models have presented a good performance in methanol and acetonitrile, with mean unsigned error equal or less than 0.66 and 0.55 kcal mol-1 in methanol and acetonitrile, respectively. However, the correlation is worse in dimethyl sulfoxide, where the SMD and SM8 methods present mean unsigned error of 1.02 and 0.95 kcal mol-1, respectively. Our results point out the SMx family of models need be improved for dimethyl sulfoxide solvent.

Theoretical analysis of co-solvent effect on the proton transfer reaction of glycine in a water–acetonitrile mixture

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

Kasai, Yukako; Yoshida, Norio, E-mail: noriwo@chem.kyushu-univ.jp; Nakano, Haruyuki

2015-05-28

The co-solvent effect on the proton transfer reaction of glycine in a water–acetonitrile mixture was examined using the reference interaction-site model self-consistent field theory. The free energy profiles of the proton transfer reaction of glycine between the carboxyl oxygen and amino nitrogen were computed in a water–acetonitrile mixture solvent at various molar fractions. Two types of reactions, the intramolecular proton transfer and water-mediated proton transfer, were considered. In both types of the reactions, a similar tendency was observed. In the pure water solvent, the zwitterionic form, where the carboxyl oxygen is deprotonated while the amino nitrogen is protonated, is moremore » stable than the neutral form. The reaction free energy is −10.6 kcal mol{sup −1}. On the other hand, in the pure acetonitrile solvent, glycine takes only the neutral form. The reaction free energy from the neutral to zwitterionic form gradually increases with increasing acetonitrile concentration, and in an equally mixed solvent, the zwitterionic and neutral forms are almost isoenergetic, with a difference of only 0.3 kcal mol{sup −1}. The free energy component analysis based on the thermodynamic cycle of the reaction also revealed that the free energy change of the neutral form is insensitive to the change of solvent environment but the zwitterionic form shows drastic changes. In particular, the excess chemical potential, one of the components of the solvation free energy, is dominant and contributes to the stabilization of the zwitterionic form.« less

Electrochemical reduction of carbon fluorine bond in 4-fluorobenzonitrile Mechanistic analysis employing Marcus Hush quadratic activation-driving force relation

NASA Astrophysics Data System (ADS)

Muthukrishnan, A.; Sangaranarayanan, M. V.

2007-10-01

The reduction of carbon-fluorine bond in 4-fluorobenzonitrile in acetonitrile as the solvent, is analyzed using convolution potential sweep voltammetry and the dependence of the transfer coefficient on potential is investigated within the framework of Marcus-Hush quadratic activation-driving force theory. The validity of stepwise mechanism is inferred from solvent reorganization energy estimates as well as bond length calculations using B3LYP/6-31g(d) method. A novel method of estimating the standard reduction potential of the 4-fluorobenzonitrile in acetonitrile is proposed.

Stability of dendriplexes formed by anti-HIV genetic material and poly(propylene imine) dendrimers in the presence of glucosaminoglycans.

PubMed

Szewczyk, Michal; Drzewinska, Joanna; Dzmitruk, Volha; Shcharbin, Dzmitry; Klajnert, Barbara; Appelhans, Dietmar; Bryszewska, Maria

2012-12-20

There are several barriers to the application of dendriplexes formed by poly(propylene imine) dendrimers and genetic material for gene therapy. One limitation is their interaction with extracellular matrix components such as glucosaminoglycans. These can displace the genetic material from the dendriplexes, affecting their transfection activity. In this study, we analyzed the interaction between dendriplexes and the four main glucosaminoglycans (heparin, heparan sulfate, chondroitin sulfate, and hyaluronic acid) by fluorescence polarization and gel electrophoresis. Dendriplexes were formed by combining three anti-HIV antisense oligodeoxynucleotides with three poly(propylene imine) dendrimers of the fourth generation: unmodified and partially modified with maltose and maltotriose (open shell glycodendrimers). The data showed that the effect of glucosaminoglycans on dendriplexes depends on the glucosaminoglycan type and the oligosaccharide serving as the surface group of the dendrimer. Heparin at physiological concentrations destroys dendriplexes formed by open shell glycodendrimers, but dendriplexes based on unmodified poly(propylene imine) dendrimers are stable in its presence. The other glucosaminoglycans at physiological concentrations cannot destroy dendriplexes formed by any of the dendrimers studied.

The Electrocatalytic Reduction of Carbon Dioxide Using Macrocycles of Nickel and Cobalt.

DTIC Science & Technology

1980-10-24

34 water only. Carbon monoxide was found to coprise at least 50% of the total reduced products in all cases; H was also produced in most cases. While a...experiments performed in a gas tight elec- trolysis cell followed by g.c. analysis. The solvents used were either CH3CN-H20 or water only. Carbon...these experiments, and the solvent systems used were either acetonitrile/ water or water only. Gas chromato- graphic analysis was used to determine

Chemical composition separation of a propylene-ethylene random copolymer by high temperature solvent gradient interaction chromatography.

PubMed

Liu, Yonggang; Phiri, Mohau Justice; Ndiripo, Anthony; Pasch, Harald

2017-11-03

A propylene-ethylene random copolymer was fractionated by preparative temperature rising elution fractionation (TREF). The structural heterogeneity of the bulk sample and its TREF fractions was studied by high temperature liquid chromatography with a solvent gradient elution from 1-decanol to 1,2,4-trichlorobenzene. HPLC alone cannot resolve those propylene-ethylene copolymers with high ethylene content in the bulk sample, due to their low weight fractions in the bulk sample and a small response factor of these components in the ELSD detector, as well as their broad chemical composition distribution. These components can only be detected after being separated and enriched by TREF followed by HPLC analysis. Chemical composition separations were achieved for TREF fractions with average ethylene contents between 2.1 and 22.0mol%, showing that copolymers with higher ethylene contents were adsorbed stronger in the Hypercarb column and eluted later. All TREF fractions, except the 40°C fraction, were relatively homogeneous in both molar mass and chemical composition. The 40°C fraction was rather broad in both molar mass and chemical composition distributions. 2D HPLC showed that the molar masses of the components containing more ethylene units were getting lower for the 40°C fraction. HPLC revealed and confirmed that co-crystallization influences the separation in TREF of the studied propylene-ethylene copolymer. Copyright © 2017 Elsevier B.V. All rights reserved.

Adsorption and desorption of methylene blue on porous carbon monoliths and nanocrystalline cellulose.

PubMed

He, Xiaoyun; Male, Keith B; Nesterenko, Pavel N; Brabazon, Dermot; Paull, Brett; Luong, John H T

2013-09-11

The dynamic batch adsorption of methylene blue (MB), a widely used and toxic dye, onto nanocrystalline cellulose (NCC) and crushed powder of carbon monolith (CM) was investigated using the pseudo-first- and -second-order kinetics. CM outperformed NCC with a maximum capacity of 127 mg/g compared to 101 mg/g for NCC. The Langmuir isotherm model was applicable for describing the binding data for MB on CM and NCC, indicating the homogeneous surface of these two materials. The Gibbs free energy of -15.22 kJ/mol estimated for CM unravelled the spontaneous nature of this adsorbent for MB, appreciably faster than the use of NCC (-4.47 kJ/mol). Both pH and temperature exhibited only a modest effect on the adsorption of MB onto CM. The desorption of MB from CM using acetonitrile was very effective with more than 94 % of MB desorbed from CM within 10 min to allow the reusability of this porous carbon material. In contrast, acetonitrile was less effective than ethanol in desorbing MB from NCC. The two solvents were incapable of completely desorbing MB on commercial granular coal-derived activated carbon.

Influence of electrolyte ion-solvent interactions on the performances of supercapacitors porous carbon electrodes

NASA Astrophysics Data System (ADS)

Decaux, C.; Matei Ghimbeu, C.; Dahbi, M.; Anouti, M.; Lemordant, D.; Béguin, F.; Vix-Guterl, C.; Raymundo-Piñero, E.

2014-10-01

The development of advanced and safe electrochemical supercapacitors or hybrid supercapacitors combining a battery electrode material such as graphite and a porous carbon electrode implies the use of new electrolytes containing a tetra-alkylammonium or lithium salt dissolved preferentially in a safe and environmentally friendly solvent such as alkylcarbonates. In those systems, the carbon porosity of the activated carbon electrode controls the electrochemical behavior of the whole device. In this work, it is demonstrated that electrolytes containing highly polarizing ions such as Li+ dissolved in polar solvents such as alkylcarbonates do not completely loss their solvation shell at the opposite of what is observed for poorly solvated cations like TEABF4. As a consequence, the optimal carbon pore size for obtaining the largest energy density, while keeping a high power density, is wider when strongly solvated cations, like Li+ are used than for conventional organic electrolytes using acetonitrile as solvent and TEA+ as salt cations. TEA+ cations are easily desolvated and hence are able to penetrate in small pores matching the dimensions of bare ions. The dissimilarity of behavior of alkylcarbonates and acetonitrile based electrolytes highlights the importance of ion-solvent interactions when searching the optimal porous texture for the electrode material.

Cold-induced aqueous acetonitrile phase separation: A salt-free way to begin quick, easy, cheap, effective, rugged, safe.

PubMed

Shao, Gang; Agar, Jeffrey; Giese, Roger W

2017-07-14

Cooling a 1:1 (v/v) solution of acetonitrile and water at -16° C is known to result in two clear phases. We will refer to this event as "cold-induced aqueous acetonitrile phase separation (CIPS)". On a molar basis, acetonitrile is 71.7% and 13.6% in the upper and lower phases, respectively, in our study. The phase separation proceeds as a descending cloud of microdroplets. At the convenient temperature (typical freezer) employed here the lower phase is rather resistant to solidification, although it emerges from the freezer as a solid if various insoluble matter is present at the outset. In a preliminary way, we replaced the initial (salting-out) step of a representative QuEChERS procedure with CIPS, applying this modified procedure ("CIPS-QuEChERS") to a homogenate of salmon (and partly to beef). Three phases resulted, where only the upper, acetonitrile-rich phase is a liquid (that is completely clear). The middle phase comprises ice and precipitated lipids, while the lower phase is the residual matrix of undissolved salmon or meat. Treating the upper phase from salmon, after isolation, with anhydrous MgSO 4 and C18-Si (typical QuEChERS dispersive solid phase extraction sorbents), and injecting into a GC-MS in a nontargeted mode, gives two-fold more preliminary hits for chemicals, and also number of spiked pesticides recovered, relative to that from a comparable QuEChERS method. In part, this is because of much higher background signals in the latter case. Further study of CIPS-QuEChERS is encouraged, including taking advantage of other QuERChERS conditions. Copyright © 2017 Elsevier B.V. All rights reserved.

Ultrafast vibrational energy flow in water monomers in acetonitrile

NASA Astrophysics Data System (ADS)

Dahms, Fabian; Costard, Rene; Nibbering, Erik T. J.; Elsaesser, Thomas

2016-05-01

Vibrational relaxation of the OH stretching and bending modes of water monomers in acetonitrile is studied by two-color pump-probe experiments in a frequency range from 1400 to 3800 cm-1. Measurements with resonant infrared excitation reveal vibrational lifetimes of 6.4 ± 1.0 ps of the OH stretching modes and 4.0 ± 0.5 ps of the OH bending mode. After OH stretching excitation, the OH bending mode shows an instantaneous response, a hallmark of the anharmonic coupling of stretching and bending modes, and a delayed population buildup by relaxation of the stretching via the bending mode. The relaxation steps are discussed within the framework of current theoretical pictures of water's vibrational relaxation.

Poly(ethylene terephthalate)-based carbons as electrode material in supercapacitors

NASA Astrophysics Data System (ADS)

Domingo-García, M.; Fernández, J. A.; Almazán-Almazán, M. C.; López-Garzón, F. J.; Stoeckli, F.; Centeno, T. A.

A systematic study by complementary techniques shows that PET-waste from plastic vessels is a competitive precursor of carbon electrodes for supercapacitors. PET derived-activated carbons follow the general trends observed for highly porous carbons and display specific capacitances at low current density as high as 197 F g -1 in 2 M H 2SO 4 aqueous electrolyte and 98 F g -1 in the aprotic medium 1 M (C 2H 5) 4NBF 4/acetonitrile. Additionally, high performance has also been achieved at high current densities, which confirms the potential of this type of materials for electrical energy storage. A new method based on the basic solvolysis of PET-waste and the subsequent carbonization seems to be an interesting alternative to obtain porous carbons with enhanced properties for supercapacitors.

Method for fabricating carbon/lithium-ion electrode for rechargeable lithium cell

NASA Technical Reports Server (NTRS)

Attia, Alan I. (Inventor); Halpert, Gerald (Inventor); Huang, Chen-Kuo (Inventor); Surampudi, Subbarao (Inventor)

1995-01-01

The method includes steps for forming a carbon electrode composed of graphitic carbon particles adhered by an ethylene propylene diene monomer binder. An effective binder composition is disclosed for achieving a carbon electrode capable of subsequent intercalation by lithium ions. The method also includes steps for reacting the carbon electrode with lithium ions to incorporate lithium ions into graphitic carbon particles of the electrode. An electrical current is repeatedly applied to the carbon electrode to initially cause a surface reaction between the lithium ions and to the carbon and subsequently cause intercalation of the lithium ions into crystalline layers of the graphitic carbon particles. With repeated application of the electrical current, intercalation is achieved to near a theoretical maximum. Two differing multi-stage intercalation processes are disclosed. In the first, a fixed current is reapplied. In the second, a high current is initially applied, followed by a single subsequent lower current stage. Resulting carbon/lithium-ion electrodes are well suited for use as an anode in a reversible, ambient temperature, lithium cell.

Thermal Vacuum Test of GLAS Propylene Loop Heat Pipe Development Model

NASA Technical Reports Server (NTRS)

Baker, Charles; Butler, Dan; Ku, Jentung; Kaya, Tarik; Nikitkin, Michael

2000-01-01

This paper presents viewgraphs on Thermal Vacuum Tests of the GLAS (Geoscience Laser Altimeter System) Propylene Loop Heat Pipe Development Model. The topics include: 1) Flight LHP System (Laser); 2) Test Design and Objectives; 3) DM (Development Model) LHP (Loop Heat Pipe) Test Design; 4) Starter Heater and Coupling Blocks; 5) CC Control Heaters and PRT; 6) Heater Plates (Shown in Reflux Mode); 7) Startup Tests; 8) CC Control Heater Power Tests for CC Temperature Control; and 9) Control Temperature Stability.

End-group characterisation of poly(propylene glycol)s by means of electrospray ionisation-tandem mass spectrometry (ESI-MS/MS).

PubMed

Jackson, Anthony T; Slade, Susan E; Thalassinos, Konstantinos; Scrivens, James H

2008-10-01

The end-group functionalisation of a series of poly(propylene glycol)s has been characterised by means of electrospray ionisation-tandem mass spectrometry (ESI-MS/MS). A series of peaks with mass-to-charge ratios that are close to that of the precursor ion were used to generate information on the end-group functionalities of the poly(propylene glycol)s. Fragment ions resulting from losses of both of the end groups were noted from some of the samples. An example is presented of how software can be used to significantly reduce the length of time involved in data interpretation (which is typically the most time-consuming part of the analysis).

Characterization of uranium surfaces machined with aqueous propylene glycol-borax or perchloroethylene-mineral oil coolants

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

Cristy, S.S.; Bennett, R.K. Jr.; Dillon, J.J.

1986-12-31

The use of perchloroethylene (perc) as an ingredient in coolants for machining enriched uranium at the Oak Ridge Y-12 Plant has been discontinued because of environmental concerns. A new coolant was substituted in December 1985, which consists of an aqueous solution of propylene glycol with borax (sodium tetraborate) added as a nuclear poison and with a nitrite added as a corrosion inhibitor. Uranium surfaces machined using the two coolants were compared with respects to residual contamination, corrosion or corrosion potential, and with the aqueous propylene glycol-borax coolant was found to be better than that of enriched uranium machined with themore » perc-mineral oil coolant. The boron residues on the final-finished parts machined with the borax-containing coolant were not sufficient to cause problems in further processing. All evidence indicated that the enriched uranium surfaces machined with the borax-containing coolant will be as satisfactory as those machined with the perc coolant.« less

Protective efficacy of menthol propylene glycol carbonate compared to N, N-diethyl-methylbenzamide against mosquito bites in Northern Tanzania.

PubMed

Kweka, Eliningaya J; Munga, Stephen; Mahande, Aneth M; Msangi, Shandala; Mazigo, Humphrey D; Adrias, Araceli Q; Matias, Jonathan R

2012-09-05

The reduction of malaria parasite transmission by preventing human-vector contact is critical in lowering disease transmission and its outcomes. This underscores the need for effective and long lasting arthropod/insect repellents. Despite the reduction in malaria transmission and outcomes in Tanzania, personal protection against mosquito bites is still not well investigated. This study sought to determine the efficacy of menthol propylene glycol carbonate (MR08), Ocimum suave as compared to the gold standard repellent N, N-diethyl-methylbenzamide (DEET), either as a single dose or in combination (blend), both in the laboratory and in the field against Anopheles gambiae s.l and Culex quinquefasciatus. In the laboratory evaluations, repellents were applied on one arm while the other arm of the same individual was treated with a base cream. Each arm was separately exposed in cages with unfed female mosquitoes. Repellents were evaluated either as a single dose or as a blend. Efficacy of each repellent was determined by the number of mosquitoes that landed and fed on treated arms as compared to the control or among them. In the field, evaluations were performed by human landing catches at hourly intervals from 18:00  hr to 01:00  hr. A total of 2,442 mosquitoes were collected during field evaluations, of which 2,376 (97.30%) were An. gambiae s.l while 66 (2.70%) were Cx. quinquefaciatus. MR08 and DEET had comparatively similar protective efficacy ranging from 92% to 100 for both single compound and blends. These findings indicate that MR08 has a similar protective efficacy as DEET for personal protection outside bed nets when used singly and in blends. Because of the personal protection provided by MR08, DEET and blends as topical applicants in laboratory and field situations, these findings suggest that, these repellents could be used efficiently in the community to complement existing tools. Overall, Cx. quinquefasciatus were significantly prevented from blood

Freeze-out extraction of monocarboxylic acids from water into acetonitrile under the action of centrifugal forces

NASA Astrophysics Data System (ADS)

Bekhterev, V. N.

2016-10-01

It is established that the efficiency of the freezing-out extraction of monocarboxylic acids C3-C;8 and sorbic acid from water into acetonitrile increases under the action of centrifugal forces. The linear growth of the partition coefficient in the homologous series of C2-C8 acids with an increase in molecule length, and the difference between the efficiency of extracting sorbic and hexanoic acid, are discussed using a theoretical model proposed earlier and based on the adsorption-desorption equilibrium of the partition of dissolved organic compounds between the resulting surface of ice and the liquid phase of the extract. The advantages of the proposed technique with respect to the degree of concentration over the method of low-temperature liquid-liquid extraction are explained in light of the phase diagram for the water-acetonitrile mixture.

Relative toxicities of pure propylene and ethylene glycol and formulated deicers on plant species

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

DuFresne, D.L.; Pillard, D.A.

1994-12-31

Propylene and ethylene glycol deicers are commonly used at airports in the US and other countries to remove and retard the accumulation of snow and ice on aircraft. Deicers may not only enter water bodies without treatment, due to excessive storm-related flow, but also may expose terrestrial organisms to high concentrations through surface runoff. Most available toxicity data are for aquatic vertebrates and invertebrate species; this study examined effects on terrestrial and aquatic plants. Terrestrial plant species included both a monocot (rye grass, Lolium perenne) and a dicot (lettuce, Lactuca saliva). Aquatic species included a single cell alga (Selenastrum capricomutum),more » and an aquatic macrophyte (duckweed, Lemna minor). Glycol deicers were obtained in the formulated mixtures used on aircraft. Pure ethylene and propylene glycol were obtained from Sigma{reg_sign}. Parameters measured included germination, root and shoot length, survival, and growth. Formulated deicers, like those used at airports, were generally more toxic than pure chemicals, based on glycol concentration. This greater toxicity of formulated deicers is consistent with results of tests using animal species.« less

Dilatant effect enhancers for silica dispersions in poly(propylene glycols).

PubMed

Orawiec, Marcin; Kaczorowski, Marcin; Rokicki, Gabriel

2018-05-29

Shear thickening fluids have found many applications in energy damping materials such as sports guards and liquid body armors. Therefore, an additive which could tailor the dilatant properties of such fluids without significantly affecting other properties, especially zero shear viscosity, could significantly increase the versatility of protective materials based on shear thickening fluids. In this paper, poly(propylene glycols) (PPGs) diacetates are investigated as dilatant effect enhancers for nano-silica dispersions in poly(propylene glycols). The influence of the modifiers on rheological properties of the dispersion is studied and discussed. Additionally, FTIR and rheological properties measurements are conducted in order to determine relative interactions strength between hydroxyl groups of PPGs and silica and carbonyl groups of PPG diacetates. Our findings suggest that the relative attractive interaction strength in studied systems can be arranged in the following order: COCO < COOH < OHOH. Therefore, the addition of PPG diacetate hinders the attractive interactions between liquid and solid. We report that the addition of diacetates can lead both to enhancement and deterioration of dilatant effect depending on the concentration of the modifier and its chain length. Based on conducted measurements and literature data, mechanism explaining that phenomenon is suggested. As a result, we propose an easy to make and cheap dilatant effect enhancer for widely used shear thickening fluids which, when used in small amounts (1-2.5%), raises the viscosity jump drastically. Additionally, the presence of the modifier does not significantly affect the zero shear viscosity of the shear thickening fluid. Copyright © 2018 Elsevier Inc. All rights reserved.

Hydrogenolysis Of 5-Carbon Sugars, Sugar Alcohols And Compositions For Reactions Involving Hydrogen

DOEpatents

Werpy, Todd A.; Frye, Jr., John G.; Zacher, Alan H.; Miller, Dennis J.

2004-01-13

Methods and compositions for reactions of hydrogen over a Re-containing catalyst with compositions containing a 5-carbon sugar, sugar alcohol, or lactic acid are described. It has been surprisingly discovered that reaction with hydrogen over a Re-containing multimetallic catalyst resulted in superior conversion and selectivity to desired products such as propylene glycol. A process for the synthesis of PG from lactate or lactic acid is also described.

Determination of thermodynamic affinities of various polar olefins as hydride, hydrogen atom, and electron acceptors in acetonitrile.

PubMed

Cao, Ying; Zhang, Song-Chen; Zhang, Min; Shen, Guang-Bin; Zhu, Xiao-Qing

2013-07-19

A series of 69 polar olefins with various typical structures (X) were synthesized and the thermodynamic affinities (defined in terms of the molar enthalpy changes or the standard redox potentials in this work) of the polar olefins obtaining hydride anions, hydrogen atoms, and electrons, the thermodynamic affinities of the radical anions of the polar olefins (X(•-)) obtaining protons and hydrogen atoms, and the thermodynamic affinities of the hydrogen adducts of the polar olefins (XH(•)) obtaining electrons in acetonitrile were determined using titration calorimetry and electrochemical methods. The pure C═C π-bond heterolytic and homolytic dissociation energies of the polar olefins (X) in acetonitrile and the pure C═C π-bond homolytic dissociation energies of the radical anions of the polar olefins (X(•-)) in acetonitrile were estimated. The remote substituent effects on the six thermodynamic affinities of the polar olefins and their related reaction intermediates were examined using the Hammett linear free-energy relationships; the results show that the Hammett linear free-energy relationships all hold in the six chemical and electrochemical processes. The information disclosed in this work could not only supply a gap of the chemical thermodynamics of olefins as one class of very important organic unsaturated compounds but also strongly promote the fast development of the chemistry and applications of olefins.

Propylene glycol-embodying deformable liposomes as a novel drug delivery carrier for vaginal fibrauretine delivery applications.

PubMed

Li, Wei-Ze; Hao, Xu-Liang; Zhao, Ning; Han, Wen-Xia; Zhai, Xi-Feng; Zhao, Qian; Wang, Yu-E; Zhou, Yong-Qiang; Cheng, Yu-Chuan; Yue, Yong-Hua; Fu, Li-Na; Zhou, Ji-Lei; Wu, Hong-Yu; Dong, Chun-Jing

2016-03-28

The purpose of this work was to develop and characterize the fibrauretine (FN) loaded propylene glycol-embodying deformable liposomes (FDL), and evaluate the pharmacokinetic behavior and safety of FDL for vaginal drug delivery applications. FDL was characterized for structure, particle size, zeta potential, deformability and encapsulation efficiency; the ability of FDL to deliver FN across vagina tissue in vitro and the distribution behavior of FN in rat by vaginal drug delivery were investigated, the safety of FDL to the vagina of rabbits and rats as well as human vaginal epithelial cells (VK2/E6E7) were also evaluated. Results revealed that: (i) the FDL have a closed spherical shape and lamellar structure with a homogeneous size of 185±19nm, and exhibited a negative charge of -53±2.7mV, FDL also have a good flexibility with a deformability of 92±5.6 (%phospholipids/min); (ii) the dissolving capacity of inner water phase and hydrophilicity of phospholipid bilayers of deformable liposomes were increased by the presence of propylene glycol, this may be elucidated by the fluorescent probes both lipophilic Nile red and hydrophilic calcein that were filled up the entire volume of the FDL uniformly, so the FDL with a high entrapment capacity (were calculated as percentages of total drug) for FN was 78±2.14%; (iii) the permeability of FN through vaginal mucosa was obviously improved by propylene glycol-embodying deformable liposomes, no matter whether the FN loaded in liposomes or not, although FN loaded in liposomes caused the highest permeability and drug reservoir in vagina; (iv) the FN mainly aggregated in the vagina and uterus, then the blood, spleen, liver, kidney, heart and lungs for vaginal drug delivery, this indicating vaginal delivery of FDL have a better 'vaginal local targeting effect'; and (v) the results of safety evaluation illustrate that the FDL is non-irritant and well tolerated in vivo, thereby establishing its vaginal drug delivery potential

21 CFR 172.856 - Propylene glycol mono- and diesters of fats and fatty acids.

Code of Federal Regulations, 2010 CFR

2010-04-01

... fatty acids. 172.856 Section 172.856 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH... diesters of fats and fatty acids. Propylene glycol mono- and diesters of fats and fatty acids may be safely... and/or fatty acids in compliance with § 172.860 and/or oleic acid derived from tall oil fatty acids in...

21 CFR 172.856 - Propylene glycol mono- and diesters of fats and fatty acids.

Code of Federal Regulations, 2011 CFR

2011-04-01

... fatty acids. 172.856 Section 172.856 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH... diesters of fats and fatty acids. Propylene glycol mono- and diesters of fats and fatty acids may be safely... and/or fatty acids in compliance with § 172.860 and/or oleic acid derived from tall oil fatty acids in...

Photochromic ruthenium sulfoxide complexes: evidence for isomerization through a conical intersection.

PubMed

McClure, Beth Anne; Mockus, Nicholas V; Butcher, Dennis P; Lutterman, Daniel A; Turro, Claudia; Petersen, Jeffrey L; Rack, Jeffrey J

2009-09-07

The complexes [Ru(bpy)(2)(OS)](PF(6)) and [Ru(bpy)(2)(OSO)](PF(6)), where bpy is 2,2'-bipyridine, OS is 2-methylthiobenzoate, and OSO is 2-methylsulfinylbenzoate, have been studied. The electrochemical and photochemical reactivity of [Ru(bpy)(2)(OSO)](+) is consistent with an isomerization of the bound sulfoxide from S-bonded (S-) to O-bonded (O-) following irradiation or electrochemical oxidation. Charge transfer excitation of [Ru(bpy)(2)(OSO)](+) in MeOH results in the appearance of two new metal-to-ligand charge transfer (MLCT) maxima at 355 and 496 nm, while the peak at 396 nm diminishes in intensity. The isomerization is reversible at room temperature in alcohol or propylene carbonate solution. In the absence of light, solutions of O-[Ru(bpy)(2)(OSO)](+) revert to S-[Ru(bpy)(2)(OSO)](+). Kinetic analysis reveals a biexponential decay with rate constants of 5.66(3) x 10(-4) s(-1) and 3.1(1) x 10(-5) s(-1). Cyclic voltammograms of S-[Ru(bpy)(2)(OSO)](+) are consistent with electron-transfer-triggered isomerization of the sulfoxide. Analysis of these voltammograms reveal E(S)(o)' = 0.86 V and E(O)(o)' = 0.49 V versus Ag/Ag(+) for the S- and O-bonded Ru(3+/2+) couples, respectively, in propylene carbonate. We found k(S-->O) = 0.090(15) s(-1) in propylene carbonate and k(S-->O) = 0.11(3) s(-1) in acetonitrile on Ru(III), which is considerably slower than has been reported for other sulfoxide isomerizations on ruthenium polypyridyl complexes following oxidation. The photoisomerization quantum yield (Phi(S-->O) = 0.45, methanol) is quite large, indicating a rapid excited state isomerization rate constant. The kinetic trace at 500 nm is monoexponential with tau = 150 ps, which is assigned to the excited S-->O isomerization rate. There is no spectroscopic or kinetic evidence for an O-bonded (3)MLCT excited state in the spectral evolution of S-[Ru(bpy)(2)(OSO)](+) to O-[Ru(bpy)(2)(OSO)](+). Thus, isomerization occurs nonadiabatically from an S-bonded (or eta(2

Characterization of Propylene Glycol-Mitigated Freeze/Thaw Agglomeration of a Frozen Liquid nOMV Vaccine Formulation by Static Light Scattering and Micro-Flow Imaging.

PubMed

Mensch, Christopher D; Davis, Harrison B; Blue, Jeffrey T

2015-01-01

The purpose of this work was to investigate the susceptibility of an aluminum adjuvant and an aluminum-adjuvanted native outer membrane vesicle (nOMV) vaccine formulation to freeze/thaw-induced agglomeration using static light scattering and micro-flow Imaging analysis; and to evaluate the use of propylene glycol as a vaccine formulation excipient by which freeze/thaw-induced agglomeration of a nOMV vaccine formulation could be mitigated. Our results indicate that including 7% v/v propylene glycol in an nOMV containing aluminum adjuvanted vaccine formulation, mitigates freeze/thaw-induced agglomeration. We evaluated the effect of freeze-thawing on an aluminum adjuvant and an aluminum adjuvanted native outer membrane vesicle (nOMV) vaccine formulation. Specifically, we characterized the freeze/thaw-induced agglomeration through the use of static light scattering, micro-flow imaging, and cryo-electron microscopy analysis. Further, we evaluated the use of 0-9% v/v propylene glycol as an excipient which could be included in the formulation for the purpose of mitigating the agglomeration induced by freeze/thaw. The results indicate that using 7% v/v propylene glycol as a formulation excipient is effective at mitigating agglomeration of the nOMV vaccine formulation, otherwise induced by freeze-thawing. © PDA, Inc. 2015.

Solubility of pioglitazone hydrochloride in binary mixtures of polyethylene glycol 400 with ethanol, propylene glycol, N-methyl-2-pyrrolidone, and water at 25 degrees C.

PubMed

Jouyban, Abolghasem; Soltanpour, Shahla

2010-09-01

The solubility of pioglitazone hydrochloride in binary mixtures of polyethylene glycol 400 with ethanol, N-methyl-2-pyrrolidone, propylene glycol, and water at 25 degrees C are reported. The generated data are fitted to the Jouyban-Acree model and the mean relative deviations are 2.6%, 1.5%, 5.8%, and 7.4%, respectively for ethanol, N-methyl-2-pyrrolidone, propylene glycol, and water.

Ethylene-Propylene Terpolymer Rubber Processing by Electron Beam Irradiation

NASA Astrophysics Data System (ADS)

Manaila, Elena N.; Zuga, Maria Daniela T.; Martin, Diana I.; Craciun, Gabriela D.; Ighigeanu, Daniel I.; Matei, Constantin I.

2007-04-01

The investigations on the cross-linking by accelerated electrons of 6.23 MeV in lowly unsaturated elastomers of EPDM (ethylene-propylene terpolymer rubber) type are presented. Two rubber blends based EPDM were prepared and irradiated at different doses up to 250kGy: blend A - based on EPDM maleinized with polyethylene, zinc oxide, plasticizers, filler, and blend B - based on EPDM / PE (50 % EPDM and 50% polyethylene). Blends were prepared on a laboratory electrically heated rubber mill at temperatures of 150-160°C to enable the polyethylene (PE) melting to be reached. Plates of 150 × 150 × 2 mm were obtained in a laboratory electrical press at 170°C.

Evaluation of propylene glycol and glycerol infusions as treatments for ketosis in dairy cows.

PubMed

Piantoni, P; Allen, M S

2015-08-01

To evaluate propylene glycol (PG) and glycerol (G) as potential treatments for ketosis, we conducted 2 experiments lasting 4 d each in which cows received one bolus infusion per day. Blood was collected before infusion, over 240min postinfusion, as well as 24 h postinfusion. Experiment 1 used 6 ruminally cannulated cows (26±7 d in milk) randomly assigned to 300-mL infusions of PG or G (both ≥99.5% pure) in a crossover design experiment with 2 periods. Within each period, cows were assigned randomly to infusion site sequence: abomasum (A)-cranial reticulorumen (R) or the reverse, R-A. Glucose precursors were infused into the R to simulate drenching and the A to prevent metabolism by ruminal microbes. Glycerol infused in the A increased plasma glucose concentration the most (15.8mg/dL), followed by PG infused in the R (12.6mg/dL), PG infused in the A (9.11mg/dL), and G infused in the R (7.3mg/dL). Infusion of PG into the R increased plasma insulin and insulin area under the curve (AUC) the most compared with all other treatments (7.88 vs. 2.13μIU/mL and 321 vs. 31.9min×μIU/mL, respectively). Overall, PG decreased plasma BHBA concentration after infusion (-6.46 vs. -4.55mg/dL) and increased BHBA AUC (-1,055 vs. -558min ×mg/dL) compared with G. Plasma NEFA responses were not different among treatments. Experiment 2 used 8 ruminally cannulated cows (22±5 d in milk) randomly assigned to treatment sequence in a Latin square design experiment balanced for carryover effects. Treatments were 300mL of PG, 300mL of G, 600mL of G (2G), and 300mL of PG + 300mL of G (GPG), all infused into the R. Treatment contrasts compared PG with each treatment containing glycerol (G, 2G, and GPG). Propylene glycol increased plasma glucose (14.0 vs. 5.35mg/dL) and insulin (7.59 vs. 1.11μIU/mL) concentrations compared with G, but only tended to increase glucose and insulin concentrations compared with 2G. Propylene glycol increased AUC for glucose (1,444 vs. 94.3mg/dL) and insulin (326

A novel carbon electrode material for highly improved EDLC performance.

PubMed

Fang, Baizeng; Binder, Leo

2006-04-20

Porous materials, developed by grafting functional groups through chemical surface modification with a surfactant, represent an innovative concept in energy storage. This work reports, in detail, the first practical realization of a novel carbon electrode based on grafting of vinyltrimethoxysilane (vtmos) functional group for energy storage in electric double layer capacitor (EDLC). Surface modification with surfactant vtmos enhances the hydrophobisation of activated carbon and the affinity toward propylene carbonate (PC) solvent, which improves the wettability of activated carbon in the electrolyte solution based on PC solvent, resulting in not only a lower resistance to the transport of electrolyte ions within micropores of activated carbon but also more usable surface area for the formation of electric double layer, and accordingly, higher specific capacitance, energy density, and power capability available from the capacitor based on modified carbon. Especially, the effects from surface modification become superior at higher discharge rate, at which much better EDLC performance (i.e., much higher energy density and power capability) has been achieved by the modified carbon, suggesting that the modified carbon is a novel and very promising electrode material of EDLC for large current applications where both high energy density and power capability are required.

Ultra-Violet/Electron Beam Detoxification of Nitroglycerin/Propylene Glycol Dinrate Waste Water, Phase 1

DTIC Science & Technology

1994-03-16

University of Vienna’s Institute for Theoretical and Radiation Chemistry provided assistance in the development of chemical theory. Z. Liu, Associate...Professor of Applied Chemistry at the University of Science and Technology, Hefei, Peoples Republic of China provided support with physical measurements. The...include Glyocollic acid " Inogani Nitates> 90 nitroglycerine, propylene glycol dinitrate Inorganic Nitrates (PGDN), trimethylolethane trinitrate MDL

Glycerol conversion into value added chemicals over bimetallic catalysts in supercritical carbon dioxide

NASA Astrophysics Data System (ADS)

Hidayati, Luthfiana N.; Sudiyarmanto, Adilina, Indri B.

2017-01-01

Development of alternative energy from biomass encourage the experiments and production of biodiesel lately. Biodiesel industries widely expand because biodiesel as substitute of fossil fuel recognized as promising renewable energy. Glycerol is a byproduct of biodiesel production, which is resulted 10% wt average every production. Meanwhile, carbon dioxide is a gas that is very abundant amount in the atmosphere. Glycerol and carbon dioxide can be regarded as waste, possibly will produce value-added chemical compounds through chemically treated. In this preliminary study, conversion of glycerol and carbon dioxide using bimetallic catalyst Ni-Sn with various catalyst supports : MgO, γ-Al2O3, and hydrotalcite. Catalysts which have been prepared, then physically characterized by XRD, surface area and porosity analysis, and thermal gravity analysis. Catalytic test performance using supercritical carbon dioxide conditions. Furthermore, the products were analyzed by GC. The final product mostly contained of propylene glycol and glycerol carbonate.

Elaboration of a microstructured inkjet-printed carbon electrochemical capacitor

NASA Astrophysics Data System (ADS)

Pech, David; Brunet, Magali; Taberna, Pierre-Louis; Simon, Patrice; Fabre, Norbert; Mesnilgrente, Fabien; Conédéra, Véronique; Durou, Hugo

Carbon-based micro-supercapacitors dedicated to energy storage in self-powered modules were fabricated with inkjet printing technology on silicon substrate. An ink was first prepared by mixing an activated carbon powder with a PTFE polymer binder in ethylene glycol stabilized with a surfactant then deposited by inkjet on patterned gold current collectors with the substrate heated at 140 °C in order to assure a good homogeneity. Electrochemical micro-capacitors with electrodes in an interdigital configuration were fabricated, and characterized using electrochemical techniques in 1 M Et 4NBF 4 propylene carbonate electrolyte. These micro-devices show an excellent capacitive behavior over a wide potential range of 2.5 V for a cell capacitance of 2.1 mF cm -2. The newly developed technology will allow the integration of the storage device as close as possible to the MEMS-based energy harvesting device, minimizing power losses through connections.

Transesterification of propylene glycol methyl ether in chromatographic reactors using anion exchange resin as a catalyst.

PubMed

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

2016-09-30

Reactive chromatography using an anion exchange resin is proposed for a transesterification reaction of propylene glycol methyl ether (DOWANOL™ PM) with ethyl acetate to produce propylene glycol methyl ether acetate (DOWANOL™ PMA). This reaction is studied in batch and chromatographic reactors catalyzed by an anion exchange resin. Several anion exchange resins are tested and compared based on the performance of resin as an adsorbent and a catalyst. A chromatographic column is packed with a selected catalyst, AMBERLITE™ IRA904, and both reaction and chromatographic elution are studied at different temperatures and feed concentrations. The resulting chromatograms are fitted to a mathematical model to obtain adsorption equilibrium and reaction kinetic parameters by the inverse method. Compared to esterification investigated in a previous study, transesterification has advantages such as a higher conversion at lower temperature and easy removal of the byproduct which may lead to higher productivity. Deactivation of anion exchange resins is observed and potential solutions are suggested. Copyright © 2016 Elsevier B.V. All rights reserved.

H2O-Polyaluminium chloride-TBAB as synergistic catalysts for the synthesis of cyclic carbonate

NASA Astrophysics Data System (ADS)

Liu, X. J.; Yan, P.; Han, Y.

2018-01-01

An efficient catalytic system consisting of H2O, Polyaluminium chloride (PAC) and Tetrabutylammonium bromide (TBAB) was applied to the cycloaddition of carbon dioxide (CO2) to epoxides under mild conditions. Their catalytic cycloaddition activities were found to be well correlated with H2O and polyaluminium chloride, which had a synergetic effect with the halide anion of TBAB. The presence of H2O and PAC could remarkably improve the yield of propylene carbonate (PC) by which the reaction yield is about 4-5 times higher than TBAB. alone.The catalytic system also exhibited excellent cycloaddition activities for various epoxide substrates.

Poly(diiododiacetylene): A Potential Precursor for New All-Carbon Materials

NASA Astrophysics Data System (ADS)

Resch, Daniel Joseph

Poly(diiododiacetylene) (PIDA) is a polymer consisting entirely of carbon and iodine. The polymer is prepared by cocrystallizing a bis(nitrile) oxalamide host with the monomer diiodobutadiyne. These compounds are held together by a halogen bond and an ordered 1,4-topochemical polymerization occurs in the solid state. The formation of the monomer cocrystals was found to be highly solvent dependent. Acetonitrile was found to greatly improve the yield of cocrystals over solvents used in the past. Cocrystals could not be obtained from other solvents such as dimethoxyethane and acetone. THF did give some cocrystal but the yield was poor. The use of acetonitrile as a solvent now allows for PIDA cocrystals to be reliably prepared in excellent yield for detailed studies. The weak C-I bonds in PIDA can be broken under mild conditions with simple Lewis bases like pyrrolidine and iodide ion. Studies with small molecule models show that the mechanism of elimination is E2-like and highly solvent dependent. Polar aprotic solvents favor the reaction while non-polar solvents disfavor it. Reaction occurs in protic solvents, but the rate is much slower. Iodide was found to carry out the reaction in 1 hour d5-PhNO 2 while reaction with pyrrolidine did not reach completion in 15 hours. When PIDA is subjected to deiodination the product is an amorphous graphite-like material that contains non-carbon atoms. Depending on the reaction conditions, it is possible to incorporate sulfur or phosphorus into the final product. The source of these elements is the reducing agent that is typically added to sequester molecular iodine. Sequestering the iodine prevents it from reacting with the carbon species. New insights into the deiodination reaction have made PIDA more promising as a precursor to prepare all-carbon materials or heteroatom-functionalized carbon under mild conditions.

Distribution of pesticides in n-hexane/water and n-hexane/acetonitrile systems and estimation of possibilities of their extraction isolation and preconcentration from various matrices.

PubMed

Zayats, M F; Leschev, S M; Petrashkevich, N V; Zayats, M A; Kadenczki, L; Szitás, R; Szemán Dobrik, H; Keresztény, N

2013-04-24

Distribution of 150 most widely used pesticides of different chemical classes (amides, anilinopirimidines, aromatics, benzenesulfonates, carbamates, dicarboximides, organophosphorus compounds, phenyl esters, phenylureas, pyrazoles, pyrethroids, pyrimidines, strobilurins, sulfamides, triazines, triazoles, etc.) in n-hexane/water and n-hexane/acetonitrile systems was investigated at 25°C. Distribution constants of pesticides (P) have been calculated as ratio of pesticide concentration in n-hexane to its concentration in water or acetonitrile phase. HPLC and GC methods were used for pesticides determination in phases. It was found that the overwhelming majority of pesticides are hydrophobic, i.e. in n-hexane/water system LgP≫0, and the difference in LgP values can reach 9.1 units. Replacement of water for acetonitrile leads to dramatic fall of LgP values reaching 9.5 units. The majority of LgP values in this case are negative and their differences is strongly leveled in comparison with a hexane/water system. Thus, maximal difference in pesticides LgP values for n-hexane/acetonitrile system is 3.2 units. It is shown that n-hexane can be used for selective and efficient extraction and preconcentration of pesticides from water matrices. On the other hand, acetonitrile is effective for the isolation and preconcentration of pesticides from hydrocarbon and vegetable oil matrices. The distribution constants described in the paper may be effectively used for the estimation of possibilities of extraction isolation, preconcentration and separation of pesticides. Copyright © 2013 Elsevier B.V. All rights reserved.

Conversion of methanol to propylene over hierarchical HZSM-5: the effect of Al spatial distribution.

PubMed

Li, Jianwen; Ma, Hongfang; Chen, Yan; Xu, Zhiqiang; Li, Chunzhong; Ying, Weiyong

2018-06-08

Different silicon sources caused diverse Al spatial distribution in HZSM-5, and this affected the hierarchical structures and catalytic performance of desilicated zeolites. After being treated with 0.1 M NaOH, HZSM-5 zeolites synthesized with silica sol exhibited relatively widely distributed mesopores and channels, and possessed highly improved propylene selectivity and activity stability.

Understanding of carbon-based supercapacitors ageing mechanisms by electrochemical and analytical methods

NASA Astrophysics Data System (ADS)

Liu, Yinghui; Soucaze-Guillous, Benoît; Taberna, Pierre-Louis; Simon, Patrice

2017-10-01

In order to shed light on ageing mechanisms of Electrochemical Double Layer Capacitor (EDLC), two kinds of activated carbons are studied in tetraethyl ammonium tetrafluoroborate (Et4NBF4) in acetonitrile. In floating mode, it turns out that two different ageing mechanisms are observed, depending on the activated carbon electrode materials used. On one hand, carbon A exhibits a continuous capacitance and series resistance fall-off; on the other hand, for carbon B, only the series resistance degrades after ageing while the capacitance keeps unchanged. Additional electrochemical characterizations (Electrochemical Impedance Spectroscopy - EIS - and diffusion coefficient calculations) were carried out showing that carbon A's ageing behavior is suspected to be primarily related to the carbon degradation while for carbon B a passivation occurs leading to the formation of a Solid Electrolyte Interphase-Like (SEI-L) film. These hypotheses are supported by TG-IR and Raman spectroscopy analysis. The outcome forms the latter is an increase of carbon defects on carbon A on positive electrode.

Pyrolytic synthesis and characterization of N-doped carbon nanoflakes for electrochemical applications

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

Savilov, S.V., E-mail: savilov@chem.msu.ru; N.S. Kurnakov Institute of General and Inorganic Chemistry Of Russian Academy of Sciences, Leninsky avenue, 31, Moscow 119991; Arkhipova, E.A.

2015-09-15

Highlights: • Carbon nanoflakes doped with nitrogen were produced by a pyrolytic technique. • Quarternary, pyrrolic and pyridinic types of nitrogen are confirmed by XPS. • Nitrogen content depends on precursor used and temperature processed. • Specific surface area values decrease with increasing of synthesis duration. • N-doped carbon nanoflakes may be suitable for electrochemical applications. - Abstract: Nitrogen doped carbon nanoflakes, which are very important for many electrochemical applications, were synthesized by pyrolysis of nitrogen containing organic compounds over metal oxide template. Acetonitrile, pyridine and butylamine, which are of different volatility were tested as N-containing precursors. Morphology, structure andmore » chemical composition of the as-synthesized materials were investigated by scanning electron microscopy (SEM), high resolution transmission electron microscopy (TEM), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). It was found that materials are highly defective and consist of a few malformed graphene layers. X-ray photoelectron spectra reflect the dominant graphitic and pyridinic N-bonding configuration. It was also noted that specific surface area depends on the duration and temperature of the reaction. Increase in duration and temperature led to decrease of the specific surface area from 1000 to 160 m{sup 2}/g, 1170 to 210 m{sup 2}/g and 1180 to 480 m{sup 2}/g for acetonitrile, butylamine and pyridine precursors, respectively.« less

Chirality recognition in the glycidol···propylene oxide complex: a rotational spectroscopic study.

PubMed

Thomas, Javix; Sunahori, Fumie X; Borho, Nicole; Xu, Yunjie

2011-04-11

Chirality recognition in the hydrogen-bonded glycidol···propylene oxide complex has been studied by using rotational spectroscopy and ab initio calculations. An extensive conformational search has been performed for this binary adduct at the MP2/6-311++G(d,p) level of theory and a total of 28 homo- and heterochiral conformers were identified. The eight binary conformers, built of the two dominant glycidol monomeric conformers, g-G+ and g+G-, were predicted to be the most stable ones. Jet-cooled rotational spectra of six out of the eight conformers were observed and unambiguously assigned for the first time. The experimental stability ordering has been obtained and compared with the ab initio predictions. The relative stability of the two dominant glycidol monomeric conformers is reversed in some cases when binding to propylene oxide. The contributions of monomeric energy, deformation energy, and binary intermolecular interaction energy to the relative stability of the binary conformers are discussed. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Confocal Raman microscopy and multivariate statistical analysis for determination of different penetration abilities of caffeine and propylene glycol applied simultaneously in a mixture on porcine skin ex vivo.

PubMed

Mujica Ascencio, Saul; Choe, ChunSik; Meinke, Martina C; Müller, Rainer H; Maksimov, George V; Wigger-Alberti, Walter; Lademann, Juergen; Darvin, Maxim E

2016-07-01

Propylene glycol is one of the known substances added in cosmetic formulations as a penetration enhancer. Recently, nanocrystals have been employed also to increase the skin penetration of active components. Caffeine is a component with many applications and its penetration into the epidermis is controversially discussed in the literature. In the present study, the penetration ability of two components - caffeine nanocrystals and propylene glycol, applied topically on porcine ear skin in the form of a gel, was investigated ex vivo using two confocal Raman microscopes operated at different excitation wavelengths (785nm and 633nm). Several depth profiles were acquired in the fingerprint region and different spectral ranges, i.e., 526-600cm(-1) and 810-880cm(-1) were chosen for independent analysis of caffeine and propylene glycol penetration into the skin, respectively. Multivariate statistical methods such as principal component analysis (PCA) and linear discriminant analysis (LDA) combined with Student's t-test were employed to calculate the maximum penetration depths of each substance (caffeine and propylene glycol). The results show that propylene glycol penetrates significantly deeper than caffeine (20.7-22.0μm versus 12.3-13.0μm) without any penetration enhancement effect on caffeine. The results confirm that different substances, even if applied onto the skin as a mixture, can penetrate differently. The penetration depths of caffeine and propylene glycol obtained using two different confocal Raman microscopes are comparable showing that both types of microscopes are well suited for such investigations and that multivariate statistical PCA-LDA methods combined with Student's t-test are very useful for analyzing the penetration of different substances into the skin. Copyright © 2016 Elsevier B.V. All rights reserved.

Iodide-Photocatalyzed Reduction of Carbon Dioxide to Formic Acid with Thiols and Hydrogen Sulfide.

PubMed

Berton, Mateo; Mello, Rossella; González-Núñez, María Elena

2016-12-20

The photolysis of iodide anions promotes the reaction of carbon dioxide with hydrogen sulfide or thiols to quantitatively yield formic acid and sulfur or disulfides. The reaction proceeds in acetonitrile and aqueous solutions, at atmospheric pressure and room temperature by irradiation using a low-pressure mercury lamp. This transition-metal-free photocatalytic process for CO 2 capture coupled with H 2 S removal may have been relevant as a prebiotic carbon dioxide fixation. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effects of propylene glycol on the metabolic status and milk production of dairy buffaloes.

PubMed

Hussein, H A; Abdel-Raheem, S M; Abd-Allah, M; Senosy, W

2015-01-01

The study was designed to investigate the effects of drenching with propylene glycol (PG) on body condition, serum metabolites and milk production during the transition period of dairy buffaloes. Animals were randomly allocated to a control group (n=5) and a PG group of 10 buffaloes that were drenched with 500 ml of propylene glycol once daily from 10 (9±3) days prepartum until 2 weeks postpartum. Ultrasound measurements of backfat thickness (BFT) were performed weekly, while blood samples were taken at -4, -2, 2, 4, 6, and 8 weeks from parturition for estimation of hematological and biochemical metabolites. At -4, -3, and -2 weeks from calving, BFT did not differ between the two groups, but decreased after calving and was higher for the control group than the PG group at weeks -1 and 1. Hematological analysis revealed insignificant changes between the two groups. Serum concentrations of non-esterified fatty acids (NEFA), β-hydroxybutyric acid (BHBA) and glucose did not differ between the two groups before parturition. At 2 and 4 weeks from parturition, NEFA was higher for the control group than the PG group. Serum concentrations of BHBA were higher at 2, 4, 6, and 8 weeks in control animals than in treated buffaloes. In contrast, the glucose level was significantly increased in PG group when compared to the control group at week 2 postpartum (p<0.05). Serum concentrations of total cholesterol, triglycerides, total proteins, albumin, and globulins did not differ significantly between the two groups (p>0.05). Serum enzyme activities of aspartate aminotransferase and γ-glutamyl transferase were significantly higher in the control than in the PG group. In treated buffaloes significantly (p<0.05) higher average 60-day milk yields were recorded (8.4±0.22 vs. 10.7±0.40 kg/day). Milk composition did not differ between the two groups. Drenching of dairy buffaloes with propylene glycol may reduce the risk of ketosis, improve the metabolic status, and increase the milk

Ultrafast studies of excess electrons in liquid acetonitrile: revisiting the solvated electron/solvent dimer anion equilibrium.

PubMed

Doan, Stephanie C; Schwartz, Benjamin J

2013-04-25

We examine the ultrafast relaxation dynamics of excess electrons injected into liquid acetonitrile using air- and water-free techniques and compare our results to previous work on this system [Xia, C. et al. J. Chem. Phys. 2002, 117, 8855]. Excess electrons in liquid acetonitrile take on two forms: a "traditional" solvated electron that absorbs in the near-IR, and a solvated molecular dimer anion that absorbs weakly in the visible. We find that excess electrons initially produced via charge-transfer-to-solvent excitation of iodide prefer to localize as solvated electrons, but that there is a subsequent equilibration to form the dimer anion on an ~80 ps time scale. The spectral signature of this interconversion between the two forms of the excess electron is a clear isosbestic point. The presence of the isosbestic point makes it possible to fully deconvolute the spectra of the two species. We find that solvated molecular anion absorbs quite weakly, with a maximum extinction coefficient of ~2000 M(-1)cm(-1). With the extinction coefficient of the dimer anion in hand, we are also able to determine the equilibrium constant for the two forms of excess electron, and find that the molecular anion is favored by a factor of ~4. We also find that relatively little geminate recombination takes place, and that the geminate recombination that does take place is essentially complete within the first 20 ps. Finally, we show that the presence of small amounts of water in the acetonitrile can have a fairly large effect on the observed spectral dynamics, explaining the differences between our results and those in previously published work.

Through-plane conductivities of membranes for nonaqueous redox flow batteries

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

Anderson, Travis Mark; Small, Leo J.; Pratt, III, Harry D.

In this study, nonaqueous redox flow batteries (RFB) leverage nonaqueous solvents to enable higher operating voltages compared to their aqueous counterparts. Most commercial components for flow batteries, however, are designed for aqueous use. One critical component, the ion-selective membrane, provides ionic conductance between electrodes while preventing crossover of electroactive species. Here we evaluate the area-specific conductances and through-plane conductivities of commercially available microporous separators (Celgard 2400, 2500) and anion exchange membranes (Neosepta AFX, Neosepta AHA, Fumasep FAP-450, Fumasep FAP-PK) soaked in acetonitrile, propylene carbonate, or two imidazolium-based ionic liquids. Fumasep membranes combined with acetonitrile-based electrolyte solutions provided the highest conductancemore » values and conductivities by far. When tested in ionic liquids, all anion exchange membranes displayed conductivities greater than those of the Celgard microporous separators, though the separators’ decreased thickness-enabled conductances on par with the most conductive anion exchange membranes. Ionic conductivity is not the only consideration when choosing an anion exchange membrane; testing of FAP-450 and FAP-PK membranes in a nonaqueous RFB demonstrated that the increased mechanical stability of PEEK-supported FAP-PK minimized swelling, in turn decreasing solvent mediated crossover and enabling greater electrochemical yields (40% vs. 4%) and Coulombic efficiencies (94% vs. 90%) compared to the unsupported, higher conductance FAP-450.« less

Through-plane conductivities of membranes for nonaqueous redox flow batteries

DOE PAGES

Anderson, Travis Mark; Small, Leo J.; Pratt, III, Harry D.; ...

2015-08-13

In this study, nonaqueous redox flow batteries (RFB) leverage nonaqueous solvents to enable higher operating voltages compared to their aqueous counterparts. Most commercial components for flow batteries, however, are designed for aqueous use. One critical component, the ion-selective membrane, provides ionic conductance between electrodes while preventing crossover of electroactive species. Here we evaluate the area-specific conductances and through-plane conductivities of commercially available microporous separators (Celgard 2400, 2500) and anion exchange membranes (Neosepta AFX, Neosepta AHA, Fumasep FAP-450, Fumasep FAP-PK) soaked in acetonitrile, propylene carbonate, or two imidazolium-based ionic liquids. Fumasep membranes combined with acetonitrile-based electrolyte solutions provided the highest conductancemore » values and conductivities by far. When tested in ionic liquids, all anion exchange membranes displayed conductivities greater than those of the Celgard microporous separators, though the separators’ decreased thickness-enabled conductances on par with the most conductive anion exchange membranes. Ionic conductivity is not the only consideration when choosing an anion exchange membrane; testing of FAP-450 and FAP-PK membranes in a nonaqueous RFB demonstrated that the increased mechanical stability of PEEK-supported FAP-PK minimized swelling, in turn decreasing solvent mediated crossover and enabling greater electrochemical yields (40% vs. 4%) and Coulombic efficiencies (94% vs. 90%) compared to the unsupported, higher conductance FAP-450.« less

Evaluation of Propylene Glycol-Based Fluids for Constellation Habitats and Vehicles

NASA Technical Reports Server (NTRS)

Lee, Steve

2009-01-01

Two fluid life tests have been conducted to evaluate propylene glycol-based fluids for use in Constellation habitats and vehicles. The first test was conducted from November 2008 to January 2009 to help determine the compatibility of the propylene glycol-based fluid selected for Orion at the time. When the first test uncovered problems with the fluid selection, an investigation and selection of a new fluid were conducted. A second test was started in March 2010 to evaluate the new selection. For the first test, the fluid was subjected to a thermal fluid loop that had flight-like properties, as compared to Orion. The fluid loop had similar wetted materials, temperatures, flow rates, and aluminum wetted surface area to fluid volume ratio. The test was designed to last for 10 years, the life expectancy of the lunar habitat. However, the test lasted less than two months. System filters became clogged with precipitate, rendering the fluid system inoperable. Upon examination of the precipitate, it was determined that the precipitate composition contained aluminum, which could have only come from materials in the test stand, as aluminum is not part of the original fluid composition. Also, the fluid pH was determined to have increased from 10.1, at the first test sample, to 12.2, at the completion of the test. This high of a pH is corrosive to aluminum and was certainly a contributing factor to the development of precipitate. Due to the problems encountered during this test, the fluid was rejected as a coolant candidate for Orion. A new propylene glycol-based fluid was selected by the Orion project for use in the Orion vehicle. The Orion project has conducted a series of screening tests to help verify that there will be no problems with the new fluid selection. To compliment testing performed by the Orion project team, a new life test was developed to test the new fluid. The new test bed was similar to the original test bed, but with some improvements based on experience

Hydrogenolysis of 5-carbon sugars, sugar alcohols, and other methods and compositions for reactions involving hydrogen

DOEpatents

Werpy, Todd A [West Richland, WA; Zacher, Alan H [Kennewick, WA

2002-11-12

Methods and compositions for reactions of hydrogen over a Re-containing catalyst with compositions containing a 5-carbon sugar, sugar alcohol, or lactic acid are described. It has been surprisingly discovered that reaction with hydrogen over a Re-containing multimetallic catalyst resulted in superior conversion and selectivity to desired products such as propylene glycol. A process for the synthesis of PG from lactate or lactic acid is also described.

Synthesis of Metal Nanoparticles and Metal Fluoride Nanoparticles from Metal Amidinate Precursors in 1-Butyl-3-Methylimidazolium Ionic Liquids and Propylene Carbonate.

PubMed

Schütte, Kai; Barthel, Juri; Endres, Manuel; Siebels, Marvin; Smarsly, Bernd M; Yue, Junpei; Janiak, Christoph

2017-02-01

Decomposition of transition-metal amidinates [M{MeC(N i Pr) 2 } n ] [M(AMD) n ; M=Mn II , Fe II , Co II , Ni II , n= 2; Cu I , n= 1) induced by microwave heating in the ionic liquids (ILs) 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIm][BF 4 ]), 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIm][PF 6 ]), 1-butyl-3-methylimidazolium trifluoromethanesulfonate (triflate) ([BMIm][TfO]), and 1-butyl-3-methylimidazolium tosylate ([BMIm][Tos]) or in propylene carbonate (PC) gives transition-metal nanoparticles (M-NPs) in non-fluorous media (e.g. [BMIm][Tos] and PC) or metal fluoride nanoparticles (MF 2 -NPs) for M=Mn, Fe, and Co in [BMIm][BF 4 ]. FeF 2 -NPs can be prepared upon Fe(AMD) 2 decomposition in [BMIm][BF 4 ], [BMIm][PF 6 ], and [BMIm][TfO]. The nanoparticles are stable in the absence of capping ligands (surfactants) for more than 6 weeks. The crystalline phases of the metal or metal fluoride synthesized in [BMIm][BF 4 ] were identified by powder X-ray diffraction (PXRD) to exclusively Ni- and Cu-NPs or to solely MF 2 -NPs for M=Mn, Fe, and Co. The size and size dispersion of the nanoparticles were determined by transmission electron microscopy (TEM) to an average diameter of 2(±2) to 14(±4) nm for the M-NPs, except for the Cu-NPs in PC, which were 51(±8) nm. The MF 2 -NPs from [BMIm][BF 4 ] were 15(±4) to 65(±18) nm. The average diameter from TEM is in fair agreement with the size evaluated from PXRD with the Scherrer equation. The characterization was complemented by energy-dispersive X-ray spectroscopy (EDX). Electrochemical investigations of the CoF 2 -NPs as cathode materials for lithium-ion batteries were simply evaluated by galvanostatic charge/discharge profiles, and the results indicated that the reversible capacity of the CoF 2 -NPs was much lower than the theoretical value, which may have originated from the complex conversion reaction mechanism and residue on the surface of the nanoparticles.

Highly crystalline lithium titanium oxide sheets coated with nitrogen-doped carbon enable high-rate lithium-ion batteries.

PubMed

Han, Cuiping; He, Yan-Bing; Li, Baohua; Li, Hongfei; Ma, Jun; Du, Hongda; Qin, Xianying; Yang, Quan-Hong; Kang, Feiyu

2014-09-01

Sheets of Li4Ti5O12 with high crystallinity are coated with nitrogen-doped carbon (NC-LTO) using a controlled process, comprising hydrothermal reaction followed by chemical vapor deposition (CVD). Acetonitrile (CH3 CN) vapor is used as carbon and nitrogen source to obtain a thin coating layer of nitrogen-doped carbon. The layer enables the NC-LTO material to maintain its sheet structure during the high-temperature CVD process and to achieve high crystallinity. Doping with nitrogen introduces defects into the carbon coating layer, and this increased degree of disorder allows fast transportation of lithium ions in the layer. An electrode of NC-LTO synthesized at 700 °C exhibits greatly improved rate and cycling performance due to a markedly decreased total cell resistance and enhanced Li-ion diffusion coefficient (D(Li)). Specific capacities of 159.2 and 145.8 mA h g(-1) are obtained using the NC-LTO sheets, at charge/discharge rates of 1 and 10 C, respectively. These values are much higher than values for LTO particles did not undergo the acetonitrile CVD treatment. A capacity retention value as high as 94.7% is achieved for the NC-LTO sheets after 400 cycles in a half-cell at 5 C discharge rate. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A special method for analyzing anisotropic nuclear magnetic resonance parameters: Acetonitrile in liquid crystals

NASA Astrophysics Data System (ADS)

Lounila, Juhani; Ala-Korpela, Mika; Jokisaari, Jukka

1990-12-01

A reliable analysis of the nuclear magnetic resonance (NMR) spectral parameters of partially oriented molecules requires the calculation of the effects of the correlation between the molecular vibration and rotation. However, in many cases the information content of the spectral data is not sufficient for an unambiguous determination of all the adjustable parameters involved in such an analysis. The present paper describes a special method to simplify the analysis significantly, so as to make seemingly underdetermined problems solvable. The method is applicable to the molecules which contain segments composed of one or more light bonds attached to a heavier bond. It is applied to the anisotropic couplings Dij of acetonitrile (CH3CN) oriented in various liquid crystals. The analysis leads to the following rα geometry: ∠HCH=109.22°±0.06°, rCH/rCC =0.751±0.002 and rCN/rCC =0.788±0.005. In addition, detailed information on (1) the indirect coupling anisotropies ΔJCC and 2ΔJCN, (2) the 1H and 13C chemical shift anisotropies, (3) the external torques acting on the CH bonds, and (4) the orientational order parameters of the CH3C segment of the acetonitrile molecule is obtained.

Potential harmful health effects of inhaling nicotine-free shisha-pen vapor: a chemical risk assessment of the main components propylene glycol and glycerol.

PubMed

Kienhuis, Anne S; Soeteman-Hernandez, Lya G; Bos, Peter Mj; Cremers, Hans Wjm; Klerx, Walther N; Talhout, Reinskje

2015-01-01

A shisha-pen is an electronic cigarette variant that is advertised to mimic the taste of a water pipe, or shisha. The aim of this study was to assess the potential harmful health effects caused by inhaling the vapor of a nicotine-free shisha-pen. Gas chromatography analysis was performed to determine the major components in shisha-pen vapor. Risk assessment was performed using puff volumes of e-cigarettes and "normal" cigarettes and a 1-puff scenario (one-time exposure). The concentrations that reached the airways and lungs after using a shisha-pen were calculated and compared to data from published toxicity studies. The main components in shisha-pen vapor are propylene glycol and glycerol (54%/46%). One puff (50 to 70 mL) results in exposure of propylene glycol and glycerol of 430 to 603 mg/m(3) and 348 to 495 mg/m(3), respectively. These exposure concentrations were higher than the points of departure for airway irritation based on a human study (propylene glycol, mean concentration of 309 mg/m(3)) and a rat study (glycerol, no-observed adverse effect level of 165 mg/m(3)). Already after one puff of the shisha-pen, the concentrations of propylene glycol and glycerol are sufficiently high to potentially cause irritation of the airways. New products such as the shisha-pen should be detected and risks should be assessed to inform regulatory actions aimed at limiting potential harm that may be caused to consumers and protecting young people to take up smoking.

Probing potential Li-ion battery electrolyte through first principles simulation of atomic clusters

NASA Astrophysics Data System (ADS)

Kushwaha, Anoop Kumar; Sahoo, Mihir Ranjan; Nayak, Saroj

2018-04-01

Li-ion battery has wide area of application starting from low power consumer electronics to high power electric vehicles. However, their large scale application in electric vehicles requires further improvement due to their low specific power density which is an essential parameter and is closely related to the working potential windows of the battery system. Several studies have found that these parameters can be taken care of by considering different cathode/anode materials and electrolytes. Recently, a unique approach has been reported on the basis of cluster size in which the use of Li3 cluster has been suggested as a potential component of the battery electrode material. The cluster based approach significantly enhances the working electrode potential up to 0.6V in the acetonitrile solvent. In the present work, using ab-initio quantum chemical calculation and the dielectric continuum model, we have investigated various dielectric solvent medium for the suitable electrolyte for the potential component Li3 cluster. This study suggests that high dielectric electrolytic solvent (ethylene carbonate and propylene carbonate) could be better for lithium cluster due to improvement in the total electrode potential in comparison to the other dielectric solvent.

A novel strategy for acetonitrile wastewater treatment by using a recombinant bacterium with biofilm-forming and nitrile-degrading capability.

PubMed

Li, Chunyan; Yue, Zhenlei; Feng, Fengzhao; Xi, Chuanwu; Zang, Hailian; An, Xuejiao; Liu, Keran

2016-10-01

There is a great need for efficient acetonitrile removal technology in wastewater treatment to reduce the discharge of this pollutant in untreated wastewater. In this study, a nitrilase gene (nit) isolated from a nitrile-degrading bacterium (Rhodococcus rhodochrous BX2) was cloned and transformed into a biofilm-forming bacterium (Bacillus subtilis N4) that expressed the recombinant protein upon isopropylthio-β-galactoside (IPTG) induction. The recombinant bacterium (B. subtilis N4-pHT01-nit) formed strong biofilms and had nitrile-degrading capability. Further testing demonstrated that biofilms formed by B. subtilis N4-pHT01-nit were highly resistant to loading shock from acetonitrile and almost completely degraded the initial concentration of acetonitrile (800 mg L(-1)) within 24 h in a moving bed biofilm reactor (MBBR) after operation for 35 d. The bacterial composition of the biofilm, identified by high-throughput sequencing, in a reactor in which the B. subtilis N4-pHT01-nit bacterium was introduced indicated that the engineered bacterium was successfully immobilized in the reactor and became dominant genus. This work demonstrates that an engineered bacterium with nitrile-degrading and biofilm-forming capacity can improve the degradation of contaminants in wastewater. This approach offers a novel strategy for enhancing the biological oxidation of toxic pollutants in wastewater. Copyright © 2016 Elsevier Ltd. All rights reserved.

Environmental Compliance Assessment System (ECAS). South Carolina Supplement. U.S. Army

DTIC Science & Technology

1994-04-01

Cyanamide. 156627 2.50 Captan 133062 25.00 Carbaryl 63252 25.00 Carbon Disulfide 75150 150.00 Carbon Tetrachloride 56235 150.00. Carbonyl Sulfide...1120714 + b-Propiolactone 57578 7.50 Propoxur 114261 2.50 Propylene Dichloride 78875 1750.00 1,2 Propylene Oxide 75569 250.00 Propylenimine (1,2

Mechanochemistry-assisted synthesis of hierarchical porous carbons applied as supercapacitors

PubMed Central

Leistenschneider, Desirée; Jäckel, Nicolas; Hippauf, Felix; Presser, Volker

2017-01-01

A solvent-free synthesis of hierarchical porous carbons is conducted by a facile and fast mechanochemical reaction in a ball mill. By means of a mechanochemical ball-milling approach, we obtained titanium(IV) citrate-based polymers, which have been processed via high temperature chlorine treatment to hierarchical porous carbons with a high specific surface area of up to 1814 m2 g−1 and well-defined pore structures. The carbons are applied as electrode materials in electric double-layer capacitors showing high specific capacitances with 98 F g−1 in organic and 138 F g−1 in an ionic liquid electrolyte as well as good rate capabilities, maintaining 87% of the initial capacitance with 1 M TEA-BF4 in acetonitrile (ACN) and 81% at 10 A g−1 in EMIM-BF4. PMID:28781699

Sorption of adamantane phenylamide derivatives on hyper-cross-linked polystyrene from water-acetonitrile eluents

NASA Astrophysics Data System (ADS)

Shafigulin, R. V.; Konstantinov, A. V.; Bulanova, A. V.; Il'in, M. M.; Davankov, V. A.

2016-11-01

Study of the main physicochemical features of the sorption of phenylamide adamantane derivatives on hyper-cross-linked polystyrene from water-acetonitrile solutions shows that both hydrophobic and electronic interactions make a large contribution to retention, especially for a chlorine-containing derivative in which there are π- p and π- d interactions between the outer-shell electrons of the chlorine atom in addition to π- π interactions between aromatic fragments of the sorbate and sorbent.

Effect of gamma irradiation on ethylene propylene diene terpolymer rubber composites

NASA Astrophysics Data System (ADS)

Abou Zeid, M. M.; Rabie, S. T.; Nada, A. A.; Khalil, A. M.; Hilal, R. H.

2008-01-01

Composites of ethylene propylene dine terpolymer rubber (EPDM), high density polyethylene (HDPE) and ground tire rubber powder (GTR) at different ratios were subjected to gamma irradiation at various doses up to 250 kGy. The physical, mechanical and thermal properties were investigated as a function of irradiation dose and blend composition. Gamma irradiation led to a significant improvement in the properties for all blend compositions. The results indicate that the improvement in properties is inversely proportional to the substituted ratio of GTR, attributed to the development of an interfacial adhesion between GTR and blend components. The results were confirmed by examining the fracture surfaces by scanning electron microscopy.

Molecular Simulation Results on Charged Carbon Nanotube Forest-Based Supercapacitors.

PubMed

Muralidharan, Ajay; Pratt, Lawrence R; Hoffman, Gary G; Chaudhari, Mangesh I; Rempe, Susan B

2018-06-22

Electrochemical double-layer capacitances of charged carbon nanotube (CNT) forests with tetraethyl ammonium tetrafluoro borate electrolyte in propylene carbonate are studied on the basis of molecular dynamics simulation. Direct molecular simulation of the filling of pore spaces of the forest is feasible even with realistic, small CNT spacings. The numerical solution of the Poisson equation based on the extracted average charge densities then yields a regular experimental dependence on the width of the pore spaces, in contrast to the anomalous pattern observed in experiments on other carbon materials and also in simulations on planar slot-like pores. The capacitances obtained have realistic magnitudes but are insensitive to electric potential differences between the electrodes in this model. This agrees with previous calculations on CNT forest supercapacitors, but not with experiments which have suggested electrochemical doping for these systems. Those phenomena remain for further theory/modeling work. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Environmental Compliance Assessment and Management Program (ECAMP), South Carolina Supplement

DTIC Science & Technology

1994-04-01

Carbaryl 63252 25.00 Carbon Disulfide 75150 150.00 Carbon Tetrachloride 56235 150.00. Carbonyl Sulfide 463581 12250.00 Catechol 120809 297.00...7.50 Propoxur H4261 2.50 Propylene Dichloride 78875 1750.00 1.2 Propylene Oxide 75569 250.00 Propylenimine (1.2-) 75558 23.35 Pyrethrin 1 121211 25(X

Carbon deposition in the Bosch process with ruthenium and ruthenium-iron alloy catalysts. M.S. Thesis. Final Report, Jan. 1981 - Jul. 1982

NASA Technical Reports Server (NTRS)

Manning, M. P.; Reid, R. C.; Sophonpanich, C.

1982-01-01

The effectiveness of ruthenium and the alloys 50Ru50Fe and 33Ru67Fe as alternatives to iron, nickel, and cobalt catalysts in recovering oxygen from metabolic carbon dioxide was investigated. Carbon deposition boundaries over the unsupported alloys are reported. Experiments were also carried out over 50Ru50Fe and 97Ru3Fe3 catalysts supported on gamma-alumina to determine their performance in the synthesis of low molecular weight olefins. High production of ethylene and propylene would be beneficial for an improvement of an overall Bosch process, as a gas phase containing high olefin content would enhance carbon deposition in a Bosch reactor.

Maintenance of storage properties of pediatric aliquots of apheresis platelets in fluoroethylene propylene containers.

PubMed

Skripchenko, Andrey; Myrup, Andrew; Thompson-Montgomery, Dedeene; Awatefe, Helen; Wagner, Stephen J

2013-04-01

Platelet (PLT) aliquots for pediatric use have been shown to retain in vitro properties when stored in gas-impermeable syringes for up to 6 hours. As an alternative, PLT aliquots can be stored for longer periods in containers used for storage of whole blood-derived PLTs. These containers are not available separate from whole blood collection sets and PLT volumes less than 35 mL either have not been evaluated or may be unsuitable for PLT storage. Gas-permeable fluoroethylene propylene (FEP) containers have been used in the storage of cell therapy preparations and are available in multiple sizes as single containers but have not been evaluated for PLT storage. A single apheresis unit was divided on Day 3 into small aliquots with volume ranging from 20 to 60 mL, transferred using a sterile connection device, and stored for an additional 2 days either in CLX (control) or in FEP containers. PLT storage properties of PLTs stored in FEP containers were compared to those stored in CLX containers. Standard PLT in vitro assays were performed (n =6). PLT storage properties were either similar to those of CLX containers or differed by less than 20% excepting carbon dioxide levels, which varied less than 60%. Pediatric PLT aliquots of 20, 30, and 60mL transferred on Day 3 into FEP cell culture containers adequately maintain PLT properties for an additional 2days of storage. © 2012 American Association of Blood Banks.

Effect of multi-walled carbon nanotubes aspect ratio and temperature on the dielectric behavior of alternating alkene-carbon monoxide polyketone nanocomposites

NASA Astrophysics Data System (ADS)

Abu-Surrah, Adnan S.; Abdul Jawad, Saadi; Al-Ramahi, Esraa; Hallak, Awni B.; Khattari, Z.

2015-04-01

New alternating poly(propylene-alt-carbon monoxide/ethylene-alt-carbon monoxide) (PECO)/multiwalled carbon nanotubes (MWCNTs) composites have been prepared. Dielectric permittivity, electric modulus and ac conductivity of the isolated materials were investigated as a function of fiber aspect ratio, frequency and temperature. For aspect ratio of 30 and 200, a transition from insulator to semiconductor was observed at frequency 1×104. However, for high aspect ratio sample (660), no transition was observed and the conductivity is frequency independent in the measured frequency range of 10-106 Hz. The conductivity increases from about 1×10-4 for the sample that contain fibers of aspect ratio 30 and reaches 5×10-2 (Ω m)-1 for aspect ratio was 660. This behavior can be modeled by a circuit that consists of a contact resistance in series with a parallel combination of resistance (R) and capacitance (C). The calculated activation energy for sample filled with fibers having aspect ratio 30 is about 0.26 eV and decreases to about 0.16 eV when the aspect ratio is 660.

Enantioselective complexation of chiral propylene oxide by an enantiopure water-soluble cryptophane.

PubMed

Bouchet, Aude; Brotin, Thierry; Linares, Mathieu; Ågren, Hans; Cavagnat, Dominique; Buffeteau, Thierry

2011-05-20

ECD and NMR experiments show that the complexation of propylene oxide (PrO) within the cavity of an enantiopure water-soluble cryptophane 1 in NaOH solution is enantioselective and that the (R)-PrO@PP-1 diastereomer is more stable than the (S)-PrO@PP-1 diastereomer with a free energy difference of 1.7 kJ/mol. This result has been confirmed by molecular dynamics (MD) and ab initio calculations. The enantioselectivity is preserved in LiOH and KOH solutions even though the binding constants decrease, whereas PrO is not complexed in CsOH solution.

Laboratory-scale evaluation of a combined soil amendment for the enhanced biodegradation of propylene glycol-based aircraft de-icing fluids.

PubMed

Libisch, Balázs; French, Helen K; Hartnik, Thomas; Anton, Attila; Biró, Borbála

2012-01-01

A combined soil amendment was tested in microcosm experiments with an aim to enhance the aerobic biodegradation of propylene glycol (PG)-based aircraft de-icing fluids during and following the infiltration of contaminated snowmelt. A key objective under field conditions is to increase degradation of organic pollutants in the surface soil where higher microbial activity and plant rhizosphere effects may contribute to a more efficient biodegradation of PG, compared to subsoil ground layers, where electron acceptors and nutrients are often depleted. Microcosm experiments were set up in Petri dishes using 50 g of soil mixed with appropriate additives. The samples contained an initial de-icing fluid concentration of 10,000 mg/kg soil. A combined amendment using calcium peroxide, activated carbon and 1 x Hoagland solution resulted in significantly higher degradation rates for PG both at 4 and 22 degrees C. Most probable numbers of bacteria capable of utilizing 10,000 mg/kg de-icing fluid as a sole carbon source were about two orders of magnitude higher in the amended soil samples compared to unamended controls at both temperatures. The elevated numbers of such bacteria in surface soil may be a source of cells transported to the subsoil by snowmelt infiltration. The near-surface application of amendments tested here may enhance the growth of plants and plant roots in the contaminated area, as well as microbes to be found at greater depth, and hence increase the degradation of a contaminant plume present in the ground.

Performance of Multi Walled Carbon Nanotubes Grown on Conductive Substrates as Supercapacitors Electrodes using Organic and Ionic liquid electrolytes

NASA Astrophysics Data System (ADS)

Winchester, Andrew; Ghosh, Sujoy; Turner, Ben; Zhang, X. F.; Talapatra, Saikat

2012-02-01

In this work we will present the use of Multi Walled Carbon Nanotubes (MWNT) directly grown on inconel substrates via chemical vapor deposition, as electrode materials for electrochemical double layer capacitors (EDLC). The performance of the MWNT EDLC electrodes were investigated using two electrolytes, an organic electrolyte, tetraethylammonium tetrafluoroborate in propylene carbonate (Et4NBF4 in PC), and a room temperature ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate (BMIM-PF6). Cyclic voltammetry, galvanostatic charge-discharge, and electrochemical impedance spectroscopy measurements to obtain values for the capacitance and internal resistance of these devices will be presented and compared.

Two-electron carbon dioxide reduction catalyzed by rhenium(I) bis(imino)acenaphthene carbonyl complexes.

PubMed

Portenkirchner, Engelbert; Kianfar, Elham; Sariciftci, Niyazi Serdar; Knör, Günther

2014-05-01

Rhenium(I) carbonyl complexes carrying substituted bis(arylimino)acenaphthene ligands (BIAN-R) have been tested as potential catalysts for the two-electron reduction of carbon dioxide. Cyclic voltammetric studies as well as controlled potential electrolysis experiments were performed using CO2-saturated solutions of the complexes in acetonitrile and acetonitrile-water mixtures. Faradaic efficiencies of more than 30 % have been determined for the electrocatalytic production of CO. The effects of ligand substitution patterns and water content of the reaction medium on the catalytic performance of the new catalysts are discussed. © 2014 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.

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

PubMed

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

2006-11-02

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

Large scale exact quantum dynamics calculations: Ten thousand quantum states of acetonitrile

NASA Astrophysics Data System (ADS)

Halverson, Thomas; Poirier, Bill

2015-03-01

'Exact' quantum dynamics (EQD) calculations of the vibrational spectrum of acetonitrile (CH3CN) are performed, using two different methods: (1) phase-space-truncated momentum-symmetrized Gaussian basis and (2) correlated truncated harmonic oscillator basis. In both cases, a simple classical phase space picture is used to optimize the selection of individual basis functions-leading to drastic reductions in basis size, in comparison with existing methods. Massive parallelization is also employed. Together, these tools-implemented into a single, easy-to-use computer code-enable a calculation of tens of thousands of vibrational states of CH3CN to an accuracy of 0.001-10 cm-1.

NH 3-SCR on Cu, Fe and Cu + Fe exchanged beta and SSZ-13 catalysts: Hydrothermal aging and propylene poisoning effects

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

Wang, Aiyong; Wang, Yilin; Walter, Eric D.

Cu, Fe and Cu + Fe ion exchanged Beta and SSZ-13 catalysts were prepared by solution ion exchange using commercial NH 4/Beta, and NH 4/SSZ-13 that was prepared in-house. To study hydrothermal aging effects, Beta supported catalysts were aged hydrothermally at 700 °C and SSZ-13 supported catalysts were aged at 750 °C. In order to reveal the effects of Fe addition in the co-exchanged catalysts, these catalysts were characterized by means of powder X-ray diffraction (XRD), N 2 adsorption-desorption, electron paramagnetic resonance (EPR), 27Al-nuclear magnetic resonance ( 27Al-NMR) and propylene coking followed with temperature programmed reaction (TPR), and further testedmore » with standard NH 3-SCR with and without the presence of propylene. Collectively, the catalyst characterizations and reaction testing indicated minor beneficial effects of Fe addition in Cu,Fe/Beta, where NH 3-SCR activity, N 2 selectivity and hydrothermal stability were all slightly improved. In contrast, Fe addition did not show apparent beneficial effects in low-temperature SCR for the Cu,Fe/SSZ-13 case. In conclusion, at elevated reaction temperatures, however, the presence of Fe indeed considerably improved NO conversion and N 2 selectivity for the hydrothermally aged Cu,Fe/SSZ-13 catalyst in the presence of propylene.« less

NH 3-SCR on Cu, Fe and Cu + Fe exchanged beta and SSZ-13 catalysts: Hydrothermal aging and propylene poisoning effects

DOE PAGES

Wang, Aiyong; Wang, Yilin; Walter, Eric D.; ...

2017-10-07

Cu, Fe and Cu + Fe ion exchanged Beta and SSZ-13 catalysts were prepared by solution ion exchange using commercial NH 4/Beta, and NH 4/SSZ-13 that was prepared in-house. To study hydrothermal aging effects, Beta supported catalysts were aged hydrothermally at 700 °C and SSZ-13 supported catalysts were aged at 750 °C. In order to reveal the effects of Fe addition in the co-exchanged catalysts, these catalysts were characterized by means of powder X-ray diffraction (XRD), N 2 adsorption-desorption, electron paramagnetic resonance (EPR), 27Al-nuclear magnetic resonance ( 27Al-NMR) and propylene coking followed with temperature programmed reaction (TPR), and further testedmore » with standard NH 3-SCR with and without the presence of propylene. Collectively, the catalyst characterizations and reaction testing indicated minor beneficial effects of Fe addition in Cu,Fe/Beta, where NH 3-SCR activity, N 2 selectivity and hydrothermal stability were all slightly improved. In contrast, Fe addition did not show apparent beneficial effects in low-temperature SCR for the Cu,Fe/SSZ-13 case. In conclusion, at elevated reaction temperatures, however, the presence of Fe indeed considerably improved NO conversion and N 2 selectivity for the hydrothermally aged Cu,Fe/SSZ-13 catalyst in the presence of propylene.« less

Effects of a single glucocorticoid injection on propylene glycol-treated cows with clinical ketosis.

PubMed

van der Drift, Saskia G A; Houweling, Martin; Bouman, Marina; Koets, Ad P; Tielens, Aloysius G M; Nielen, Mirjam; Jorritsma, Ruurd

2015-05-01

This study investigated the metabolic effects of glucocorticoids when administered to propylene glycol-treated cows with clinical ketosis. Clinical ketosis was defined by depressed feed intake and milk production, and a maximal score for acetoacetate in urine. All cows received 250 mL oral propylene glycol twice daily for 3 days and were randomly assigned to a single intramuscular injection with sterile isotonic saline solution (n = 14) or dexamethasone-21-isonicotinate (n = 17). Metabolic blood variables were monitored for 6 days and adipose tissue variables for 3 days. β-Hydroxybutyrate (BHBA) concentrations in blood decreased in all cows during treatment, but were lower in glucocorticoid-treated cows. Cows treated with glucocorticoids had higher plasma glucose and insulin concentrations, whereas concentrations of non-esterified fatty acids, 3-methylhistidine and growth hormone were unaffected. mRNA expression of hormone-sensitive lipase, BHBA receptor and peroxisome proliferator-activated receptor type γ in adipose tissue was not affected. This shows that lipolytic effects do not appear to be important in ketotic cows when glucocorticoids are combined with PG. Plasma 3-methyl histidine concentrations were similar in both groups, suggesting that glucocorticoids did not increase muscle breakdown and that the greater rise in plasma glucose in glucocorticoid-treated cows may not be due to increased supply of glucogenic amino acids from muscle. Copyright © 2015 Elsevier Ltd. All rights reserved.

Phosphoniums as catalysts for metal-free polymerization: Synthesis of well-defined poly(propylene oxide)

NASA Astrophysics Data System (ADS)

Zhang, Jie; Liu, Quan; Ren, Haojun; Zhang, Nanjie; Li, Pengfei; Yang, Kang

2017-11-01

The anionic ring-opening polymerization of propylene oxide (PO) was initiated with glycerol and catalyzed by three new synthetic phosphonium salts, tetrakis (pyrrolidino) phosphonium (Py4P1+), tetrakis (piperidino) phosphonium (Pi4P1+), tetrakis (morpholino) phosphonium (Mo4P1+), and the known tetrakis [cyclohexyl (methyl) amino] phosphonium (Cy4P1+) and tetrakis [tris (dimethylamino) phosphonoamino] phosphazene (P5+). The effects of substituents on the polymerization behavior, especially the molecular weight and its distribution, degree of unsaturation, and the sequential structures of poly (propylene oxide) (PPO) were investigated. The structures of these catalysts and PPOs were characterized by FT-IR, 1H and 13C NMR, and GPC. The results indicate that Cy4P1+, Py4P1+, and Pi4P1+ have lower optimum reaction temperatures at 90, 70, and 70 °C, respectively, and are better than traditional catalysts KOH and double metal cyanide. PPO samples with high molecular weight, narrow polydispersity, and high functionality were accessible when catalyzed with Cy4P1+, Pi4P1+, and P5+ at the optimum temperature. Notably, Pi4P1+ formed unimodal distribution PPO with 9000 g/mol, 2.93 of functionality, and 0.008 mmol/g degree of unsaturation. Majority segments of PPO from five catalysts adopted the stereoregular head-to-tail structure, exhibiting excellent regularity.

Mechanism of [m+h]+ formation in atmospheric pressure photoionization mass spectrometry: identification of propionitrile in acetonitrile with high mass accuracy measurement and tandem mass spectrometry and evidence for its involvement in the protonation phenomenon.

PubMed

Kamel, Amin; Jeanville, Patrick; Colizza, Kevin; J-Rivera, Lauren Elizabeth

2008-11-01

The role of propionitrile in the production of [M+H]+ under atmospheric pressure photoionization (APPI) was investigated. In dopant-assisted APPI using acetone and anisole, protonated acetone and anisole radical cations were the most prominent ions observed. In dopant-free or direct APPI in acetonitrile, however, a major ion in acetonitrile was detected and identified as propionitrile, using high accuracy mass measurement and collision induced dissociation studies. Vaporizing ca. 10(-5) M althiazide and bendroflumethazide under direct APPI in acetonitrile produced their corresponding protonated species [M+H]+. In addition to protonated acetonitrile, its dimers, and acetonitrile/water clusters, protonated propionitrile, propionitrile dimer, and propionitrile/water clusters were also observed. The role of propionitrile, an impurity in acetonitrile and/or a possible product of ion-molecule reaction, in the production of [M+H]+ of althiazide and bendroflumethazide was further investigated in the absence of dopant using propionitrile-d5. The formation of [M+D]+ species was observed, suggesting a possible role of propionitrile in the protonation process. Additionally, an increase in the [M+H]+ signal of althiazide and bendroflumethazide was observed as a function of propionitrile concentration in acetonitrile. Theoretical data from the literature supported the assumption that one possible mechanism, among others, for the formation of [M+H]+ could be attributed to photo-initiated isomerization of propionitrile. The most stable isomers of propionitrile, based on their calculated ionization energy (IE) and relative energy (DeltaE), were assumed to undergo proton transfer to the analytes, and mechanisms were proposed.

Molecular mechanism of carbon nanotube to activate Subtilisin Carlsberg in polar and non-polar organic media

NASA Astrophysics Data System (ADS)

Zhang, Liyun; Li, Yuzhi; Yuan, Yuan; Jiang, Yuanyuan; Guo, Yanzhi; Li, Menglong; Pu, Xuemei

2016-11-01

In the work, we mainly used molecular dynamics (MD) simulation and protein structure network (PSN) to study subtilisin Carlsberg (SC) immobilized onto carbon nanotube (CNT) in water, acetonitrile and heptane solvents, in order to explore activation mechanism of enzymes in non-aqueous media. The result indicates that the affinity of SC with CNT follows the decreasing order of water > acetonitrile > heptane. The overall structure of SC and the catalytic triad display strong robustness to the change of environments, responsible for the activity retaining. However, the distances between two β-strands of substrate-binding pocket are significantly expanded by the immobilization in the increasing order of water < acetonitrile < heptane, contributing to the highest substrate-binding energy in heptane media. PSN analysis further reveals that the immobilization enhances structural communication paths to the substrate-binding pocket, leading to its larger change than the free-enzymes. Interestingly, the increase in the number of the pathways upon immobilization is not dependent on the absorbed extent but the desorbed one, indicating significant role of shifting process of experimental operations in influencing the functional region. In addition, some conserved and important hot-residues in the paths are identified, providing molecular information for functional modification.

Micro-supercapacitors from carbide derived carbon (CDC) films on silicon chips

NASA Astrophysics Data System (ADS)

Huang, Peihua; Heon, Min; Pech, David; Brunet, Magali; Taberna, Pierre-Louis; Gogotsi, Yury; Lofland, Samuel; Hettinger, Jeffrey D.; Simon, Patrice

2013-03-01

Interdigitated on-chip micro-supercapacitors based on Carbide Derived Carbon (CDC) films were fabricated and tested. A titanium carbide (TiC) film was patterned and treated with chlorine to obtain a TiC derived carbon (TiC-CDC) film, followed by the deposition of two types of current collectors (Ti/Au and Al) using standard micro-fabrication processes. CDC based micro-supercapacitors were electrochemically characterized by cyclic voltammetry and impedance spectroscopy using a 1 M tetraethylammonium tetrafluoroborate, NEt4BF4, in propylene carbonate (PC) electrolyte. A capacitance of 0.78 mF for the device and 1.5 mF cm-2 as the specific capacitance for the footprint of the device was measured for a 2 V potential range at 100 mV s-1. A specific energy of 3.0 mJ cm-2 and a specific power of 84 mW cm-2 were calculated for the devices. These devices provide a pathway for fabricating pure carbon-based micro-supercapacitors by micro-fabrication, and can be used for powering micro-electromechanical systems (MEMS) and electronic devices.

Investigating effectiveness of activated carbons of natural sources on various supercapacitors

NASA Astrophysics Data System (ADS)

Faisal, Md. Shahnewaz Sabit; Rahman, Muhammad M.; Asmatulu, Ramazan

2016-04-01

Activated carbon can be produced from natural sources, such as pistachio and acorn shells, which can be an inexpensive and sustainable sources of natural wastes for the energy storage devices, such as supercapacitors. The carbonaceous materials used in this study were carbonized at the temperatures of 700°C and 900°C after the stabilization process at 240°C for two hours. These shells showed approximately 60% carbon yield. Carbonized nutshells were chemically activated using1wt% potassium hydroxide (KOH). Activated carbon powders with polyvinylidene fluoride (PVdF) were used to construct carbon electrodes. A 1M of tetraethylammonium tetrafluoroborate (TEABF4) and propylene carbonate (PC) were used as electrolytes. Electrochemical techniques, such as cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were used for the characterization of the supercapacitors. Scanning electron microscopy (SEM) was used to inspect the surface texture of the activated carbons. Activated pistachio shells carbonized at 700°C showed more porous surface texture than those carbonized at 900°C. Effects of the carbonization temperatures were studied for their electrochemical characteristics. The shells carbonized at 700°C showed better electrochemical characteristics compared to those carbonized at 900°C. The test results provided about 27,083 μF/g specific capacitance at a scan rate of 10mV/s. This study showed promising results for using these activated carbons produced from the natural wastes for supercapacitor applications.

On the structure of an aqueous propylene glycol solution.

PubMed

Rhys, Natasha H; Gillams, Richard J; Collins, Louise E; Callear, Samantha K; Lawrence, M Jayne; McLain, Sylvia E

2016-12-14

Using a combination of neutron diffraction and empirical potential structure refinement computational modelling, the interactions in a 30 mol. % aqueous solution of propylene glycol (PG), which govern both the hydration and association of this molecule in solution, have been assessed. From this work it appears that PG is readily hydrated, where the most prevalent hydration interactions were found to be through both the PG hydroxyl groups but also alkyl groups typically considered hydrophobic. Hydration interactions of PG dominate the solution over PG self-self interactions and there is no evidence of more extensive association. This hydration behavior for PG in solutions suggests that the preference of PG to be hydrated rather than to be self-associated may translate into a preference for PG to bind to lipids rather than itself, providing a potential explanation for how PG is able to enhance the apparent solubility of drug molecules in vivo.

On the structure of an aqueous propylene glycol solution

NASA Astrophysics Data System (ADS)

Rhys, Natasha H.; Gillams, Richard J.; Collins, Louise E.; Callear, Samantha K.; Lawrence, M. Jayne; McLain, Sylvia E.

2016-12-01

Using a combination of neutron diffraction and empirical potential structure refinement computational modelling, the interactions in a 30 mol. % aqueous solution of propylene glycol (PG), which govern both the hydration and association of this molecule in solution, have been assessed. From this work it appears that PG is readily hydrated, where the most prevalent hydration interactions were found to be through both the PG hydroxyl groups but also alkyl groups typically considered hydrophobic. Hydration interactions of PG dominate the solution over PG self-self interactions and there is no evidence of more extensive association. This hydration behavior for PG in solutions suggests that the preference of PG to be hydrated rather than to be self-associated may translate into a preference for PG to bind to lipids rather than itself, providing a potential explanation for how PG is able to enhance the apparent solubility of drug molecules in vivo.

Propylene epoxidation over biogenic Au/TS-1 catalysts by Cinnamomum camphora extract in the presence of H2 and O2

NASA Astrophysics Data System (ADS)

Du, Mingming; Huang, Jiale; Sun, Daohua; Li, Qingbiao

2016-03-01

The Au/TS-1 catalysts with different Au nanoparticles (NPs) sizes ranging from 3.1 to 8.4 nm but the same Au loading of 0.5 wt% were prepared by Cinnamomum camphora (CC) extract, and were used for propylene epoxidation. The results showed that the interaction between Au and TS-1 support surface is important for propylene epoxidation and much smaller Au NPs (<3 nm) are the dominant active sites. After reaction of 100 h, there is no decreasing in both the activity and the PO selectivity for the Au/TS-1 catalysts, and only 1.8 wt% of the carbonaceous deposits on the surface of the catalyst after reaction, suggesting that the desorption of the product from the modified catalysts surface by residual biomolecules is much easier.

Venting of a Water/Inhibited Propylene Glycol Mixture in a Vacuum Environment-Characterization and Representative Test Results

NASA Technical Reports Server (NTRS)

Ungar, Eugene K.; Erickson, Lisa R.

2011-01-01

A planned use of the Orion space vehicle involves its residence at the International Space Station for six months at a time. One concept of operations involves temporarily venting portions of the idle Orion active thermal control system (ATCS) during the docked phase, preventing freezing. The venting would have to be reasonably complete with few, if any, completely filled pockets of frozen liquid. Even if pockets of frozen liquid did not damage the hardware during the freezing process, they could prevent the system from filling completely prior to its reactivation. The venting of single component systems in a space environment has been performed numerous times and is well understood. Local nucleation occurs at warm, relatively massive parts of the system, which creates vapor and forces the bulk liquid out of the system. The remnants of the liquid will freeze, then evaporate over time through local heating. Because the Orion ATCS working fluid is a 50/50 mixture of water and inhibited propylene glycol, its boiling behavior was expected to differ from that of a pure fluid. It was thought that the relatively high vapor pressure water might evaporate preferentially, leaving behind a mixture enriched with the low vapor pressure propylene glycol, which would be vaporization ]resistant. Owing to this concern, a test was developed to compare the evaporation behavior of pure water, a 50/50 mixture of water and inhibited propylene glycol, and inhibited propylene glycol. The test was performed using room temperature fluids in an instrumented thin walled stainless steel vertical tube. The 1 in x 0.035 in wall tube was instrumented with surface thermocouples and encased in closed cell polyurethane foam. Reticulated polyurethane foam was placed inside the tube to reduce the convection currents. A vacuum system connected to the top of the tube set the pressure boundary condition. Tests were run for the three fluids at back pressures ranging from 1 to 18 torr. During each test

UV stabilization of wood by nano metal oxides dispersed in propylene glycol.

PubMed

Nair, Sreeja; Nagarajappa, Giridhar B; Pandey, Krishna K

2018-06-01

Nanoparticles of some of the metal oxides are known to have high UV protective efficiency. The UV filtering efficiency of nanoparticles invariably depends on their size and stability in the dispersion. In the present work, a stable dispersion of nanoparticles of three metal oxides, zinc oxide (ZnO), cerium oxide (CeO 2 ) and titanium dioxide (TiO 2 ), was prepared in propylene glycol (PG) using ultrasonication. The method is easy and useful as no additional surfactant or dispersant is needed. The particle size and its distribution was confirmed by Scanning Electron Microscopy and Dynamic Light Scattering. The stability of dispersion was assessed by UV-visible absorption spectroscopy. The UV stability of wood surfaces of Wrightia tinctoria coated with nanodispersions of ZnO, CeO 2 and TiO 2 was evaluated under laboratory conditions in an accelerated weathering tester. Changes in the colour and FTIR spectra of exposed specimens were measured periodically. Rapid colour darkening (yellowing) was observed in uncoated and PG coated specimens. In contrast, nanodispersion coated specimens prevented photo-yellowing considerably with significant reduction in colour changes examined by CIE L*, a*, b* and ΔE*. Increase in concentration of nanoparticles in the dispersion imparted higher resistance to UV induced degradation. However, increased concentration of nanoparticles reduced the transparency of the coating. FTIR analysis indicated rapid degradation of lignin in uncoated and PG coated specimens due to UV exposure. Coating of wood surfaces with nanodispersions restricted lignin degradation. The study also demonstrates the potential of propylene glycol as a dispersant for developing stable and efficient UV protective nanodispersions for wood coating. Copyright © 2018 Elsevier B.V. All rights reserved.

High-frequency carbon supercapacitors from polyfurfuryl alcohol

NASA Astrophysics Data System (ADS)

Ruiz, V.; Pandolfo, A. G.

Porous carbons with controllable and narrow pore-size distributions are prepared from the chemical activation of polyfurfuryl alcohol (PFA). High apparent BET surface areas, up to 2600 m 2 g -1 (2611 m 2 g -1 by Density Functional Theory (DFT)), and good electrical conductivities (up to ∼130 S cm -1) are obtained. By varying the potassium hydroxide: carbon precursor ratio, the preparation of carbons with different proportions of micro- and fine mesoporosity (<5 nm) can be tailored to provide an ideal electronic and ionic pore structure for electrochemical energy-storage devices, such as electrical double-layer capacitors. High specific capacitance values are obtained up to 147 F g -1 in a voltage window of 2.5 V using 1 M tetraethyl ammonium tetrafluoroborate in acetonitrile. Moreover, excellent high-current and high-frequency performance is demonstrated: 100 F g -1 at 225 A g -1 (10 Hz) and ∼30 F g -1 at 100 Hz. When comparing the performance with commercial activated carbons (ACs) of similar textural properties, the PFA-derived ACs demonstrated better performance in terms of higher capacitance values and improved rate capabilities. There is a 125% increase in capacitance values at 1 kHz.

AZEOTROPIC RECTIFICATION OF A MIXTURE OF SILICON TETRACHLORIDE WITH TRIMETHYLCHLOROSILANE IN THE PRESENCE OF ACETONITRILE,

DTIC Science & Technology

Batch and continuous units are described for separating binary azeotropes consisting of SiCl4 plus acetonitrile(CH3CN) (b.p. 49.1C) and (CH3)3SiCl...separated from the crude SiCl4 and (CH3)3SiCl mixture. In the second and third, SiCl4 and (CH3) 3SiCl are separated. The experimental results were in close agreement (9 to 12 percent deviation) with those calculated. (Author)

Hydroxyl group as IR probe to detect the structure of ionic liquid-acetonitrile mixtures

NASA Astrophysics Data System (ADS)

Xu, Jing; Deng, Geng; Zhou, Yu; Ashraf, Hamad; Yu, Zhi-Wu

2018-06-01

Task-specific ionic liquids (ILs) are those with functional groups introduced in the cations or anions of ILs to bring about specific properties for various tasks. In this work, the hydrogen bonding interactions between a hydroxyl functionalized IL 1-(2-hydroxylethyl)-3-methylimidazolium tetrafluoroborate ([C2OHMIM][BF4]) and acetonitrile were investigated in detail by infrared spectroscopy, excess spectroscopy, two-dimensional correlation spectroscopy, combined with hydrogen nuclear magnetic resonance and density functional theory calculations (DFT). The hydroxyl group rather than C2sbnd H is found to be the main interaction site in the cation. And the ν(Osbnd H) is more sensitive than v(C-Hs) to the environment, which has been taken as an intrinsic probe to reflect the structural change of IL. Examining the region of ν(Osbnd H), by combining excess spectroscopy and DFT calculation, a number of species were identified in the mixtures. Other than the hydrogen bond between a cation and an anion, the hydroxyl group allows the formation of a hydrogen bond between two like-charged cations. The Osbnd H⋯O hydrogen bonding interactions in the hydroxyl-mediated cation-cation complexes are cooperative, while Osbnd H⋯F and C2sbnd H⋯F hydrogen bonding interactions in cation-anion complexes are anti-cooperative. These in-depth studies on the properties of the ionic liquid-acetonitrile mixtures may shed light on exploring their applications as mixed solvents and understanding the nature of doubly ionic hydrogen bonds.

Study of the acetonitrile poisoning of platinum cathodes on proton exchange membrane fuel cell spatial performance using a segmented cell system

NASA Astrophysics Data System (ADS)

Reshetenko, Tatyana V.; St-Pierre, Jean

2015-10-01

Due to the wide applications of acetonitrile as a solvent in the chemical industry, acetonitrile can be present in the air and should be considered a possible pollutant. In this work, the spatial proton exchange membrane fuel cell performance exposed to air with 20 ppm CH3CN was studied using a segmented cell system. The injection of CH3CN led to performance losses of 380 mV at 0.2 A cm-2 and 290 mV at 1.0 A cm-2 accompanied by a significant change in the current density distribution. The observed local currents behavior is likely attributed to acetonitrile chemisorption and the subsequent two consecutive reduction/oxidation reactions. The hydrolysis of CH3CN and its intermediate imine species resulted in NH4+ formation, which increased the high-frequency resistance of the cell and affected oxygen reduction and performance. Other products of hydrolysis can be oxidized to CO2 under the operating conditions. The reintroduction of pure air completely recovered cell performance within 4 h at 1.0 A cm-2, while at 0.2 A cm-2 the cell recovery was only partial. A detailed analysis of the current density distribution, its correlation with spatial electrochemical impedance spectroscopy data, possible CH3CN oxidation/reduction mechanisms and mitigation strategies are presented and discussed.

Temperature dependent fluorescence spectra arise from change in excited-state intramolecular proton transfer potential of 4‧-N,N-dimethylamino-3-hydroxyflavone-doped acetonitrile crystals

NASA Astrophysics Data System (ADS)

Furukawa, Kazuki; Yamamoto, Norifumi; Hino, Kazuyuki; Sekiya, Hiroshi

2016-01-01

The effect of intermolecular interaction on excited-state intramolecular proton transfer (ESIPT) in 4‧-N,N-dimethylamino-3-hydroxyflavone (DMHF) doped in acetonitrile crystals was investigated by measuring the temperature dependence of fluorescence excitation and fluorescence spectra. A solid/solid phase transition of DMHF-doped acetonitrile crystals occurred in the temperature between 210 and 218 K. Significant differences in the spectral profiles and shifts in the fluorescence spectra were observed in the low- and high-temperature regions of the phase transition. The temperature dependence of the ESIPT potential of DMHF is discussed.

Time-weighted average sampling of airborne propylene glycol ethers by a solid-phase microextraction device.

PubMed

Shih, H C; Tsai, S W; Kuo, C H

2012-01-01

A solid-phase microextraction (SPME) device was used as a diffusive sampler for airborne propylene glycol ethers (PGEs), including propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), and dipropylene glycol monomethyl ether (DPGME). Carboxen-polydimethylsiloxane (CAR/PDMS) SPME fiber was selected for this study. A polytetrafluoroethylene (PTFE) tubing was used as the holder, and the SPME fiber assembly was inserted into the tubing as a diffusive sampler. The diffusion path length and area of the sampler were 0.3 cm and 0.00086 cm(2), respectively. The theoretical sampling constants at 30°C and 1 atm for PGME, PGMEA, and DPGME were 1.50 × 10(-2), 1.23 × 10(-2) and 1.14 × 10(-2) cm(3) min(-1), respectively. For evaluations, known concentrations of PGEs around the threshold limit values/time-weighted average with specific relative humidities (10% and 80%) were generated both by the air bag method and the dynamic generation system, while 15, 30, 60, 120, and 240 min were selected as the time periods for vapor exposures. Comparisons of the SPME diffusive sampling method to Occupational Safety and Health Administration (OSHA) organic Method 99 were performed side-by-side in an exposure chamber at 30°C for PGME. A gas chromatography/flame ionization detector (GC/FID) was used for sample analysis. The experimental sampling constants of the sampler at 30°C were (6.93 ± 0.12) × 10(-1), (4.72 ± 0.03) × 10(-1), and (3.29 ± 0.20) × 10(-1) cm(3) min(-1) for PGME, PGMEA, and DPGME, respectively. The adsorption of chemicals on the stainless steel needle of the SPME fiber was suspected to be one of the reasons why significant differences between theoretical and experimental sampling rates were observed. Correlations between the results for PGME from both SPME device and OSHA organic Method 99 were linear (r = 0.9984) and consistent (slope = 0.97 ± 0.03). Face velocity (0-0.18 m/s) also proved to have no effects on the sampler

Adsorption and Structure of Chiral Epoxides on Pd(111): Propylene Oxide and Glycidol

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

Mahapatra, Mausumi; Tysoe, Wilfred T.

Here, the adsorption of enantiopure versus racemic propylene oxide (PO) on Pd(111) is studied by temperature-programmed desorption (TPD) to explore possible differences in their saturation coverage. It is found that that the saturation coverage of enantiopure PO on Pd(111) is identical to that of racemic PO, in contrast to results on Pt(111) where significant coverage differences were found. The surface structures of enantiopure PO on Pd(111) were characterized by scanning tunneling microscopy (STM), which shows the formation of linear chains and hexagonal structures proposed to be due to freely rotating PO, in contrast to the relatively disordered PO overlayers foundmore » on Pt(111). STM experiments were carried out for enantiopure glycidol, which contains the same epoxy ring as PO, but where the methyl group of propylene oxide is replaced by a -CH 2OH group to provide a hydrogen-bonding sites. Glycidol STM images show the formation of completely different surface structures; at low coverages, glycidol forms pseudohexagonal structures which assemble from glycidol dimers, while at high coverages the surface shows extensive hydrogen-bonded networks. Density functional theory (DFT) calculations were carried out to model the enantiopure PO linear chain and the glycidol dimers that are observed by STM. Similar calculations were carried out for racemic PO and glycidol structures. The calculated interaction energies for the enantiopure and the racemic pairs reveal that there is no difference for homochiral versus heterochiral structures for both PO and glycidol on Pd(111).« less

Adsorption and Structure of Chiral Epoxides on Pd(111): Propylene Oxide and Glycidol

DOE PAGES

Mahapatra, Mausumi; Tysoe, Wilfred T.

2018-01-03

Here, the adsorption of enantiopure versus racemic propylene oxide (PO) on Pd(111) is studied by temperature-programmed desorption (TPD) to explore possible differences in their saturation coverage. It is found that that the saturation coverage of enantiopure PO on Pd(111) is identical to that of racemic PO, in contrast to results on Pt(111) where significant coverage differences were found. The surface structures of enantiopure PO on Pd(111) were characterized by scanning tunneling microscopy (STM), which shows the formation of linear chains and hexagonal structures proposed to be due to freely rotating PO, in contrast to the relatively disordered PO overlayers foundmore » on Pt(111). STM experiments were carried out for enantiopure glycidol, which contains the same epoxy ring as PO, but where the methyl group of propylene oxide is replaced by a -CH 2OH group to provide a hydrogen-bonding sites. Glycidol STM images show the formation of completely different surface structures; at low coverages, glycidol forms pseudohexagonal structures which assemble from glycidol dimers, while at high coverages the surface shows extensive hydrogen-bonded networks. Density functional theory (DFT) calculations were carried out to model the enantiopure PO linear chain and the glycidol dimers that are observed by STM. Similar calculations were carried out for racemic PO and glycidol structures. The calculated interaction energies for the enantiopure and the racemic pairs reveal that there is no difference for homochiral versus heterochiral structures for both PO and glycidol on Pd(111).« less

Synthesis of Metal Nanoparticles and Metal Fluoride Nanoparticles from Metal Amidinate Precursors in 1‐Butyl‐3‐Methylimidazolium Ionic Liquids and Propylene Carbonate

PubMed Central

Schütte, Kai; Barthel, Juri; Endres, Manuel; Siebels, Marvin; Smarsly, Bernd M.; Yue, Junpei

2016-01-01

Abstract Decomposition of transition‐metal amidinates [M{MeC(NiPr)2}n] [M(AMD)n; M=MnII, FeII, CoII, NiII, n=2; CuI, n=1) induced by microwave heating in the ionic liquids (ILs) 1‐butyl‐3‐methylimidazolium tetrafluoroborate ([BMIm][BF4]), 1‐butyl‐3‐methylimidazolium hexafluorophosphate ([BMIm][PF6]), 1‐butyl‐3‐methylimidazolium trifluoromethanesulfonate (triflate) ([BMIm][TfO]), and 1‐butyl‐3‐methylimidazolium tosylate ([BMIm][Tos]) or in propylene carbonate (PC) gives transition‐metal nanoparticles (M‐NPs) in non‐fluorous media (e.g. [BMIm][Tos] and PC) or metal fluoride nanoparticles (MF2‐NPs) for M=Mn, Fe, and Co in [BMIm][BF4]. FeF2‐NPs can be prepared upon Fe(AMD)2 decomposition in [BMIm][BF4], [BMIm][PF6], and [BMIm][TfO]. The nanoparticles are stable in the absence of capping ligands (surfactants) for more than 6 weeks. The crystalline phases of the metal or metal fluoride synthesized in [BMIm][BF4] were identified by powder X‐ray diffraction (PXRD) to exclusively Ni‐ and Cu‐NPs or to solely MF2‐NPs for M=Mn, Fe, and Co. The size and size dispersion of the nanoparticles were determined by transmission electron microscopy (TEM) to an average diameter of 2(±2) to 14(±4) nm for the M‐NPs, except for the Cu‐NPs in PC, which were 51(±8) nm. The MF2‐NPs from [BMIm][BF4] were 15(±4) to 65(±18) nm. The average diameter from TEM is in fair agreement with the size evaluated from PXRD with the Scherrer equation. The characterization was complemented by energy‐dispersive X‐ray spectroscopy (EDX). Electrochemical investigations of the CoF2‐NPs as cathode materials for lithium‐ion batteries were simply evaluated by galvanostatic charge/discharge profiles, and the results indicated that the reversible capacity of the CoF2‐NPs was much lower than the theoretical value, which may have originated from the complex conversion reaction mechanism and residue on the surface of the nanoparticles. PMID:28168159

Studies on Poly(propylene fumarate-co-caprolactone diol) Thermoset Composites towards the Development of Biodegradable Bone Fixation Devices

PubMed Central

Jayabalan, M.

2009-01-01

The effect of reinforcement in the cross-linked poly(propylene fumarate-co-caprolactone diol) thermoset composites based on Kevlar fibres and hydroxyapatite was studied. Cross-linked poly(propylene fumarate-co-caprolactone diol) was also studied without any reinforcement for comparison. The reinforcing fibre acts as a barrier for the curing reaction leading to longer setting time and lesser cross-link density. The fibre and HA reinforced composites have almost the same compressive strength. Nonreinforced material undergoes greater degree of swelling. Among the reinforced materials, the hydroxyapatite reinforced composite has a much higher swelling percentage than the fibre reinforced one. The studies on in vitro degradation of the cured materials reveal hydrolytic degradation in Ringer's solution and PBS medium during aging. All the three materials are found to swell initially in Ringer's solution and PBS medium during aging and then undergo gradual degradation. Compression properties of these cross-linked composites increase with aging; HA reinforced composite has the highest compressive strength and compressive modulus, whereas the aged fibre-reinforced composite has the least compressive strength and modulus. PMID:20126578

Studies on Poly(propylene fumarate-co-caprolactone diol) Thermoset Composites towards the Development of Biodegradable Bone Fixation Devices.

PubMed

Jayabalan, M

2009-01-01

The effect of reinforcement in the cross-linked poly(propylene fumarate-co-caprolactone diol) thermoset composites based on Kevlar fibres and hydroxyapatite was studied. Cross-linked poly(propylene fumarate-co-caprolactone diol) was also studied without any reinforcement for comparison. The reinforcing fibre acts as a barrier for the curing reaction leading to longer setting time and lesser cross-link density. The fibre and HA reinforced composites have almost the same compressive strength. Nonreinforced material undergoes greater degree of swelling. Among the reinforced materials, the hydroxyapatite reinforced composite has a much higher swelling percentage than the fibre reinforced one. The studies on in vitro degradation of the cured materials reveal hydrolytic degradation in Ringer's solution and PBS medium during aging. All the three materials are found to swell initially in Ringer's solution and PBS medium during aging and then undergo gradual degradation. Compression properties of these cross-linked composites increase with aging; HA reinforced composite has the highest compressive strength and compressive modulus, whereas the aged fibre-reinforced composite has the least compressive strength and modulus.

Irradiation effects of 12 eV oxygen ions on polyimide and fluorinated ethylene propylene

NASA Astrophysics Data System (ADS)

Majeed, R. M. A.; Purohit, V. S.; Bhoraskar, S. V.; Mandale, A. B.; Bhoraskar, V. N.

2006-08-01

Polyimide (PI) and Fluorinated Ethylene Propylene (FEP) samples (15mm x 15mm x 50 mu m ) were exposed to atomic oxygen ions of average energy similar to 12 eV and flux similar to 5x10(13) ions cm(-2) s(-1) , produced in the Electron Cyclotron Resonance (ECR) plasma. The energy and the flux of the oxygen ions at different positions in the plasma were measured by a retarding field analyzer. The fluence of the oxygen ions was varied from sample to sample in the range of similar to 5x10(16) to 2x10(17) ions cm(-2) by changing the irradiation period. The pre- and the post-irradiated samples were characterized by the weight loss, Scanning Electron Microscopy (SEM), X-ray Photoelectron Spectroscopy (XPS), and Fourier Transform Infrared (FTIR) techniques. The weight of the PI and FEP samples decreased with increasing the ion fluence. However, the erosion yield for the PI is found to be higher, by almost a factor five, when compared with that of FEP. On the surface region of irradiated samples, the concentrations of the carbon, fluorine, and oxygen and their corresponding chemical bonds have changed appreciably. Moreover, blisters and nanoglobules were also observed even at a fluence of similar to 10(17) ions cm(-2) . This oxygen ion fluence is almost two orders of magnitude lower than that of the 5 eV atomic oxygen, which a satellite encounters in the space, at the low Earth orbit, during its mission period of about 7 years.

[Ethylene glycol and propylene glycol ethers - Reproductive and developmental toxicity].

PubMed

Starek-Świechowicz, Beata; Starek, Andrzej

2015-01-01

Both ethylene and propylene glycol alkyl ethers (EGAEs and PGAEs, respectively) are widely used, mainly as solvents, in industrial and household products. Some EGAEs demonstrate gonadotoxic, embriotoxic, fetotoxic and teratogenic effects in both humans and experimental animals. Due to the noxious impact of these ethers on reproduction and development of organisms EGAEs are replaced for considerably less toxic PGAEs. The data on the mechanisms of testicular, embriotoxic, fetotoxic and teratogenic effects of EGAEs are presented in this paper. Our particular attention was focused on the metabolism of some EGAEs and their organ-specific toxicities, apoptosis of spermatocytes associated with changes in the expression of various genes that code for oxidative stress factors, protein kinases and nuclear hormone receptors. This work is available in Open Access model and licensed under a CC BY-NC 3.0 PL license.

Surface characterisation of ethylene propylene diene rubber upon exposure to aqueous acidic solution

NASA Astrophysics Data System (ADS)

Mitra, Susanta; Ghanbari-Siahkali, Afshin; Kingshott, Peter; Hvilsted, Søren; Almdal, Kristoffer

2006-07-01

Two types of pure ethylene propylene diene rubbers were exposed to two different acids for varying period of time. Surface characterisation was carried out using X-ray photoelectron spectroscopy (XPS). Two EPDM rubbers selected for this study were comparable in co-monomer compositions but significantly different with respect to molar mass and the presence of long chain branching. Both rubbers contained 5-ethylidene-2-norbornene (ENB) as diene. Solution cast films of pure EPDM samples were exposed in two different acidic solutions, viz. chromosulphuric (Cr (VI)/H 2SO 4) and sulphuric acid (H 2SO 4) (20%, v/v) at ambient temperature from 1 to 12 weeks. XPS analysis indicated that several oxygenated species were formed on the surface of both rubbers after exposure. It was postulated from the XPS analyses that both aqueous acidic solutions attacked the olefinic double bonds (C dbnd C) of ENB. Furthermore, 20% Cr (VI)/H 2SO 4 also attacked the allylic carbon-hydrogen (C sbnd H) bonds of ENB resulting in more oxygenated species on the surface compared to 20% H 2SO 4 under identical conditions. Cr (VI) in the 20% Cr (VI)/H 2SO 4 was found to play an important role in alteration of surface chemistry. Studies using a model system consisting of EPDM mixed with Cr (VI) and Cr (III) salts revealed that the change of oxidation state from Cr (VI) to Cr (III) as a consequence of direct involvement of Cr (VI) in the chemical alteration of EPDM surfaces. Interestingly, the presence of long chain branching and molar mass did not significantly influence the chemical processes owing to the acid treatment.

Single-Ion Solvation Free Energies and the Normal Hydrogen Electrode Potential in Methanol, Acetonitrile, and Dimethyl Sulfoxide

PubMed Central

Kelly, Casey P.; Cramer, Christopher J.; Truhlar, Donald G.

2008-01-01

The division of thermodynamic solvation free energies of electrolytes into ionic constituents is conventionally accomplished by using the single-ion solvation free energy of one reference ion, conventionally the proton, to set the single-ion scales. Thus the determination of the free energy of solvation of the proton in various solvents is a fundamental issue of central importance in solution chemistry. In the present article, relative solvation free energies of ions and ion-solvent clusters in methanol, acetonitrile, and dimethyl sulfoxide (DMSO) have been determined using a combination of experimental and theoretical gas-phase free energies of formation, solution-phase reduction potentials and acid dissociation constants, and gas-phase clustering free energies. Applying the cluster pair approximation to differences between these relative solvation free energies leads to values of −263.5, −260.2, and −273.3 kcal/mol for the absolute solvation free energy of the proton in methanol, acetonitrile, and DMSO, respectively. The final absolute proton solvation free energies are used to assign absolute values for the normal hydrogen electrode potential and the solvation free energies of other single ions in the above solvents. PMID:17214493

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

Das, S.; Ghosh, A., E-mail: sspag@iacs.res.in

We have studied ionic conductivity and dielectric permittivity of PEO-LiClO{sub 4} solid polymer electrolyte plasticized with propylene carbonate. Differential scanning calorimetry and X-ray diffraction studies confirm minimum volume fraction of crystalline phase for the polymer electrolyte with 40 wt. % propylene carbonate. The ionic conductivity exhibits a maximum for the same composition. The temperature dependence of the ionic conductivity has been well interpreted using Vogel-Tamman-Fulcher equation. Ion-ion interactions in the polymer electrolytes have been studied using Raman spectra and the concentrations of free ions, ion-pairs and ion-aggregates have been determined. The ionic conductivity increases due to the increase of freemore » ions with the increase of propylene carbonate content. But for higher content of propylene carbonate, the ionic conductivity decreases due to the increase of concentrations of ion-pairs and ion-aggregates. To get further insights into the ion dynamics, the experimental data for the complex dielectric permittivity have been studied using Havriliak–Negami function. The variation of relaxation time with temperature obtained from this formalism follows Vogel-Tamman-Fulcher equation similar to the ionic conductivity.« less

Acetonitrile covalent adduct chemical ionization mass spectrometry for double bond localization in non-methylene-interrupted polyene fatty acid methyl esters.

PubMed

Lawrence, Peter; Brenna, J Thomas

2006-02-15

Covalent adduct chemical ionization (CACI) using a product of acetonitrile self-reaction, (1-methyleneimino)-1-ethenylium (MIE; CH2=C=N+=CH2), has been investigated as a method for localizing double bonds in a series of 16 non-methylene-interrupted fatty acid methyl esters (NMI-FAME) of polyenes with three and more double bonds. As with polyunsaturated homoallylic (methylene-interrupted) FAME and conjugated dienes, MIE (m/z 54) reacts across double bonds to yield molecular ions 54 mass units above the parent analyte. [M + 54]+ ions of several 20- and 22-carbon FAME that include one double bond in the C2-C3 position separated by two to five methylene units from a three, four, or five C homoallylic system dissociated according to rules for the homoallylic system, with an additional fragment corresponding to cleavage between the lone double bond and the carboxyl group and defining the position of the lone double bond. Triene FAME with both methylene and ethylene interruption yielded characteristic fragments distinguishable from homoallylic trienes. Fragmentation of fully conjugated trienes in the MS-1 spectra yields ratios of [M + 54]+/[M + 54 - 32]+ (loss of methanol) near unity, which distinguishes them from homoallylic FAME having a ratio of 8 or more; collisionally activated dissociation of [M + 54]+ yields a series of ions, including some rearrangement products, indicative of double bond position. Unlike conjugated dienes, fully conjugated triene diagnostic ion signal ratios did not follow any pattern based on double bond geometry. Partially conjugated trienes behave similarly to monoenes and conjugated dienes, yielding [M + 54]+/[M + 54 - 32]+ of 2-3 and, permitting them to be assigned as partially conjugated FAME using the MS-1 spectrum. They yield unique MS/MS spectra with weaker but assignable fragment ions, along with a diagnostic fragment that locates the lone double bond and permits 6,10,12-octatrienoate to be distinguished from 6,8,12-octatrienoate. The

Evaluation of some antioxidants in radiation vulcanized ethylene-propylene diene (EPDM) rubber

NASA Astrophysics Data System (ADS)

Abdel-Aziz, M. M.; Basfar, A. A.

2001-12-01

Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) have been used to study the oxidation of γ-ray vulcanized ethylene-propylene diene rubber (EPDM) stabilized with various types of antioxidants. The antioxidants used were pentaerythrityl tetrakis(3,5-di-tert-butyl(-4-hydroxyphenyl))propionate (Irganox 1010), Irganox 1035, Irganox 1520D, as primary antioxidants; Irganox B561 and Irganox B900, as synergistic blends; hindered amine light stabilizer (HALS), i.e. Tinuvin 622 LD; N-isopropyl- N-phenyl- p-phenylene diamine (IPPD) and trimethyl quinoline (TMQ) and their mixtures. The measurements were carried out under atmospheric conditions. The effects of antioxidant type and its selected concentration were determined and mechanism of reaction proposed.

Insights into the effects of solvent properties in graphene based electric double-layer capacitors with organic electrolytes

NASA Astrophysics Data System (ADS)

Zhang, Shuo; Bo, Zheng; Yang, Huachao; Yang, Jinyuan; Duan, Liangping; Yan, Jianhua; Cen, Kefa

2016-12-01

Organic electrolytes are widely used in electric double-layer capacitors (EDLCs). In this work, the microstructure of planar graphene-based EDLCs with different organic solvents are investigated with molecular dynamics simulations. Results show that an increase of solvent polarity could weaken the accumulation of counter-ions nearby the electrode surface, due to the screen of electrode charges and relatively lower ionic desolvation. It thus suggests that solvents with low polarity could be preferable to yield high EDL capacitance. Meanwhile, the significant effects of the size and structure of solvent molecules are reflected by non-electrostatic molecule-electrode interactions, further influencing the adsorption of solvent molecules on electrode surface. Compared with dimethyl carbonate, γ-butyrolactone, and propylene carbonate, acetonitrile with relatively small-size and linear structure owns weak non-electrostatic interactions, which favors the easy re-orientation of solvent molecules. Moreover, the shift of solvent orientation in surface layer, from parallel orientation to perpendicular orientation relative to the electrode surface, deciphers the solvent twin-peak behavior near negative electrode. The as-obtained insights into the roles of solvent properties on the interplays among particles and electrodes elucidate the solvent influences on the microstructure and capacitive behavior of EDLCs using organic electrolytes.

Secondary organic aerosol formation from propylene irradiations in a chamber study

NASA Astrophysics Data System (ADS)

Ge, Shuangshuang; Xu, Yongfu; Jia, Long

2017-05-01

Some studies have shown that low-molecular-weight VOCs such as ethylene and acetylene can form SOA. However, so far propylene (C3H6) has not been studied. The current work systematically investigates irradiations of propylene in the presence of NOx (x = 1, 2) in a self-made indoor chamber. Only a small amount of secondary organic aerosols (SOA) was formed under 5% and 80% RH conditions without sodium chloride (NaCl) seed particles or in the presence of solid NaCl. When NaCl was in the form of droplets, liquid water content (LWC) increased from 34.5 to 169.8 μg m-3 under different initial NaCl concentrations, and correspondingly the amount of SOA linearly increased from 5.9 to 29.8 μg m-3 (SOA = 0.0164 × LWC+1.137, R2 = 0.97) at the C3H6/NOx ratio of 32.2-44.9 (ppbC/ppb). The initial C3H6/NOx concentration ratio considerably impacted the formation of SOA, in which the amount of SOA increased from 12.1 to 47.9 μg m-3 exponentially as the ratio decreased from 46.5 to 6.3 with an important point of the ratio value of 11. At the ratio of less than 11 in the regime under the control of C3H6, SOA concentrations decreased considerably with increasing ratio, whereas at the ratio value of larger than 11 in the NOx controlled regime, SOA slightly decreased with increasing ratio. From combination of the analysis of different functional groups of particles by IR spectra and ESI-Exactive-Orbitrap mass spectrometer, the constituents of SOA were identified to be hydroperoxides (e.g. HOCH2CCl(CH3)OOH), esters (e.g. CH2ClC(O)OCHClCHO), organic nitrates (e.g. HO2CH(CH2Cl)C(O)OCCl(CH2Cl)C(O)OCHClCH2ONO2), etc. Furthermore, a liquid-phase mechanism of SOA formation has been proposed in this study.

DEVELOPMENT OF A PHYSIOLOGICALLY BASED PHARMACOKINETIC MODEL FOR PROPYLENE GLYCOL MONOMETHYL ETHER AND ITS ACETATE IN RATS AND HUMANS

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

Corley, Rick A.; Gies, Richard A.; Wu, Hong

2005-03-05

Propylene glycol monomethyl ether (PM), along with its acetate, is the most widely used of the propylene glycol ether family of solvents. The most common toxic effects of PM observed in animal studies include sedation, very slight alpha2u globulin-mediated nephropathy (male rats only) and hepatomegally at high exposures (typically >1000 ppm). Sedation in animal studies usually resolves within a few exposures to 3000 ppm (the highest concentration used in subchronic and chronic inhalation studies) due to the induction of metabolizing enzymes. Data from a variety of pharmacokinetic and mechanistic studies have been incorporated into a PBPK model for PM andmore » its acetate in rats and mice. Published controlled exposure and workplace biomonitoring studies have also been included for comparisons of the internal dosimetry of PM and its acetate between laboratory animals and humans. PM acetate is rapidly hydrolyzed to PM, which is further metabolized to either glucuronide or sulphate conjugates (minor pathways) or propylene glycol (major pathway). In vitro half-lives for PM acetate range from 14-36 min depending upon the tissue and species. In vivo half-lives are considerably faster, reflecting the total contributions of esterases in the blood and tissues of the body, and are on the order of just a few minutes. Thus, very little PM acetate is found in vivo and, other than potential portal of entry irritation, the toxicity of PM acetate is related to PM. Regardless of the source for PM (either PM or its acetate), rats were predicted to have a higher Cmax and AUC for PM in blood than humans, especially at concentrations greater than the current ACGIH TLV of 100 ppm. This would indicate that the major systemic effects of PM would be expected to be less severe in humans than rats at comparable inhalation exposures.« less

Toward Tailor-Made Biocide Materials Based on Poly(propylene)/Copper Nanoparticles.

PubMed

Palza, Humberto; Gutiérrez, Sebastian; Delgado, Katherine; Salazar, Oriana; Fuenzalida, Victor; Avila, Jonathan I; Figueroa, Guillermo; Quijada, Raúl

2010-03-16

A set of poly(propylene) composites containing different amounts of copper nanoparticles (CNP) were prepared by the melt mixed method and their antimicrobial behavior was quantitatively studied. The time needed to reduce the bacteria to 50% dropped to half with only 1 v/v % of CNP, compared to the polymer without CNP. After 4 h, this composite killed more than 99.9% of the bacteria. The biocide kinetics can be controlled by the nanofiller content; composites with CNP concentrations higher than 10 v/v % eliminated 99% of the bacteria in less than 2 h. X-ray photoelectron spectroscopy did not detect CNP at the surface, therefore the biocide behavior was attributed to copper in the bulk of the composite. Copyright © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Increase of porosity by combining semi-carbonization and KOH activation of formaldehyde resins to prepare high surface area carbons for supercapacitor applications

NASA Astrophysics Data System (ADS)

Heimböckel, Ruben; Kraas, Sebastian; Hoffmann, Frank; Fröba, Michael

2018-01-01

A series of porous carbon samples were prepared by combining a semi-carbonization process of acidic polymerized phenol-formaldehyde resins and a following chemical activation with KOH used in different ratios to increase specific surface area, micropore content and pore sizes of the carbons which is favourable for supercapacitor applications. Samples were characterized by nitrogen physisorption, powder X-ray diffraction, Raman spectroscopy and scanning electron microscopy. The results show that the amount of KOH, combined with the semi-carbonization step had a remarkable effect on the specific surface area (up to SBET: 3595 m2 g-1 and SDFT: 2551 m2 g-1), pore volume (0.60-2.62 cm3 g-1) and pore sizes (up to 3.5 nm). The carbons were tested as electrode materials for electrochemical double layer capacitors (EDLC) in a two electrode setup with tetraethylammonium tetrafluoroborate in acetonitrile as electrolyte. The prepared carbon material with the largest surface area, pore volume and pore sizes exhibits a high specific capacitance of 145.1 F g-1 at a current density of 1 A g-1. With a high specific energy of 31 W h kg-1 at a power density of 33028 W kg-1 and a short time relaxation constant of 0.29 s, the carbon showed high power capability as an EDLC electrode material.

Thymol nanoemulsified by whey protein-maltodextrin conjugates: the enhanced emulsifying capacity and antilisterial properties in milk by propylene glycol.

PubMed

Xue, Jia; Davidson, P Michael; Zhong, Qixin

2013-12-26

The objective of this research was to enhance the capability of whey protein isolate-maltodextrin conjugates in nanoemulsifying thymol using propylene glycol to improve antilisterial properties in milk. Thymol was predissolved in PG and emulsified in 7% conjugate solution. Transparent dispersions with mean diameters of <30 nm were observed up to 1.5%w/v thymol. In skim and 2% reduced fat milk, Listeria monocytogenes Scott A was reduced from ∼5 log CFU/mL to below the detection limit in 6 h by 0.1% w/v and 0.45% w/v nanoemulsified thymol, respectively, contrasting with gradual reductions to 1.15 and 2.26 log CFU/mL after 48 h by same levels of free thymol. In full fat milk, L. monocytogenes was gradually reduced to be undetectable after 48 h by 0.6% w/v nanoemulsified thymol, contrasting with the insignificant reduction by free thymol. The improved antilisterial activities of nanoemulsified thymol resulted from the increased solubility in milk and synergistic activity with propylene glycol.

Ice recrystallization inhibition in ice cream by propylene glycol monostearate.

PubMed

Aleong, J M; Frochot, S; Goff, H D

2008-11-01

The effectiveness of propylene glycol monostearate (PGMS) to inhibit ice recrystallization was evaluated in ice cream and frozen sucrose solutions. PGMS (0.3%) dramatically reduced ice crystal sizes in ice cream and in sucrose solutions frozen in a scraped-surface freezer before and after heat shock, but had no effect in quiescently frozen solutions. PGMS showed limited emulsifier properties by promoting smaller fat globule size distributions and enhanced partial coalescence in the mix and ice cream, respectively, but at a much lower level compared to conventional ice cream emulsifier. Low temperature scanning electron microscopy revealed highly irregular crystal morphology in both ice cream and sucrose solutions frozen in a scraped-surface freezer. There was strong evidence to suggest that PGMS directly interacts with ice crystals and interferes with normal surface propagation. Shear during freezing may be required for its distribution around the ice and sufficient surface coverage.

Synthesis and characterization of microporous inorganic membranes for propylene/propane separation

NASA Astrophysics Data System (ADS)

Ma, Xiaoli

Membrane-based gas separation is promising for efficient propylene/propane (C3H6/C3H8) separation with low energy consumption and minimum environment impact. Two microporous inorganic membrane candidates, MFI-type zeolite membrane and carbon molecular sieve membrane (CMS) have demonstrated excellent thermal and chemical stability. Application of these membranes into C3H6/C3H 8 separation has not been well investigated. This dissertation presents fundamental studies on membrane synthesis, characterization and C3H 6/C3H8 separation properties of MFI zeolite membrane and CMS membrane. MFI zeolite membranes were synthesized on α-alumina supports by secondary growth method. Novel positron annihilation spectroscopy (PAS) techniques were used to non-destructively characterize the pore structure of these membranes. PAS reveals a bimodal pore structure consisting of intracrystalline zeolitic micropores of ~0.6 nm in diameter and irregular intercrystalline micropores of 1.4 to 1.8 nm in size for the membranes. The template-free synthesized membrane exhibited a high permeance but a low selectivity in C3H 6/C3H8 mixture separation. CMS membranes were synthesized by coating/pyrolysis method on mesoporous gamma-alumina support. Such supports allow coating of thin, high-quality polymer films and subsequent CMS membranes with no infiltration into support pores. The CMS membranes show strong molecular sieving effect, offering a high C3H 6/C3H8 mixture selectivity of ~30. Reduction in membrane thickness from 500 nm to 300 nm causes an increase in C3H8 permeance and He/N2 selectivity, but a decrease in the permeance of He, N 2 and C3H6 and C3H6/C 3H8 selectivity. This can be explained by the thickness dependent chain mobility of the polymer film resulting in final carbon membrane of reduced pore size with different effects on transport of gas of different sizes, including possible closure of C3H6-accessible micropores. CMS membranes demonstrate excellent C3H6/C 3H8 separation

Graphite-Conjugated Rhenium Catalysts for Carbon Dioxide Reduction

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

Oh, Seokjoon; Gallagher, James R.; Miller, Jeffrey T.

2016-02-17

Condensation of fac-Re(5,6-diamino-1,10-phenanthroline)(CO)(3)Cl to o-quinone edge defects on graphitic carbon surfaces generates graphite-conjugated rhenium (GCC-Re) catalysts that are highly active for CO2 reduction to CO in acetonitrile electrolyte. X-ray photo-electron and X-ray absorption spectroscopies establish the formation of surface-bound Re centers with well-defined coordination environments. GCC-Re species on glassy carbon surfaces display catalytic currents greater than 50 mA cm(-2) with 96 +/- 3% Faradaic efficiency for CO production. Normalized for the number of Re active sites, GCC-Re catalysts exhibit higher turnover frequencies than that of a soluble molecular analogue, fac-Re(1,10-phenanthroline)(CO)(3)Cl, and turnover numbers greater than 12,000. In contrast to themore » molecular analogue, GCC-Re surfaces display a Tafel slope of 150 mV/decade, indicative of a catalytic mechanism involving rate-limiting one-electron transfer. This work establishes graphite conjugation as a powerful strategy for generating well-defined, tunable, heterogeneous electrocatalysts on ubiquitous graphitic carbon surfaces.« less

Syntheses, Structures, and Binding Constants of Cyclic Ether and Thioether Adducts of Soluble Cadmium(II) Carboxylates. Intermediates in the Homopolymerization of Oxiranes and Thiiranes and in Carbon Dioxide Coupling Processes.

PubMed

Darensbourg, Donald J.; Niezgoda, Sharon A.; Holtcamp, Matthew W.; Draper, Jennifer D.; Reibenspies, Joseph H.

1997-05-21

A synthetic methodology for the preparation of a large variety of eta(3)-HB(3-Phpz)(3)Cd(acetate) adducts is presented which involves replacement of toluene in the eta(3)-HB(3-Phpz)(3)Cd(acetate) solvate complex by the appropriate cyclic ether or cyclic thioether. In this manner, adducts of THF, dioxane, propylene oxide, cyclohexene oxide, and propylene sulfide were isolated. The solid-state structures of several of these complexes were determined by X-ray crystallography, revealing a six-coordinate complex where the acetate ligand is shown to be fairly symmetrically bonded to the cadmium center. In methylene chloride solution, the cyclic ether or thioether readily dissociates to afford the five-coordinate complex, as demonstrated by (113)Cd NMR. A quantitative assessment of the binding of these base adducts of eta(3)-HB(3-Phpz)(3)Cd(acetate) was determined by measuring the temperature dependence of the equilibrium constants for the five- and six-coordinate derivatives. The presence of one sharp (113)Cd resonance in this equilibrium mixture is indicative of rapid intermolecular exchange between the five- and six-coordinate complexes when compared to the chemical shift differences in these two species ( approximately 6600 Hz at 89 MHz). The order established for ether binding is THF > dioxane > propylene sulfide > cyclohexene oxide >/= propylene oxide, with DeltaH degrees and DeltaS degrees spanning the ranges -27.7 to 24.3 kJ/mol and -89.7 to -94.1 J/(mol K). The epoxide and thioepoxide adducts were shown to serve as models for the initiation step in the copolymerization of epoxides with carbon dioxide catalyzed by metal carboxylates. That is, the carboxylate ligand was shown to ring-open the epoxide or thioepoxide, subsequently affording polyethers or polythioethers with ester end groups. By way of contrast, in the presence of CO(2) and epoxides, this system led to cyclic carbonate production.

IMPACT OF AEROSOL LIQUID WATER ON SECONDARY ORGANIC AEROSOL YIELDS OF IRRADIATED TOLUENE/PROPYLENE/NOX/(NH4)2SO4/AIR MIXUTRES

EPA Science Inventory

Laboratory experiments were conducted to assess whether the presence of liquid water on pre-existing submicron ammonium sulfate aerosols affects yields of condensible organic compounds. Toluene/propylene/NOX/air mixtures were irradiated in the presence of submicron ammonium su...

Direct observation of metal nanoparticles as heterogeneous nuclei for the condensation of supersaturated organic vapors: nucleation of size-selected aluminum nanoparticles in acetonitrile and n-hexane vapors.

PubMed

Abdelsayed, Victor; El-Shall, M Samy

2014-08-07

This work reports the direct observation and separation of size-selected aluminum nanoparticles acting as heterogeneous nuclei for the condensation of supersaturated vapors of both polar and nonpolar molecules. In the experiment, we study the condensation of supersaturated acetonitrile and n-hexane vapors on charged and neutral Al nanoparticles by activation of the metal nanoparticles to act as heterogeneous nuclei for the condensation of the organic vapor. Aluminum seed nanoparticles with diameters of 1 and 2 nm are capable of acting as heterogeneous nuclei for the condensation of supersaturated acetonitrile and hexane vapors. The comparison between the Kelvin and Fletcher diameters indicates that for the heterogeneous nucleation of both acetonitrile and hexane vapors, particles are activated at significantly smaller sizes than predicted by the Kelvin equation. The activation of the Al nanoparticles occurs at nearly 40% and 65% of the onset of homogeneous nucleation of acetonitrile and hexane supersaturated vapors, respectively. The lower activation of the charged Al nanoparticles in acetonitrile vapor is due to the charge-dipole interaction which results in rapid condensation of the highly polar acetonitrile molecules on the charged Al nanoparticles. The charge-dipole interaction decreases with increasing the size of the Al nanoparticles and therefore at low supersaturations, most of the heterogeneous nucleation events are occurring on neutral nanoparticles. No sign effect has been observed for the condensation of the organic vapors on the positively and negatively charged Al nanoparticles. The present approach of generating metal nanoparticles by pulsed laser vaporization within a supersaturated organic vapor allows for efficient separation between nucleation and growth of the metal nanoparticles and, consequently controls the average particle size, particle density, and particle size distribution within the liquid droplets of the condensing vapor. Strong

Direct observation of metal nanoparticles as heterogeneous nuclei for the condensation of supersaturated organic vapors: Nucleation of size-selected aluminum nanoparticles in acetonitrile and n-hexane vapors

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

Abdelsayed, Victor; Samy El-Shall, M., E-mail: mselshal@vcu.edu

This work reports the direct observation and separation of size-selected aluminum nanoparticles acting as heterogeneous nuclei for the condensation of supersaturated vapors of both polar and nonpolar molecules. In the experiment, we study the condensation of supersaturated acetonitrile and n-hexane vapors on charged and neutral Al nanoparticles by activation of the metal nanoparticles to act as heterogeneous nuclei for the condensation of the organic vapor. Aluminum seed nanoparticles with diameters of 1 and 2 nm are capable of acting as heterogeneous nuclei for the condensation of supersaturated acetonitrile and hexane vapors. The comparison between the Kelvin and Fletcher diameters indicatesmore » that for the heterogeneous nucleation of both acetonitrile and hexane vapors, particles are activated at significantly smaller sizes than predicted by the Kelvin equation. The activation of the Al nanoparticles occurs at nearly 40% and 65% of the onset of homogeneous nucleation of acetonitrile and hexane supersaturated vapors, respectively. The lower activation of the charged Al nanoparticles in acetonitrile vapor is due to the charge-dipole interaction which results in rapid condensation of the highly polar acetonitrile molecules on the charged Al nanoparticles. The charge-dipole interaction decreases with increasing the size of the Al nanoparticles and therefore at low supersaturations, most of the heterogeneous nucleation events are occurring on neutral nanoparticles. No sign effect has been observed for the condensation of the organic vapors on the positively and negatively charged Al nanoparticles. The present approach of generating metal nanoparticles by pulsed laser vaporization within a supersaturated organic vapor allows for efficient separation between nucleation and growth of the metal nanoparticles and, consequently controls the average particle size, particle density, and particle size distribution within the liquid droplets of the condensing vapor

Effect of the pasteurization process on the contents of ascorbigen, indole-3-carbinol, indole-3-acetonitrile, and 3,3'-diindolylmethane in fermented cabbage.

PubMed

Ciska, Ewa; Honke, Joanna

2012-04-11

The aim of the study was to investigate the effect of the pasteurization process on the content of ascorbigen, indole-3-carbinol, indole-3-acetonitrile, and 3,3'-diindolylmethane in fermented cabbage. Pasteurization was run at a temperature of 80 °C for 5-30 min. Significant changes were only observed in contents of ascorbigen and 3,3'-diindolylmethane. The total content of the compounds analyzed in cabbage pasteurized for 10-30 min was found to be decreased by ca. 20%, and the losses were due to thermal degradation of the predominating ascorbigen. Pasteurization was found not to exert any considerable effect on contents of indole-3-acetonitrile and indole-3-carbinol in cabbage nor did it affect contents of the compounds analyzed in juice.

Effect of the physicochemical parameters of benzimidazole molecules on their retention by a nonpolar sorbent from an aqueous acetonitrile solution

NASA Astrophysics Data System (ADS)

Shafigulin, R. V.; Safonova, I. A.; Bulanova, A. V.

2015-09-01

The effect of the structure of benzimidazoles on their chromatographic retention on octadecyl silica gel from an aqueous acetonitrile eluent was studied. One- and many-parameter correlation equations were obtained by linear regression analysis, and their prognostic potential in determining the retention factors of benzimidazoles under study was analyzed.

Biodegradation of propylene glycol and associated hydrodynamic effects in sand.

PubMed

Bielefeldt, Angela R; Illangasekare, Tissa; Uttecht, Megan; LaPlante, Rosanna

2002-04-01

At airports around the world, propylene glycol (PG) based fluids are used to de-ice aircraft for safe operation. PG removal was investigated in 15-cm deep saturated sand columns. Greater than 99% PG biodegradation was achieved for all flow rates and loading conditions tested, which decreased the hydraulic conductivity of the sand by 1-3 orders of magnitude until a steady-state minimum was reached. Under constant loading at 120 mg PG/d for 15-30 d, the hydraulic conductivity (K) decreased by 2-2.5 orders of magnitude when the average linear velocity of the water was 4.9-1.4 cm/h. Variable PG loading in recirculation tests resulted in slower conductivity declines and lower final steady-state conductivity than constant PG feeding. After significant sand plugging, endogenous periods of time without PG resulted in significant but partial recovery of the original conductivity. Biomass growth also increased the dispersivity of the sand.

Cobalt(II) chloride adducts with acetonitrile, propan-2-ol and tetrahydrofuran: considerations on nuclearity, reactivity and synthetic applications.

PubMed

Stinghen, Danilo; Rüdiger, André Luis; Giese, Siddhartha O K; Nunes, Giovana G; Soares, Jaísa F; Hughes, David L

2017-02-01

High-spin cobalt(II) complexes are considered useful building blocks for the synthesis of single-molecule magnets (SMM) because of their intrinsic magnetic anisotropy. In this work, three new cobalt(II) chloride adducts with labile ligands have been synthesized from anhydrous CoCl 2 , to be subsequently employed as starting materials for heterobimetallic compounds. The products were characterized by elemental, spectroscopic (EPR and FT-IR) and single-crystal X-ray diffraction analyses. trans-Tetrakis(acetonitrile-κN)bis(tetrahydrofuran-κO)cobalt(II) bis[(acetonitrile-κN)trichloridocobaltate(II)], [Co(C 2 H 3 N) 4 (C 4 H 8 O) 2 ][CoCl 3 (C 2 H 3 N)] 2 , (1), comprises mononuclear ions and contains both acetonitrile and tetrahydrofuran (thf) ligands, The coordination polymer catena-poly[[tetrakis(propan-2-ol-κO)cobalt(II)]-μ-chlorido-[dichloridocobalt(II)]-μ-chlorido], [Co 2 Cl 4 (C 3 H 8 O) 4 ], (2'), was prepared by direct reaction between anhydrous CoCl 2 and propan-2-ol in an attempt to rationalize the formation of the CoCl 2 -alcohol adduct (2), probably CoCl 2 (HO i Pr) m . The binuclear complex di-μ-chlorido-1:2κ 4 Cl:Cl-dichlorido-2κ 2 Cl-tetrakis(tetrahydrofuran-1κO)dicobalt(II), [Co 2 Cl 4 (C 4 H 8 O) 4 ], (3), was obtained from (2) after recrystallization from tetrahydrofuran. All three products present cobalt(II) centres in both octahedral and tetrahedral environments, the former usually less distorted than the latter, regardless of the nature of the neutral ligand. Product (2') is stabilized by an intramolecular hydrogen-bond network that appears to favour a trans arrangement of the chloride ligands in the octahedral moiety; this differs from the cis disposition found in (3). The expected easy displacement of the bound solvent molecules from the metal coordination sphere makes the three compounds good candidates for suitable starting materials in a number of synthetic applications.

Photocatalytic oxidation of propylene on La and N codoped TiO2 nanoparticles

NASA Astrophysics Data System (ADS)

Liu, Jinfeng; Li, Haiyan; Zong, Lanlan; Li, Qiuye; Wang, Xiaodong; Zhang, Min; Yang, Jianjun

2015-02-01

Lanthanum- and nitrogen-codoped TiO2 photocatalysts was synthesized using orthorhombic nanotubes titanic acid as the precursor by a simple impregnation and subsequent calcination method. The morphology, phase structure, and properties of La- and N-codoped TiO2 were well characterized by transmission electron microscopy, X-ray diffraction, Raman spectra, X-ray photoelectron spectroscopy, and UV-Vis diffuse reflectance spectra. The La-/N-codoped TiO2 showed excellent photoactivity of propylene oxidation compared with the single-doped TiO2 and La-/N-codoped P25 TiO2 nanoparticles under visible light irradiation. The origin of the enhancement of the visible light-responsive photocatalytic activity was discussed in detail.

A solution blending route to ethylene propylene diene terpolymer/layered double hydroxide nanocomposites

PubMed Central

Acharya, H; Bhowmick, Anil K

2007-01-01

Ethylene propylene diene terpolymer (EPDM)/MgAl layered double hydroxide (LDH) nanocomposites have been synthesized by solution intercalation using organically modified LDH (DS-LDH). The molecular level dispersion of LDH nanolayers has been verified by the disappearance of basal XRD peak of DS-LDH in the composites. The internal structures, of the nanocomposite with the dispersion nature of LDH particles in EPDM matrix have been studied by TEM and AFM. Thermogravimetric analysis (TGA) shows thermal stability of nanocomposites improved by ≈40 °C when 10% weight loss was selected as point of comparison. The degradation for pure EPDM is faster above 380 °C while in case of its nanocomposites, it is much slower.

Solvent effects on static and dynamic polarizability and hyperpolarizabilities of acetonitrile

NASA Astrophysics Data System (ADS)

Cammi, Roberto; Cossi, Maurizio; Mennucci, Benedetta; Tomasi, Jacopo

1997-12-01

An application of the theory recently developed to calculate SCF static and dynamic (hyper)polarizabilities of molecular solutes within the framework of the polarizable continuum model is presented here. The specific system under analysis is given by the acetonitrile molecule both in vacuo and in two different dilute solutions, water and benzene. The numerical results reported in the present paper are focused on an evaluation of the main changes produced by the presence of a solvent on the static and dynamic polarizability, α, and first and second hyperpolarizabilities, β and ρ, with respect to the corresponding quantities in the gas phase. The limits of the present calculations, and the prospects for their refinement, are discussed with a view to giving a preliminary hint and a first tool for future reliable prediction of the behavior of this kind of response function when the molecule is perturbed by the presence of a surrounding medium.

The thermochemical characteristics of solution of phenol and benzoic acid in water-dimethylsulfoxide and water-acetonitrile mixtures

NASA Astrophysics Data System (ADS)

Zakharov, A. G.; Voronova, M. I.; Batov, D. V.; Smirnova, K. V.

2011-03-01

The solution of phenol and benzoic acid in water-dimethylsulfoxide (DMSO) and water-acetonitrile (AN) mixtures was studied. As distinct from benzoic acid, the thermodynamic characteristics of solution of phenol sharply change at concentrations corresponding to a change in the character of cluster formation in water-DMSO and water-AN mixtures. Differences in the solvation of phenol and benzoic acid are explained by different mechanisms of the interaction of the solutes with clusters existing in binary mixtures.

Crystallization of toxic glycol solvates of rifampin from glycerin and propylene glycol contaminated with ethylene glycol or diethylene glycol.

PubMed

de Villiers, Melgardt M; Caira, Mino R; Li, Jinjing; Strydom, Schalk J; Bourne, Susan A; Liebenberg, Wilna

2011-06-06

This study was initiated when it was suspected that syringe blockage experienced upon administration of a compounded rifampin suspension was caused by the recrystallization of toxic glycol solvates of the drug. Single crystal X-ray structure analysis, powder X-ray diffraction, thermal analysis and gas chromatography were used to identify the ethylene glycol in the solvate crystals recovered from the suspension. Controlled crystallization and solubility studies were used to determine the ease with which toxic glycol solvates crystallized from glycerin and propylene glycol contaminated with either ethylene or diethylene glycol. The single crystal structures of two distinct ethylene glycol solvates of rifampin were solved while thermal analysis, GC analysis and solubility studies confirmed that diethylene glycol solvates of the drug also crystallized. Controlled crystallization studies showed that crystallization of the rifampin solvates from glycerin and propylene glycol depended on the level of contamination and changes in the solubility of the drug in the contaminated solvents. Although the exact source of the ethylene glycol found in the compounded rifampin suspension is not known, the results of this study show how important it is to ensure that the drug and excipients comply with pharmacopeial or FDA standards.

Bis(1,3-di-tert-butylimidazolin-2-iminato) titanium complexes as effective catalysts for the monodisperse polymerization of propylene.

PubMed

Sharma, Manab; Yameen, Haneen Simaan; Tumanskii, Boris; Filimon, Sabina-Alexandra; Tamm, Matthias; Eisen, Moris S

2012-10-17

The use of bis(1,3-di-tert-butylimidazolin-2-iminato) titanium dichloride (1) and dimethyl (2) complexes in the polymerization of propylene is presented. The complexes were activated using different amounts of methylalumoxane (MAO), giving in each case a very active catalytic mixture and producing polymers with a narrow molecular weight distribution (polydispersity = 1.10). The use of the cocatalyst triphenylcarbenium (trityl) tetra(pentafluorophenyl)borate totally inhibits the reaction, producing the corresponding bis(1,3-di-tert-butylimidazolin-2-iminato) titanium(III) methyl complex, the trityl radical ((•)CPh(3)), the anionic MeB(C(6)F(5))(4)(-), B(C(6)F(5))(3), and the bis(1,3-di-tert-butylimidazolin-2-iminato) titanium(IV) dimethyl·B(C(6)F(5))(3) complex. The use of a combination of physical methods such as NMR, ESR-C(60), and MALDI-TOF analyses enabled us to propose a plausible mechanism for the polymerization of propylene, presenting that the polymerization is mainly carried out in a living fashion. In addition, we present a slow equilibrium toward a small amount of a dormant species responsible for 2,1-misinsertions and chain transfer processes.

Influence of solvents on species crossover and capacity decay in non-aqueous vanadium redox flow batteries: Characterization of acetonitrile and 1, 3 dioxolane solvent mixture

NASA Astrophysics Data System (ADS)

Bamgbopa, Musbaudeen O.; Almheiri, Saif

2017-02-01

The importance of the choice of solvent in a non-aqueous redox flow battery (NARFB) cannot be overemphasized. Several studies demonstrated the influence of the solvent on electrolyte performance in terms of reaction rates, energy/power densities, and efficiencies. In this work, we investigate capacity decay as a direct consequence of varying reactant crossover rates through membranes in different solvent environments. Specifically, we demonstrate the superiority of an 84/16 vol% acetonitrile/1,3 dioxolane solvent mixture over pure acetonitrile in terms of energy efficiency (up to 89%) and capacity retention for vanadium NARFBs - while incorporating a Nafion 115 membrane. The permeability of Nafion to the vanadium acetylacetonate active species is an order of magnitude lower when pure acetonitrile is replaced by the solvent mixture. A method to estimate relative membrane permeability is formulated from numerical analysis of self-discharge experimental data. Furthermore, tests on a modified Nafion/SiO2 membrane, which generally offered low species permeability, also show that different solvents alter membrane permeability. Elemental and morphological analyses of cycled Nafion and NafionSi membranes in different solvent environments indicate that different crossover rates induced by the choice of solvent during cycling are due to changes in the membrane microstructure, intrinsic permeability, swelling rates, and chemical stability.

Irradiation and measurements of fluorinated ethylene-propylene-A on silicon solar cells in vacuum

NASA Technical Reports Server (NTRS)

Marsik, S. J.; Broder, J. D.

1975-01-01

Silicon monoxide (SiO) coated silicon solar cells covered with fluorinated ethylene-propylene-A (FEP-A) were irradiated by 1-MeV electrons in vacuum. The effect of irradiation on the light transmittance of FEP-A was checked by measuring the short-circuit current of the cells while in vacuum after each dose increment, immediately after the irradiation, and again after a minimum elapsed time of 16 hr. The results indicated no apparent loss in transmission due to irradiation of FEP-A and no delamination from the SiO surface while the cells were in vacuum, but embrittlement of FEP-A occurred at the accumulated dose.

Erosion characteristics of ethylene propylene diene monomer composite insulation by high-temperature dense particles

NASA Astrophysics Data System (ADS)

Li, Jiang; Guo, Meng-fei; Lv, Xiang; Liu, Yang; Xi, Kun; Guan, Yi-wen

2018-04-01

In this study, a dense particles erosion test motor which can simulate the erosion state of a solid rocket motor under high acceleration was developed. Subsequently, erosion experiments were carried out for the ethylene propylene diene monomer composite insulation and the microstructure of the char layer analysed. A turning point effect was found from the influence of the particle impact velocity on the ablation rate, and three erosion modes were determined according to the micro-morphology of the char layer. A reasonable explanation for the different structures of the char layer in the three modes was presented based on the formation mechanism of the compact/loose structure of the char layer.

Effect of end segment on physicochemical properties and platelet compatibility of poly(propylene glycol)-initiated poly(methyl methacrylate).

PubMed

Fukuda, Chihiro; Yahata, Chie; Kinoshita, Takuya; Watanabe, Takafumi; Tsukamoto, Hideo; Mochizuki, Akira

2017-10-01

It is well known that polyether-based copolymers have good blood compatibility, although many mechanisms have been proposed to explain their favorable performance. Our objective in carrying out the present study was to obtain a better understanding of the effect of the (poly)ether segment on blood compatibility. Therefore, we synthesized poly(propylene glycol) (PPG)-based initiators for atom transfer polymerization, where the number of propylene glycol (PG) units in the PPG (Pn(PG) was varied from 1 to 94. Methyl methacrylate (MMA) was polymerized using the initiators, resulting in the formation of polyMMAs with a PG-based ether part at the polymer terminal. We mainly investigated the effects of Pn(PG) on the surface properties and platelet compatibility of the PPG-polyMMA. X-ray photoelectron spectroscopy and surface contact angle (CA) analysis revealed the exposure of the PG units at the surface of the polymer. The platelet compatibility of the polymers was improved compared with a commercial polyMMA, even when Pn(PG) = 1. These results suggest that PG units have an important influence on favorable blood compatibility, regardless of the Pn(PG) value. We also investigated protein adsorption behavior in terms of the amount and deformation of fibrinogen adsorbed on the polymer surface.

Carbon-encapsulated cobalt nanoparticles: synthesis, properties, and magnetic particle hyperthermia efficiency

NASA Astrophysics Data System (ADS)

Kotoulas, A.; Dendrinou-Samara, C.; Sarafidis, C.; Kehagias, Th.; Arvanitidis, J.; Vourlias, G.; Angelakeris, M.; Kalogirou, Orestis

2017-12-01

A facile and low-cost method for structuring carbon-encapsulated cobalt nanoparticles (Co@C) is presented. Three samples were solvothermally prepared in one step at 220 °C and one in two steps at 200 °C. Three different polyols such as propylene glycol, triethylene glycol, and tetraethylene glycol were used as carbon sources, solvents, and reducing agents. The samples were characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), and Raman spectroscopy. Concerning the crystal structure of the particles, a mixture of hcp/ fcc Co phases was obtained in three of the samples, independently of the polyol used. The coexistence of cubic and hexagonal phases was revealed both from XRD and high-resolution TEM (HRTEM). The formation of the cubic fcc structure, despite the relatively low reaction temperature, is attributed to the role of the interface between carbon coating and metallic core. The presence of carbon coating was demonstrated by Raman spectrometry, exhibiting the characteristic D and G graphitic bands, and by HRTEM observations. All samples showed ferromagnetic behavior with saturation magnetization up to 158 emu/g and coercivity up to 206 Oe. From the magnetic particle hyperthermia measurements recorded at a frequency of 765 kHz, a maximum SLP value of 241 W/g was obtained.

Acetylcholinesterase and Acetylcholine Receptor.

DTIC Science & Technology

1986-01-21

Cl3CCH2OH) binds similarly to its carbon analogue, neopentyl alcohol, and chloral binds better than its carbon analogue, pivalaldehyde. In the latter case...III. Since the 3H-DFP was obtained in propylene glycol , the stability of DFP in the hydroxylic solvent and thus its true concentration was investi...solution of unlabeled DFP in propylene glycol was obtained from NEN for use in model experi- ments and found to have no inhibiting activity. We turned

A randomized controlled trial of dexamethasone as an adjunctive therapy to propylene glycol for treatment of hyperketonemia in postpartum dairy cattle.

PubMed

Tatone, Elise H; Duffield, Todd F; Capel, Michael B; DeVries, Trevor J; LeBlanc, Stephen J; Gordon, Jessica L

2016-11-01

Treatment of hyperketonemia with oral propylene glycol has proven efficacy but the cure rate remains moderate. Dexamethasone has long been suggested as a treatment for hyperketonemia, even though evidence of its efficacy is contradictory. The objective of this randomized controlled trial was to evaluate the effect of adding a single intramuscular injection of 20mg of dexamethasone to oral propylene glycol therapy for hyperketonemia [blood β-hydroxybutyrate (BHB) ≥1.2mmol/L]. All cows between 3 and 16d in milk on 4 dairy farms in New York State were tested once weekly for hyperketonemia using a handheld ketone meter. All enrolled animals received 312g (300mL) of propylene glycol orally once daily for 4d and either a single injection of dexamethasone or an equivalent volume of sterile saline. A total of 509 animals were enrolled, with 254 and 255 in the placebo and dexamethasone groups, respectively. Treatment with dexamethasone decreased the odds of being hyperketonemic in the second week posttreatment; however, the odds of hyperketonemia in the first week posttreatment only decreased in those animals that were treated at a BHB blood concentration between 1.2 and 1.5mmol/L. For the 8% of cows with blood BHB >3.2mmol/L at enrollment, receiving dexamethasone increased the odds of being hyperketonemic the following week. We detected no difference between treatment groups in the odds of postpartum disease or in milk production. For cows with initial BHB of 1.2 to 1.5mmol/L, treatment with dexamethasone tended to reduce the odds of pregnancy at first insemination. Based on the small and conditional benefits of dexamethasone and a lack of difference in milk yield or disease incidence, we do not recommend the use of dexamethasone to treat hyperketonemia. Copyright © 2016 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Liquid for absorption of solar heat

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

Nakamura, T.; Iwamoto, Y.; Kadotani, K.

A liquid for the absorption of solar heat, useful as an heat-absorbing medium in water heaters and heat collectors comprises: a dispersing medium selected from the group consisting of propylene glycol, mixture of propylene glycol with water, mixture of propylene glycol with water and glycerin, and mixture of glycerin with water, a dispersant selected from the group consisting of polyvinylpyrrolidone, caramel, and mixture of polyvinylpyrrolidone with caramel, and a powdered activated carbon as a black coloring material.

Roles of Poly(propylene Glycol) During Solvent-Based Lamination of Ceramic Green Tapes

NASA Technical Reports Server (NTRS)

Suppakarn, Nitinat; Ishida, Hatsuo; Cawley, James D.; Levine, Stanley R. (Technical Monitor)

2000-01-01

Solvent lamination for alumina green tapes is readily accomplished using a mixture of ethanol, toluene and poly(propylene glycol). After lamination, the PPG is clearly present as a discrete film at the interface between the laminated tapes. This condition, however, does not generate delamination during firing. Systematic sets of experiments are undertaken to determine the role of PPG in the lamination process and, specifically, the mechanism by which it is redistributed during subsequent processing. PPG slowly diffuses through the organic binder film at room temperature. The PPG diffusion rapidly increases as temperature is increased to 80 C. The key to the efficiency of adhesives during green-tape lamination is mutual solubility of the nonvolatile component of the glue and the base polymeric binder.

Occurrence of enzymes involved in biosynthesis of indole-3-acetic acid from indole-3-acetonitrile in plant-associated bacteria, Agrobacterium and Rhizobium.

PubMed Central

Kobayashi, M; Suzuki, T; Fujita, T; Masuda, M; Shimizu, S

1995-01-01

The occurrence of a hitherto unknown pathway involving the action of two enzymes, a nitrile hydratase and an amidase for the biosynthesis of indole-3-acetic acid was discovered in phytopathogenic bacteria Agrobacterium tumefaciens and in leguminous bacteria Rhizobium. The nitrile hydratase acting on indole-3-acetonitrile was purified to homogeneity through only two steps from the cell-free extract of A. tumefaciens. The molecular mass of the purified enzyme estimated by HPLC was about 102 kDa, and the enzyme consisted of four subunits identical in molecular mass. The enzyme exhibited a broad absorption spectrum in the visible range with absorption maxima at 408 nm and 705 nm, and it contained cobalt and iron. The enzyme stoichiometrically catalyzed the hydration of indole-3-acetonitrile into indole-3-acetamide with a specific activity of 13.7 mol per min per mg and a Km of 7.9 microM. Images Fig. 1 PMID:11607511

Combinatorial Optimization of Heterogeneous Catalysts Used in the Growth of Carbon Nanotubes

NASA Technical Reports Server (NTRS)

Cassell, Alan M.; Verma, Sunita; Delzeit, Lance; Meyyappan, M.; Han, Jie

2000-01-01

Libraries of liquid-phase catalyst precursor solutions were printed onto iridium-coated silicon substrates and evaluated for their effectiveness in catalyzing the growth of multi-walled carbon nanotubes (MWNTs) by chemical vapor deposition (CVD). The catalyst precursor solutions were composed of inorganic salts and a removable tri-block copolymer (EO)20(PO)70(EO)20 (EO = ethylene oxide, PO = propylene oxide) structure-directing agent (SDA), dissolved in ethanol/methanol mixtures. Sample libraries were quickly assayed using scanning electron microscopy after CVD growth to identify active catalysts and CVD conditions. Composition libraries and focus libraries were then constructed around the active spots identified in the discovery libraries to understand how catalyst precursor composition affects the yield, density, and quality of the nanotubes. Successful implementation of combinatorial optimization methods in the development of highly active, carbon nanotube catalysts is demonstrated, as well as the identification of catalyst formulations that lead to varying densities and shapes of aligned nanotube towers.

Vacuum ultraviolet radiation/atomic oxygen synergism in fluorinated ethylene propylene Teflon erosion

NASA Technical Reports Server (NTRS)

Stiegman, A. E.; Brinza, David E.; Laue, Eric G.; Anderson, Mark S.; Liang, Ranty H.

1992-01-01

A micrographic investigation is reported of samples of the fluorinated ethylene propylene (FEP) Teflon thermal-blanketing materials recovered from the Long-Duration Exposure Facility (LDEF) satellite. The samples are taken from the trailing edge and row 8 which correspond to exposures to vacuum UV (VUV) and VUV + atomic O, respectively. Data are taken from SEM and IR-spectra observations, and the LDEF leading-edge FEP shows a high degree of erosion, roughening, and sharp peaks angled in the direction of the flow of atomic O. The trailing edge sample influenced primarily by VUV shows a hard brittle layer and some cracked mosaic patterns. Comparisons to a reference sample suggest that the brittle layer is related to exposure to VUV and is removed by atomic-O impingement. Polymers that are stable to VUV radiation appear to be more stable in terms of atomic oxygen.

Microbial Degradation of Propylene Glycol - Modelling Approach of a Batch Experiment

NASA Astrophysics Data System (ADS)

Dathe, Annette; Fernandez, Perrine; Bakken, Lars; Bloem, Esther; French, Helen

2016-04-01

De-icing chemicals are applied in large amounts at airports during winter conditions to keep the runways and aircrafts ice-free. At Gardermoen airport, Norway, most of the applied chemicals can be captured, but about 10 to 20 % infiltrate into the soil along the runways and during take-off. While the commonly used propylene glycol (PG) is easily degradable by local microbial communities, its biological oxygen demand is high, anoxic zones can develop and soluble Fe+2 and Mn+2 ions eventually can reach the groundwater. The objectives of the presented study are to quantify the mechanisms, which control the order of reduction processes in an unsaturated sandy soil, and to test whether measured redox potentials can help to determine underlying biogeochemical reactions. To investigate the mechanisms of microbial degradation, the water phase of soil samples from Gardermoen Airport was replaced by deionized water with 10 mMol PG or 10 mMol glutamate and the samples were incubated at 10°C for about two weeks. The gas phase was sampled and analyzed automatically every three hours. Microbial degradation of the substrate (PG or glutamate) was modelled following a Monod kinetics using the FME (Flexible Modelling Environment) package of R (Project for Statistical Computing). The model was calibrated against measurements of O2 depletion and CO2 production. The initial concentrations of O2, CO2 and PG or glutamate are known and microbial yields and stoichiometric constants can be calculated from the measurements. Parameter values for the initial microbial population size, maximum microbial growth rate, the half saturation constant, and microbial degradation and respiration rates were fitted using the FME package. The model accounts for carbon from the substrate (PG or glutamate) incorporated into the biomass. Results are promising, but because of the large number of parameters needed to fit a Monod kinetics it is challenging to accurately model a whole redox sequence. The

Novel vaginal drug delivery system: deformable propylene glycol liposomes-in-hydrogel.

PubMed

Vanić, Željka; Hurler, Julia; Ferderber, Kristina; Golja Gašparović, Petra; Škalko-Basnet, Nataša; Filipović-Grčić, Jelena

2014-03-01

Deformable propylene glycol-containing liposomes (DPGLs) incorporating metronidazole or clotrimazole were prepared and evaluated as an efficient drug delivery system to improve the treatment of vaginal microbial infections. The liposome formulations were optimized based on sufficient trapping efficiencies for both drugs and membrane elasticity as a prerequisite for successful permeability and therapy. An appropriate viscosity for vaginal administration was achieved by incorporating the liposomes into Carbopol hydrogel. DPGLs were able to penetrate through the hydrogel network more rapidly than conventional liposomes. In vitro studies of drug release from the liposomal hydrogel under conditions simulating human treatment confirmed sustained and diffusion-based drug release. Characterization of the rheological and textural properties of the DPGL-containing liposomal hydrogels demonstrated that the incorporation of DPGLs alone had no significant influence on mechanical properties of hydrogels compared to controls. These results support the great potential of DPGL-in-hydrogel as an efficient delivery system for the controlled and sustained release of antimicrobial drugs in the vagina.

Compensated Arrhenius formalism applied to a conductivity study in poly(propylene glycol) diacrylate monomers.

PubMed

Dubois, F; Derouiche, Y; Leblond, J M; Maschke, U; Douali, R

2015-09-01

The temperature dependence of the ionic conductivity is studied in a series of poly(propylene glycol) diacrylate monomers. The experimental data are analyzed by means of the approach recently proposed by Petrowsky et al. [J. Phys. Chem. B. 113, 5996 (2009)10.1021/jp810095g]. This so-called compensated Arrhenius formalism (CAF) approach takes into account the influence of the dielectric permittivity on the exponential prefactor in the classical Arrhenius equation. The experimental data presented in this paper show a good agreement with the CAF; this means that the exponential prefactor is principally dielectric permittivity dependent. The compensated data revealed two conduction processes with different activation energies; they correspond to low and high temperature ranges, respectively.

Compensated Arrhenius formalism applied to a conductivity study in poly(propylene glycol) diacrylate monomers

NASA Astrophysics Data System (ADS)

Dubois, F.; Derouiche, Y.; Leblond, J. M.; Maschke, U.; Douali, R.

2015-09-01

The temperature dependence of the ionic conductivity is studied in a series of poly(propylene glycol) diacrylate monomers. The experimental data are analyzed by means of the approach recently proposed by Petrowsky et al. [J. Phys. Chem. B. 113, 5996 (2009), 10.1021/jp810095g]. This so-called compensated Arrhenius formalism (CAF) approach takes into account the influence of the dielectric permittivity on the exponential prefactor in the classical Arrhenius equation. The experimental data presented in this paper show a good agreement with the CAF; this means that the exponential prefactor is principally dielectric permittivity dependent. The compensated data revealed two conduction processes with different activation energies; they correspond to low and high temperature ranges, respectively.

Two-Electron Carbon Dioxide Reduction Catalyzed by Rhenium(I) Bis(imino)acenaphthene Carbonyl Complexes

PubMed Central

Portenkirchner, Engelbert; Kianfar, Elham; Sariciftci, Niyazi Serdar; Knör, Günther

2014-01-01

Rhenium(I) carbonyl complexes carrying substituted bis(arylimino)acenaphthene ligands (BIAN-R) have been tested as potential catalysts for the two-electron reduction of carbon dioxide. Cyclic voltammetric studies as well as controlled potential electrolysis experiments were performed using CO2-saturated solutions of the complexes in acetonitrile and acetonitrile–water mixtures. Faradaic efficiencies of more than 30 % have been determined for the electrocatalytic production of CO. The effects of ligand substitution patterns and water content of the reaction medium on the catalytic performance of the new catalysts are discussed. PMID:24737649

Effect of the Hydrofluoroether Cosolvent Structure in Acetonitrile-Based Solvate Electrolytes on the Li+ Solvation Structure and Li-S Battery Performance.

PubMed

Shin, Minjeong; Wu, Heng-Liang; Narayanan, Badri; See, Kimberly A; Assary, Rajeev S; Zhu, Lingyang; Haasch, Richard T; Zhang, Shuo; Zhang, Zhengcheng; Curtiss, Larry A; Gewirth, Andrew A

2017-11-15

We evaluate hydrofluoroether (HFE) cosolvents with varying degrees of fluorination in the acetonitrile-based solvate electrolyte to determine the effect of the HFE structure on the electrochemical performance of the Li-S battery. Solvates or sparingly solvating electrolytes are an interesting electrolyte choice for the Li-S battery due to their low polysulfide solubility. The solvate electrolyte with a stoichiometric ratio of LiTFSI salt in acetonitrile, (MeCN) 2 -LiTFSI, exhibits limited polysulfide solubility due to the high concentration of LiTFSI. We demonstrate that the addition of highly fluorinated HFEs to the solvate yields better capacity retention compared to that of less fluorinated HFE cosolvents. Raman and NMR spectroscopy coupled with ab initio molecular dynamics simulations show that HFEs exhibiting a higher degree of fluorination coordinate to Li + at the expense of MeCN coordination, resulting in higher free MeCN content in solution. However, the polysulfide solubility remains low, and no crossover of polysulfides from the S cathode to the Li anode is observed.

Effect of the Hydrofluoroether Cosolvent Structure in Acetonitrile-Based Solvate Electrolytes on the Li+ Solvation Structure and Li-S Battery Performance.

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

Shin, Minjeong; Wu, Heng-Liang; Narayanan, Badri

We evaluate hydrofluoroether (HFE) cosolvents with varying degrees of fluorination in the acetonitrile-based solvate electrolyte to determine the effect of the HFE structure on the electrochemical performance of the Li-S battery. Solvates or sparingly solvating electrolytes are an interesting electrolyte choice for the Li-S battery due to their low polysulfide solubility. The solvate electrolyte with a stoichiometric ratio of LiTFSI salt in acetonitrile, (MeCN)(2)-LiTFSI, exhibits limited polysulfide solubility due to the high concentration of LiTFSI. We demonstrate that the addition of highly fluorinated HFEs to the solvate yields better capacity retention compared to that of less fluorinated HFE cosolvents. Ramanmore » and NMR spectroscopy coupled with ab initio molecular dynamics simulations show that HFEs exhibiting a higher degree of fluorination coordinate to Li+ at the expense of MeCN coordination, resulting in higher free MeCN content in solution. However, the polysulfide solubility remains low, and no crossover of polysulfides from the S cathode to the Li anode is observed.« less

Solvent-Free Mechanochemical Synthesis of Nitrogen-Doped Nanoporous Carbon for Electrochemical Energy Storage.

PubMed

Schneidermann, Christina; Jäckel, Nicolas; Oswald, Steffen; Giebeler, Lars; Presser, Volker; Borchardt, Lars

2017-06-09

Nitrogen-doped nanoporous carbons were synthesized by a solvent-free mechanochemically induced one-pot synthesis. This facile approach involves the mechanochemical treatment and carbonization of three solid materials: potassium carbonate, urea, and lignin, which is a waste product from pulp industry. The resulting nitrogen-doped porous carbons offer a very high specific surface area up to 3000 m 2  g -1 and large pore volume up to 2 cm 3  g -1 . The mechanochemical reaction and the impact of activation and functionalization are investigated by nitrogen and water physisorption and high-resolution X-ray photoelectron spectroscopy (XPS). Our N-doped carbons are highly suitable for electrochemical energy storage as supercapacitor electrodes, showing high specific capacitances in aqueous 1 m Li 2 SO 4 electrolyte (177 F g -1 ), organic 1 m tetraethylammonium tetrafluoroborate in acetonitrile (147 F g -1 ), and an ionic liquid (1-ethyl-3-methylimidazolium tetrafluoroborate; 192 F g -1 ). This new mechanochemical pathway synergistically combines attractive energy-storage ratings with a scalable, time-efficient, cost-effective, and environmentally favorable synthesis. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Suicide attempt with acetonitrile ingestion in a nursing mother.

PubMed

De Capitani, Eduardo Mello; Borrasca-Fernandes, Carla Fernanda; Branco Pimenta, Maíra; Prado, Camila Carbone; Soubhia, Paula Christiane; Lanaro, Rafael; Mello Moreira, Sueli; Linden, Rafael; Nóbrega, Helena Valle; Bucaretchi, Fábio; Costa, José Luiz

2017-09-01

Acetonitrile (ACN) is a solvent rapidly absorbed through lungs and intestinal tract, and is slowly metabolized to cyanide (CN) by enzymatic processes mediated by CYP2E1. To describe the clinical and laboratory evolution, ACN elimination half-life, and its presence in breast milk in a nursing mother who attempted suicide. A 25-year-old 2-month nursing mother ingested an estimated dose of 2.1 g/kg of ACN. Blood and urine samples were collected 24 h later for ACN, CN and thiocyanate analysis, and 12.5 g sodium thiosulfate i.v. in 1-h infusion was started and repeated every 24 h for 4 days. ACN results showed 200 mg/L in blood and 235 mg/L in urine. ACN analysis in the breast milk at Day 6 showed level of 21 mg/L compared to 27 mg/L in blood collected at the same time, suggesting a possible relationship of 1.3:1.0 ratio. An elimination half-life of 40.4 h was calculated, compared to 32 and 36 h showed in other studies. The clinical management must involve the use of CN antidotes for more than 24 h depending on the symptoms and blood levels of ACN. Furthermore, our data showed the possible existence of a close relationship between plasma and breast milk levels.

Systematic study on the influence of the morphology of α-MoO{sub 3} in the selective oxidation of propylene

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

Schuh, Kirsten; Kleist, Wolfgang; Høj, Martin

2015-08-15

A variety of morphologically different α-MoO{sub 3} samples were prepared by hydrothermal synthesis and applied in the selective oxidation of propylene. Their catalytic performance was compared to α-MoO{sub 3} prepared by flame spray pyrolysis (FSP) and a classical synthesis route. Hydrothermal synthesis from ammonium heptamolybdate (AHM) and nitric acid at pH 1–2 led to ammonium containing molybdenum oxide phases that were completely transformed into α-MoO{sub 3} after calcination at 550 °C. A one-step synthesis of α-MoO{sub 3} rods was possible starting from MoO{sub 3}·2H{sub 2}O with acetic acid or nitric acid and from AHM with nitric acid at 180 °C.more » Particularly, if nitric acid was used during synthesis, the rod-like morphology of the samples could be stabilized during calcination at 550 °C and the following catalytic activity tests, which was beneficial for the catalytic performance in propylene oxidation. Characterization studies using X-ray diffraction (XRD), scanning electron microscopy (SEM) and Raman spectroscopy showed that those samples, which retained their rod-like morphology during the activity tests, yielded the highest propylene conversion. - Graphical abstract: Hydrothermal synthesis from MoO{sub 3}·2H{sub 2}O in the presence of HNO{sub 3} led to rod-shaped particles which mainly expose (1 0 0) facets which are the most active surfaces. - Highlights: • Hydrothermal synthesis of MoO3 resulted in either rod or slab shaped particles depending on pH. • At pH<0 rods stable towards calcination and catalytic activity testing were formed. • Rod shaped particles had significantly higher activity than slab shaped ones. • The rod shaped particles mainly expose the (1 0 0) facets which are the most active surfaces. • Total surface area is not main determining factor for catalytic activity.« less

A toxicological review of the propylene glycols.

PubMed

Fowles, Jeff R; Banton, Marcy I; Pottenger, Lynn H

2013-04-01

The toxicological profiles of monopropylene glycol (MPG), dipropylene glycol (DPG), tripropylene glycol (TPG) and polypropylene glycols (PPG; including tetra-rich oligomers) are collectively reviewed, and assessed considering regulatory toxicology endpoints. The review confirms a rich data set for these compounds, covering all of the major toxicological endpoints of interest. The metabolism of these compounds share common pathways, and a consistent profile of toxicity is observed. The common metabolism provides scientific justification for adopting a read-across approach to describing expected hazard potential from data gaps that may exist for specific oligomers. None of the glycols reviewed presented evidence of carcinogenic, mutagenic or reproductive/developmental toxicity potential to humans. The pathologies reported in some animal studies either occurred at doses that exceeded experimental guidelines, or involved mechanisms that are likely irrelevant to human physiology and therefore are not pertinent to the exposures experienced by consumers or workers. At very high chronic doses, MPG causes a transient, slight decrease in hemoglobin in dogs and at somewhat lower doses causes Heinz bodies to form in cats in the absence of any clinical signs of anemia. Some evidence for rare, idiosyncratic skin reactions exists for MPG. However, the larger data set indicates that these compounds have low sensitization potential in animal studies, and therefore are unlikely to represent human allergens. The existing safety evaluations of the FDA, USEPA, NTP and ATSDR for these compounds are consistent and point to the conclusion that the propylene glycols present a very low risk to human health.

On-column nitrosation of amines observed in liquid chromatography impurity separations employing ammonium hydroxide and acetonitrile as mobile phase.

PubMed

Myers, David P; Hetrick, Evan M; Liang, Zhongming; Hadden, Chad E; Bandy, Steven; Kemp, Craig A; Harris, Thomas M; Baertschi, Steven W

2013-12-06

The availability of high performance liquid chromatography (HPLC) columns capable of operation at pH values up to 12 has allowed a greater selectivity space to be explored for method development in pharmaceutical analysis. Ammonium hydroxide is of particular value in the mobile phase because it is compatible with direct interfacing to electrospray mass spectrometers. This paper reports an unexpected N-nitrosation reaction that occurs with analytes containing primary and secondary amines when ammonium hydroxide is used to achieve the high pH and acetonitrile is used as the organic modifier. The nitrosation reaction has generality. It has been observed on multiple columns from different vendors and with multiple amine-containing analytes. Ammonia was established to be the source of the nitroso nitrogen. The stainless steel column frit and metal ablated from the frit have been shown to be the sites of the reactions. The process is initiated by removal of the chromium oxide protective film from the stainless steel by acetonitrile. It is hypothesized that the highly active, freshly exposed metals catalyze room temperature oxidation of ammonia to NO but that the actual nitrosating agent is likely N(2)O(3). Copyright © 2013 Elsevier B.V. All rights reserved.

Combined Theoretical and Experimental Study of Refractive Indices of Water-Acetonitrile-Salt Systems.

PubMed

An, Ni; Zhuang, Bilin; Li, Minglun; Lu, Yuyuan; Wang, Zhen-Gang

2015-08-20

We propose a simple theoretical formula for describing the refractive indices in binary liquid mixtures containing salt ions. Our theory is based on the Clausius-Mossotti equation; it gives the refractive index of the mixture in terms of the refractive indices of the pure liquids and the polarizability of the ionic species, by properly accounting for the volume change upon mixing. The theoretical predictions are tested by extensive experimental measurements of the refractive indices for water-acetonitrile-salt systems for several liquid compositions, different salt species, and a range of salt concentrations. Excellent agreement is obtained in all cases, especially at low salt concentrations, with no fitting parameters. A simplified expression of the refractive index for low salt concentration is also given, which can be the theoretical basis for determination of salt concentration using refractive index measurements.

Small-Scale Mechanical Characterization of Space-Exposed Fluorinated Ethylene Propylene Recovered from the Hubble Space Telescope

NASA Technical Reports Server (NTRS)

Jones, J. S.; Sharon, J. A.; Mohammed, J.; Hemker, K. J.

2012-01-01

Multi-layer insulation panels from the Hubble Space Telescope have been recovered after 19.1 years of on-orbit service and micro-tensile experiments have been performed to characterize the effect of space exposure on the mechanical response of the outermost layer. This outer layer, 127 m thick fluorinated ethylene propylene with a 100 nm thick vapor deposited aluminum reflective coating, maintained significant tensile ductility but exhibited a degradation of strength that scales with severity of space exposure. This change in properties is attributed to damage from incident solar flux, atomic oxygen damage, and thermal cycling.

Ruminal and intermediary metabolism of propylene glycol in lactating Holstein cows.

PubMed

Kristensen, N B; Raun, B M L

2007-10-01

Four lactating Holstein cows fitted with ruminal cannulas and permanent indwelling catheters in the mesenteric artery, mesenteric vein, hepatic portal vein, and hepatic vein were used in a cross-over design to study the metabolism of propylene glycol (PG). Each cow received 2 treatments: control (no infusion) and infusion of 650 g of PG into the rumen at the time of the morning feeding. Propylene glycol was infused on the day of sampling only. Samples of arterial, portal, and hepatic blood as well as ruminal fluid were obtained at 0.5 h before feeding and at 0.5, 1.5, 2.5, 3.5, 5, 7, 9, and 11 h after feeding. Infusion of PG did not affect ruminal pH or the total concentration of ruminal volatile fatty acids, but did decrease the molar proportion of ruminal acetate. The ruminal concentrations of PG, propanol, and propanal as well as the molar proportion of propionate increased with PG infusion. The plasma concentrations of PG, ethanol, propanol, propanal, glucose, L-lactate, propionate, and insulin increased with PG and the plasma concentrations of acetate and beta-hydroxybutyrate decreased. The net portal flux of PG, propanol, and propanal increased with PG. The hepatic uptake of PG was equivalent to 19% of the intraruminal dose. When cows were dosed with PG, the hepatic extraction of PG was between 0 and 10% depending on the plasma concentration of PG, explaining the slow decrease in arterial PG. The increased net hepatic flux of L-lactate with PG could account for the entire hepatic uptake of PG, which suggests that the primary hepatic pathway for PG is oxidation to l-lactate. The hepatic uptake of propanol increased with PG, but no effects of PG on the net hepatic and net splanchnic flux of glucose were observed. Despite no effect of PG on net portal flux and net hepatic flux of propionate, the net splanchnic flux of propionate increased and the data suggest that propionate produced from hepatic metabolism of propanol is partly released to the blood. The data

40 CFR 180.1250 - C8, C10, and C12 fatty acid monoesters of glycerol and propylene glycol; exemption from the...

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 23 2010-07-01 2010-07-01 false C8, C10, and C12 fatty acid monoesters..., C10, and C12 fatty acid monoesters of glycerol and propylene glycol; exemption from the requirement of a tolerance. The C8, C10, and C12 straight-chain fatty acid monoesters of glycerol (glycerol...

40 CFR 180.1250 - C8, C10, and C12 fatty acid monoesters of glycerol and propylene glycol; exemption from the...

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 24 2011-07-01 2011-07-01 false C8, C10, and C12 fatty acid monoesters..., C10, and C12 fatty acid monoesters of glycerol and propylene glycol; exemption from the requirement of a tolerance. The C8, C10, and C12 straight-chain fatty acid monoesters of glycerol (glycerol...

Rheological properties and thermal conductivity of AlN-poly(propylene glycol) suspensions

NASA Astrophysics Data System (ADS)

Wozniak, Maciej; Rutkowski, Pawel; Kata, Dariusz

2016-01-01

Nanofluids have recently attracted researches' attention as a new generation of heat-transferring fluids used in heat exchangers and for energy storage. Also aluminium nitride is commonly known for its considerable heat conductivity, as high as 320 W/(m K). Because of that, the compound might be a preferable dispersed phase of heat-transferring fluids. This presented studies are focused on nano-AlN-poly(propylene glycol) dispersions which can be applied as potential cooling fluids. The rheological response of the suspensions on shearing and their thermal conductivity in the function of solids concentration and temperature were measured and discussed. The most desired result of the studies is to produce dispersions with Newtonian-like flow at increased temperature and at higher shear rate. All the aforementioned parameters conjugated with significant thermal conductivity of such nanofluids could predispose them to be used as effective cooling media.

Competitive cesium-133 NMR spectroscopic study of complexation of different metal ions with dibenzo-21-crown-7 in acetonitrile-dimethylsulfoxide and nitromethane-dimethylsulfoxide mixtures.

PubMed

Sahmsipur, Mojtaba; Dastjerdi, Leila Shafiee; Alizadeh, Nader; Bijanzadeh, Hamid Reza

2008-04-01

(133)Cs NMR spectroscopy was used to determine the stoichiometry and stability of the Cs(+) ion complex with dibenzo-21-crown-7 (DB21C7) in acetonitrile-dimethylsulfoxide (96.5:3.5, w/w) and nitromethane-dimethylsulfoxide (96.5:3.5, w/w) mixtures. A competitive (133)Cs NMR technique was also employed to probe the complexation of Na(+), K(+), Rb(+), Ag(+), Tl(+), NH(4)(+), Mg(2+), Ba(2+), Hg(2+), Pb(2+) and UO(2)(2+) ions with DB21C7 in the same solvent systems. All the resulting 1:1 complexes in nitromethane-dimethylsulfoxide were more stable than those in acetonitrile-dimethylsulfoxide solution. In both solvent systems, the stability of the resulting complexes was found to vary in the order Rb(+)>K(+) approximately Ba(2+)>Tl(+)>Cs(+)>NH(4)(+) approximately Pb(2+)>Ag(+)>UO(2)(2+)>Hg(2+)>Mg(2+)>Na(+).

Evaluating the Thermodynamics of Electrocatalytic N 2 Reduction in Acetonitrile

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

Lindley, Brian M.; Appel, Aaron M.; Krogh-Jespersen, Karsten

The synthesis of ammonia by proton-coupled electroreduction of dinitrogen (N2) represents a sustainable alternative to currently practiced hydrogenation methods. Developments in this area require knowledge of the standard reduction potentials that describe the thermodynamics of N2 reduction. The first collection of N2 reduction standard potentials in organic solvent are reported here. The potentials for reduction of N2 to ammonia (NH3), hydrazine (N2H4), and diazene (N2H2) in acetonitrile (MeCN) solution are derived using thermochemical cycles. Ammonia is the thermodynamically favored product, with a 0.43 V difference between NH3 and N2H4 and a 1.26 V difference between NH3 and N2H2. The thermodynamicsmore » for reduction of N2 to the protonated products ammonium (NH4+) and hydrazinium (N2H5+) under strongly acidic conditions are also presented. Comparison with previously determined values for the H+/H2 potential in MeCN reveals a 63 mV thermodynamic preference for N2 reduction to NH3 over H2 production. Combined with knowledge of the kinetics of electrode-catalyzed H2 evolution, a wide working region is identified to guide future electrocatalytic studies.« less

Diols and anions can control the formation of an exciplex between a pyridinium boronic acid with an aryl group connected via a propylene linker.

PubMed

Huang, Yan-Jun; Jiang, Yun-Bao; Bull, Steven D; Fossey, John S; James, Tony D

2010-11-21

The exciplex formation between a pyridinium boronic acid and phenyl group connected via a propylene linker can be monitored using fluorescence. Addition of pinacol affords a cyclic boronate ester with enhanced Lewis acidity that increases the strength of its cation-π stacking interaction causing a four-fold fluorescence enhancement.

High performance liquid chromatography for the simultaneous analysis of penicillin residues in beef and milk using ion-paired extraction and binary water-acetonitrile mixture.

PubMed

Kukusamude, Chunyapuk; Burakham, Rodjana; Chailapakul, Orawon; Srijaranai, Supalax

2012-04-15

An ion-paired extraction (IPE) has been developed for the analysis of penicillin antibiotics (penicillin G, oxacillin and cloxacillin) in beef and milk samples using tetrabutylammonium bromide (TBABr) as ion-pairing agent and binary water-acetonitrile as extractant. The factors affecting the IPE efficiency were optimized including solution pH, volume of acetonitrile (ACN), concentration of TBABr and electrolyte salt (NH(4))(2)SO(4). The optimum IPE conditions were 10 mmol L(-1) phosphate buffer pH 8, 2 mL of ACN, 6 mmol L(-1) of TBABr and 2.5 mL of saturated ammonium sulfate. Under the HPLC condition: an Xbridge™ C18 reversed-phase column, isocratic elution of 5 mmol L(-1) phosphate buffer (pH 6.6) and acetonitrile (75:25, v/v) and a flow rate of 1 mL min(-1), with UV detection at 215 nm, the separation of three penicillins was achieved within 10 min. Under the selected optimum conditions, the enhancement of 21-53 folds compared to that without preconcentration and limits of detection (LODs) of 1-2 ng mL(-1) were obtained. Good reproducibility was achieved with RSD<2% for retention time and <5% for slope of calibration curves. The average recoveries higher than 85% were obtained. The proposed IPE-HPLC method has shown to be high efficient preconcentration and analysis method for penicillin residues in beef and milk with LOD lower than the maximum residue limits. Copyright © 2012 Elsevier B.V. All rights reserved.

Reactivity of nonaqueous organic electrolytes towards lithium

NASA Technical Reports Server (NTRS)

Shen, D. H.; Subbarao, S.; Deligiannis, F.; Huang, C.-K.; Halpert, G.

1990-01-01

The successful operation of an ambient temperature secondary lithium cell is primarily dependent on the stability of the electrolyte towards lithium. The lithium electrode on open circuit must be inert towards the electrolyte to achieve a long shelf life. The reactivity of tetrahydrofuran and 2-methyltetrahydrofuran based electrolytes with additives such as 2-methylfuran, ethylene carbonate, propylene carbonate, and 3-methylsulfolane was investigated by microcalorimetry and ac impedance spectroscopy techniques. Also the stability of electrolytes by open circuit stand tests was studied. Addition of ethylene carbonate and 2-methylfuran additives was found to improve the stability of tetrahydrofuran and 2-methyltetrahydrofuran based electrolytes. Long term microcalorimetry and ac impedance data clearly confirmed the higher stability of ethylene carbonate/2-methyltetrahydrofuran electrolyte compared to the 2-methyltetrahydrofuran and propylene carbonate/2-methyltetrahydrofuran electrolytes.

Addition of poly (propylene glycol) to multiblock copolymer to optimize siRNA delivery.

PubMed

Dai, Zhi; Arévalo, Maria T; Li, Junwei; Zeng, Mingtao

2014-01-01

Previous studies have examined different strategies for siRNA delivery with varying degrees of success. These include use of viral vectors, cationic liposomes, and polymers. Several copolymers were designed and synthesized based on blocks of poly(ethylene glycol) PEG, poly(propylene glycol) PPG, and poly(l-lysine). These were designated as P1, P2, and P3. We studied the copolymer self-assembly, siRNA binding, particle size, surface potential, architecture of the complexes, and siRNA delivery. Silencing of GFP using copolymer P3 to deliver GFP-specific siRNA to Neuro-2a cells expressing GFP was almost as effective as using Lipofectamine 2000, with minimal cytotoxicity. Thus, we have provided a new copolymer platform for siRNA delivery that we can continue to modify for improved delivery of siRNA in vitro and eventually in vivo.

Photochemical behavior of the quadruply metal-metal bonded [Tc 2Cl 8] 2– anion in acetonitrile

DOE PAGES

Burton-Pye, Benjamin P.; Poineau, Frederic; Bertoia, Julie; ...

2016-09-23

Here, the photochemical behavior of [Tc 2Cl 8] 2– was investigated in acetonitrile. The speciation of Tc before and after irradiation at 254 nm was performed by UV-visible spectroscopy and electrospray ionization mass spectrometry (ESI-MS). Upon irradiation at 254 nm, [Tc 2Cl 8] 2– was unstable, the scission of the Tc ≡ Tc unit occurred and the complex [TcCl 4(CH 3CN) 2] was identified. The disappearance rate of [M 2Cl 8] 2– (M = Tc, Re) under irradiation has been measured and was ~7.5 time faster for Tc than for Re.

Structure and dynamics of propylammonium nitrate-acetonitrile mixtures: An intricate multi-scale system probed with experimental and theoretical techniques.

PubMed

Campetella, Marco; Mariani, Alessandro; Sadun, Claudia; Wu, Boning; Castner, Edward W; Gontrani, Lorenzo

2018-04-07

In this article, we report the study of structural and dynamical properties for a series of acetonitrile/propylammonium nitrate mixtures as a function of their composition. These systems display an unusual increase in intensity in their X-ray diffraction patterns in the low-q regime, and their 1 H-NMR diffusion-ordered NMR spectroscopy (DOSY) spectra display unusual diffusivities. However, the magnitude of both phenomena for mixtures of propylammonium nitrate is smaller than those observed for ethylammonium nitrate mixtures with the same cosolvent, suggesting that the cation alkyl tail plays an important role in these observations. The experimental X-ray scattering data are compared with the results of molecular dynamics simulations, including both ab initio studies used to interpret short-range interactions and classical simulations to describe longer range interactions. The higher level calculations highlight the presence of a strong hydrogen bond network within the ionic liquid, only slightly perturbed even at high acetonitrile concentration. These strong interactions lead to the symmetry breaking of the NO 3 - vibrations, with a splitting of about 88 cm -1 in the ν 3 antisymmetric stretch. The classical force field simulations use a greater number of ion pairs, but are not capable of fully describing the longest range interactions, although they do successfully account for the observed concentration trend, and the analysis of the models confirms the nano-inhomogeneity of these kinds of samples.

Structure and dynamics of propylammonium nitrate-acetonitrile mixtures: An intricate multi-scale system probed with experimental and theoretical techniques

NASA Astrophysics Data System (ADS)

Campetella, Marco; Mariani, Alessandro; Sadun, Claudia; Wu, Boning; Castner, Edward W.; Gontrani, Lorenzo

2018-04-01

In this article, we report the study of structural and dynamical properties for a series of acetonitrile/propylammonium nitrate mixtures as a function of their composition. These systems display an unusual increase in intensity in their X-ray diffraction patterns in the low-q regime, and their 1H-NMR diffusion-ordered NMR spectroscopy (DOSY) spectra display unusual diffusivities. However, the magnitude of both phenomena for mixtures of propylammonium nitrate is smaller than those observed for ethylammonium nitrate mixtures with the same cosolvent, suggesting that the cation alkyl tail plays an important role in these observations. The experimental X-ray scattering data are compared with the results of molecular dynamics simulations, including both ab initio studies used to interpret short-range interactions and classical simulations to describe longer range interactions. The higher level calculations highlight the presence of a strong hydrogen bond network within the ionic liquid, only slightly perturbed even at high acetonitrile concentration. These strong interactions lead to the symmetry breaking of the NO3 - vibrations, with a splitting of about 88 cm-1 in the ν3 antisymmetric stretch. The classical force field simulations use a greater number of ion pairs, but are not capable of fully describing the longest range interactions, although they do successfully account for the observed concentration trend, and the analysis of the models confirms the nano-inhomogeneity of these kinds of samples.

Unusual solvent effect on a SN2 reaction. A quantum-mechanical and kinetic study of the Menshutkin reaction between 2-amino-1-methylbenzimidazole and iodomethane in the gas phase and in acetonitrile.

PubMed

Melo, André; Alfaia, António J I; Reis, João Carlos R; Calado, António R T

2006-02-02

The quaternization reaction between 2-amino-1-methylbenzimidazole and iodomethane was investigated in the gas phase and in liquid acetonitrile. Both experimental and theoretical techniques were used in this study. In the experimental part of this work, accurate second-order rate constants were obtained for this reaction in acetonitrile from conductivity data in the 293-323 K temperature range and at ambient pressure. From two different empirical equations describing the effect of temperature on reaction rates, thermodynamic functions of activation were calculated. In the theoretical part of this work, the mechanism of this reaction was investigated in the gas phase and in acetonitrile. Two different quantum levels (B3LYP/[6-311++G(3df,3pd)/LanL2DZ]//B3LYP/[6-31G(d)/LanL2DZ] and B3LYP/[6-311++G(3df,3pd)/LanL2DZ]//B3LYP/[6-31+G(d)/LanL2DZ]) were used in the calculations, and the acetonitrile environment was modeled using the polarized continuum model (PCM). In addition, an atoms in molecules (AIM) analysis was made aiming to characterize possible hydrogen bonding. The results obtained by both techniques are in excellent agreement and lead to new insight into the mechanism of the reaction under examination. These include the identification and thermodynamic characterization of the relevant stationary species, the rationalization of the mechanistic role played by the solvent and the amine group adjacent to the nucleophile nitrogen atom, the proposal of alternative paths on the modeled potential energy surfaces, and the origin of the marked non-Arrhenius behavior of the kinetic data in solvent acetonitrile. In particular, the AIM analysis confirmed the operation of intermolecular hydrogen bonds between reactants and between products, both in the gas phase and in solution. It is also concluded that the unusual solvent effect on this Menshutkin reaction stems from the conjunction of a nucleophile possessing a relatively complex chemical structure with a dipolar aprotic

Preparation, characterization and pharmacokinetics of fluorescence labeled propylene glycol alginate sodium sulfate

NASA Astrophysics Data System (ADS)

Li, Pengli; Li, Chunxia; Xue, Yiting; Zhang, Yang; Liu, Hongbing; Zhao, Xia; Yu, Guangli; Guan, Huashi

2014-08-01

A rapid and sensitive fluorescence labeling method was developed and validated for the microanalysis of a sulfated polysaccharide drug,namely propylene glycol alginate sodium sulfate (PSS), in rat plasma. Fluorescein isothiocyanate (FITC) was selected to label PSS, and 1, 6-diaminohexane was used to link PSS and FITC in order to prepare FITC-labeled PSS (F-PSS) through a reductive amination reaction. F-PSS was identified by UV-Vis, FT-IR and 1H-NMR spectrum. The cell stability and cytotoxicity of F-PSS were tested in Madin-Darby canine kidney (MDCK) cells. The results indicated that the labeling efficiency of F-PSS was 0.522% ± 0.0248% and the absolute bioavailability was 8.39%. F-PSS was stable in MDCK cells without obvious cytotoxicity. The method was sensitive and reliable; it showed a good linearity, precision, recovery and stability. The FITC labeling method can be applied to investigating the absorption and metabolism of PSS and other polysaccharides in biological samples.

Solvent controlled intramolecular electron transfer in mixtures of 1-butyl-3-methylimidizolium tetrafluoroborate and acetonitrile

NASA Astrophysics Data System (ADS)

Rumble, Christopher A.; Maroncelli, Mark

2018-05-01

Time-resolved emission techniques were used to study the excited-state intramolecular electron transfer of 9-(4-biphenyl)-10-methylacridinium (BPAc+) in mixtures of 1-butyl-3-methylimidizolium tetrafluoroborate ([Im41][BF4])+ acetonitrile (ACN), a mixture previously shown to be of nearly constant polarity and nearly ideal mixing behavior. Reaction times (τrxn) track solvation times (τsolv) as a function of mixture composition over a range of more than 3 orders of magnitude in τsolv. This same correlation extends to a variety of neat dipolar solvents and ionic liquids. Reaction times are ˜2-fold larger than τsolv over most of the range studied but appear to reach a limiting value of ˜3 ps in the fastest solvents.

Molten-salt treatment of waste biomass for preparation of carbon with enhanced capacitive properties and electrocatalytic activity towards oxygen reduction.

PubMed

Lu, Beihu; Zhou, Jing; Song, Yuqiao; Wang, Hailong; Xiao, Wei; Wang, Dihua

2016-08-15

Carbon powders are building blocks for electrochemical energy storage/conversion devices. Green, cost-affordable and facile preparation of carbon with applicable electrochemical properties is therefore essential for effective utilization of fluctuating renewable energy. Herein, the preparation of carbon nanoflakes via impregnation of waste biomass i.e. boiled coffee beans in molten Na2CO3-K2CO3 (with equal mass) at 800 °C and molten CaCl2 at 850 °C is reported. The microstructure and surface chemistry of the obtained carbons are specified. The correlations between synthetic conditions and microstructure/surface chemistry of the obtained carbons are rationalized. The derived carbon nanosheets are tested and compared as active materials for supercapacitors in a configuration of symmetric full cells in 1 M MeEt3NBF4 in acetonitrile and electrocatalysts towards the oxygen reduction reaction (ORR) in O2-saturated 0.1 M aqueous KOH. Despite the lower surface area, the carbon nanosheets derived in molten Na2CO3-K2CO3 exhibit enhanced capacitive properties and electrocatalytic ORR activity. The present study highlights the importance of thermal media on the microstructure, surface chemistry and electrochemistry of carbon from biomass.

Direct fabrication of ordered mesoporous carbons with super-micropore/small mesopore using mixed triblock copolymers.

PubMed

Li, Peng; Song, Yan; Tang, Zhihong; Yang, Guangzhi; Yang, Junhe

2014-01-01

Ordered mesoporous carbons (OMCs) have been prepared by the strategy of evaporation-induced organic-organic self-assembly method by employing a mixture of amphiphilic triblock copolymers poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) (PEO-PPO-PEO) and reverse PPO-PEO-PPO as templates, with soluble in ethanol, low-molecular-weight phenolic resin as precursor, followed by carbonization. It has been found that the as prepared OMCs with porosity that combines super-micropore and small mesopore size distributed from 0.8 to 4 nm, which bridges the pore size from 2 to 3 nm and also for the diversification of the soft-templating synthesis of OMCs. Furthermore, the results showed that the OMCs obtained have mesophase transition from cylindrical p6 mm to centered rectangular c2 mm structure by simply tuning the ratio of PPO-PEO-PPO/PEO-PPO-PEO. Copyright © 2013 Elsevier Inc. All rights reserved.

μ-Hexa-thio-metadiphosphato-bis-[(1,4,7,10,13,16-hexa-oxa-cyclo-octa-decane-κ(6) O)rubidium] aceto-nitrile disolvate.

PubMed

Gjikaj, Mimoza; Pook, Niels-Patrick; Qarri, Flora

2013-12-01

The asymmetric unit of the title compound, [Rb2(P2S6)(C12H24O6)2]·2CH3CN, contains one half of an [Rb(18-crown-6)2]2[P2S6] unit and one aceto-nitrile solvent mol-ecule. The [Rb(18-crown-6)]2[P2S6] unit is completed by inversion symmetry. Its Rb(+) ion is situated near the centre of the macrocyclic cavity, but is displaced by 0.8972 (1) Å from the O atoms of the crown in the direction of the [P2S6](2-) moiety. The overall coordination number of the cation is eight, defined by the six crown ether O atoms and by two terminal S atoms of the [P2S6](2-) anion. The hexa-thio-metadiphosphate anion is built up from two tetra-hedral PS4 units joined together by a common edge. The crystal structure is characterized by alternating layers of [Rb(18-crown-6)]2[P2S6] and aceto-nitrile solvent mol-ecules stacked along [010].

An HPLC-DAD and LC-MS study of condensation oscillations with S(+)-ketoprofen dissolved in acetonitrile.

PubMed

Sajewicz, Mieczysław; Gontarska, Monika; Kronenbach, Dorota; Berry, Etienne; Kowalska, Teresa

2012-03-01

In our earlier studies, a spontaneous chiral conversion of the selected low-molecular-weight carboxylic acids (i.e., amino acids, hydroxy acids, and profen drugs) dissolved in aqueous ethanol medium, running in vitro was described. Then it became clear that this spontaneous chiral conversion is accompanied by the spontaneous condensation of the discussed compounds. With several acids, it was established that this condensation is also oscillatory in nature. The theoretical models were developed aiming to give a rough explanation of the observed non-linear processes. In this paper, the results of these studies on the dynamics of condensation with S(+)-ketoprofen, a very popular profen drug, when stored for certain amount of time dissolved in a non-aqueous medium (i.e., acetonitrile) is presented. These investigations were carried out with the aid of two independent high-performance liquid chromatographic systems with the diode array detection and of a third high-performance liquid chromatographic system equipped with mass spectrometric detection. In one cycle of chromatographic measurements, it was possible to monitor condensation of S(+)-ketoprofen in 25-min intervals for 30 h, thus obtaining kinetic information on the progress of this process. Mass spectrometric detection confirmed the presence of new species in the stored solution with molecular weights much higher than that of S(+)-ketoprofen, which can be attributed to the condensation products. The obtained data show that condensation of S(+)-ketoprofen dissolved in acetonitrile progresses in a rapid manner, and that the observed oscillatory concentration changes with S(+)-ketoprofen and with the main condensation product characterize with an irregularity and shallow amplitudes. A theoretical model was referenced that jointly describes the oscillatory chiral conversion and the oscillatory condensation with the low-molecular-weight chiral carboxylic acids.

A universal model for nanoporous carbon supercapacitors applicable to diverse pore regimes, carbon materials, and electrolytes.

PubMed

Huang, Jingsong; Sumpter, Bobby G; Meunier, Vincent

2008-01-01

Supercapacitors, commonly called electric double-layer capacitors (EDLCs), are emerging as a novel type of energy-storage device with the potential to substitute batteries in applications that require high power densities. In response to the latest experimental breakthrough in nanoporous carbon supercapacitors, we propose a heuristic theoretical model that takes pore curvature into account as a replacement for the EDLC model, which is based on a traditional parallel-plate capacitor. When the pore size is in the mesopore regime (2-50 nm), counterions enter mesoporous carbon materials and approach the pore wall to form an electric double-cylinder capacitor (EDCC); in the micropore regime (<2 nm), solvated/desolvated counterions line up along the pore axis to form an electric wire-in-cylinder capacitor (EWCC). In the macropore regime (>50 nm) at which pores are large enough so that pore curvature is no longer significant, the EDCC model can be reduced naturally to the EDLC model. We present density functional theory calculations and detailed analyses of available experimental data in various pore regimes, which show the significant effects of pore curvature on the supercapacitor properties of nanoporous carbon materials. It is shown that the EDCC/EWCC model is universal for carbon supercapacitors with diverse carbon materials, including activated carbon materials, template carbon materials, and novel carbide-derived carbon materials, and with diverse electrolytes, including organic electrolytes, such as tetraethylammonium tetrafluoroborate (TEABF(4)) and tetraethylammonium methylsulfonate (TEAMS) in acetonitrile, aqueous H(2)SO(4) and KOH electrolytes, and even an ionic liquid electrolyte, such as 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (EMI-TFSI). The EDCC/EWCC model allows the supercapacitor properties to be correlated with pore size, specific surface area, Debye length, electrolyte concentration and dielectric constant, and solute ion size It

Glass transition and relaxation dynamics of propylene glycol-water solutions confined in clay

NASA Astrophysics Data System (ADS)

Elamin, Khalid; Björklund, Jimmy; Nyhlén, Fredrik; Yttergren, Madeleine; Mârtensson, Lena; Swenson, Jan

2014-07-01

The molecular dynamics of aqueous solutions of propylene glycol (PG) and propylene glycol methylether (PGME) confined in a two-dimensional layer-structured Na-vermiculite clay has been studied by broadband dielectric spectroscopy and differential scanning calorimetry. As typical for liquids in confined geometries the intensity of the cooperative α-relaxation becomes considerably more suppressed than the more local β-like relaxation processes. In fact, at high water contents the calorimetric glass transition and related structural α-relaxation cannot even be observed, due to the confinement. Thus, the intensity of the viscosity related α-relaxation is dramatically reduced, but its time scale as well as the related glass transition temperature Tg are for both systems only weakly influenced by the confinement. In the case of the PGME-water solutions it is an important finding since in the corresponding bulk system a pronounced non-monotonic concentration dependence of the glass transition related dynamics has been observed due to the growth of hydrogen bonded relaxing entities of water bridging between PGME molecules [J. Sjöström, J. Mattsson, R. Bergman, and J. Swenson, Phys. Chem. B 115, 10013 (2011)]. The present results suggest that the same type of structural entities are formed in the quasi-two-dimensional space between the clay platelets. It is also observed that the main water relaxation cannot be distinguished from the β-relaxation of PG or PGME in the concentration range up to intermediate water contents. This suggests that these two processes are coupled and that the water molecules affect the time scale of the β-relaxation. However, this is most likely true also for the corresponding bulk solutions, which exhibit similar time scales of this combined relaxation process below Tg. Finally, it is found that at higher water contents the water relaxation does not merge with, or follow, the α-relaxation above Tg, but instead crosses the �

Glass transition and relaxation dynamics of propylene glycol-water solutions confined in clay.

PubMed

Elamin, Khalid; Björklund, Jimmy; Nyhlén, Fredrik; Yttergren, Madeleine; Mårtensson, Lena; Swenson, Jan

2014-07-21

The molecular dynamics of aqueous solutions of propylene glycol (PG) and propylene glycol methylether (PGME) confined in a two-dimensional layer-structured Na-vermiculite clay has been studied by broadband dielectric spectroscopy and differential scanning calorimetry. As typical for liquids in confined geometries the intensity of the cooperative α-relaxation becomes considerably more suppressed than the more local β-like relaxation processes. In fact, at high water contents the calorimetric glass transition and related structural α-relaxation cannot even be observed, due to the confinement. Thus, the intensity of the viscosity related α-relaxation is dramatically reduced, but its time scale as well as the related glass transition temperature Tg are for both systems only weakly influenced by the confinement. In the case of the PGME-water solutions it is an important finding since in the corresponding bulk system a pronounced non-monotonic concentration dependence of the glass transition related dynamics has been observed due to the growth of hydrogen bonded relaxing entities of water bridging between PGME molecules [J. Sjöström, J. Mattsson, R. Bergman, and J. Swenson, Phys. Chem. B 115, 10013 (2011)]. The present results suggest that the same type of structural entities are formed in the quasi-two-dimensional space between the clay platelets. It is also observed that the main water relaxation cannot be distinguished from the β-relaxation of PG or PGME in the concentration range up to intermediate water contents. This suggests that these two processes are coupled and that the water molecules affect the time scale of the β-relaxation. However, this is most likely true also for the corresponding bulk solutions, which exhibit similar time scales of this combined relaxation process below Tg. Finally, it is found that at higher water contents the water relaxation does not merge with, or follow, the α-relaxation above Tg, but instead crosses the �

Basic poly(propylene glycols) as reference compounds for internal mass calibration in positive-ion matrix-assisted laser desorption/ionization mass spectrometry.

PubMed

Gross, Jürgen H

2017-12-01

Basic poly(propylene glycols), commercially available under the trade name Jeffamine, are evaluated for their potential use as internal mass calibrants in matrix-assisted laser desorption/ionization-time-of-flight-mass spectrometry. Due to their basic amino endgroups Jeffamines are expected to deliver [M+H] + ions in higher yields than neutral poly(propylene glycols) or poly(ethylene glycols). Aiming at accurate mass measurements and molecular formula determinations by matrix-assisted laser desorption/ionization-time-of-flight-mass spectrometry, four Jeffamines (M-600, M-2005, D-400, D-230) were thus compared. As a result, Jeffamine M-2005 is introduced as a new mass calibrant for positive-ion matrix-assisted laser desorption/ionization-time-of-flight-mass spectrometry in the range of m/z 200-1200 and the reference mass list is provided. While Jeffamine M-2005 is compatible with α-cyano-4-hydroxycinnamic acid, 2,5-dihydroxybenzoic acid, and 2-[(2 E)-3-(4- tert-butylphenyl)-2-methylprop-2-enylidene]malonitrile matrix, its use in combination with 2-[(2 E)-3-(4- tert-butylphenyl)-2-methylprop-2-enylidene]malonitrile provides best results due to low laser fluence requirements. Applications to PEG 300, PEG 600, the ionic liquid trihexyl(tetradecyl)-phosphonium tris(pentafluoroethyl)-trifluorophosphate, and [60]fullerene demonstrate mass accuracies of 2-5 ppm.

Evaluation of Toxic Air Emissions

DTIC Science & Technology

1995-06-01

108394 106445 98828 94757 3547044 334883 Calcium Cyanamide Caprolactam Captan Carbaryl Carbon disulfide Carbon Tetrachloride Carbonyl sulfide Catechol...Phosphorus Phthalic anhydride Polychlorinated biphenyls (Aroclors) 1,3-Propane sultone beta-Propiolactone Propionaldehyde Propoxur (Baygon) Propylene

Modelling of ceramide interactions with porous graphite carbon in non-aqueous liquid chromatography.

PubMed

West, C; Cilpa, G; Gaudin, K; Chaminade, P; Lesellier, E

2005-09-16

Interactions of solutes on porous graphitic carbon (PGC) with non-aqueous mobile phases are studied by the linear solvation energy relationship (LSER). Studies have been carried out with eight binary mixtures composed of a weak solvent (acetonitrile or methanol) and a strong solvent (tetrahydrofuran, n-butanol, CH2Cl2, 1,1,2-trichloro-2,2,1-trifluoroethane). The systematic analysis of a set of test compounds was performed for each solvent mixture in isocratic mode (50:50). The results were compared to those obtained on PGC with hydro-organic liquids and supercritical fluids. They were then correlated with the observed retention behaviour of lipid compounds, more particularly ceramides.

X-ray Raman spectroscopy of lithium-ion battery electrolyte solutions in a flow cell.

PubMed

Ketenoglu, Didem; Spiekermann, Georg; Harder, Manuel; Oz, Erdinc; Koz, Cevriye; Yagci, Mehmet C; Yilmaz, Eda; Yin, Zhong; Sahle, Christoph J; Detlefs, Blanka; Yavaş, Hasan

2018-03-01

The effects of varying LiPF 6 salt concentration and the presence of lithium bis(oxalate)borate additive on the electronic structure of commonly used lithium-ion battery electrolyte solvents (ethylene carbonate-dimethyl carbonate and propylene carbonate) have been investigated. X-ray Raman scattering spectroscopy (a non-resonant inelastic X-ray scattering method) was utilized together with a closed-circle flow cell. Carbon and oxygen K-edges provide characteristic information on the electronic structure of the electrolyte solutions, which are sensitive to local chemistry. Higher Li + ion concentration in the solvent manifests itself as a blue-shift of both the π* feature in the carbon edge and the carbonyl π* feature in the oxygen edge. While these oxygen K-edge results agree with previous soft X-ray absorption studies on LiBF 4 salt concentration in propylene carbonate, carbon K-edge spectra reveal a shift in energy, which can be explained with differing ionic conductivities of the electrolyte solutions.

Exposure of German residents to ethylene and propylene glycol ethers in general and after cleaning scenarios.

PubMed

Fromme, H; Nitschke, L; Boehmer, S; Kiranoglu, M; Göen, T

2013-03-01

Glycol ethers are a class of semi-volatile substances used as solvents in a variety of consumer products like cleaning agents, paints, cosmetics as well as chemical intermediates. We determined 11 metabolites of ethylene and propylene glycol ethers in 44 urine samples of German residents (background level study) and in urine samples of individuals after exposure to glycol ethers during cleaning activities (exposure study). In the study on the background exposure, methoxyacetic acid and phenoxyacetic acid (PhAA) could be detected in each urine sample with median (95th percentile) values of 0.11 mgL(-1) (0.30 mgL(-1)) and 0.80 mgL(-1) (23.6 mgL(-1)), respectively. The other metabolites were found in a limited number of samples or in none. In the exposure study, 5-8 rooms were cleaned with a cleaner containing ethylene glycol monobutyl ether (EGBE), propylene glycol monobutyl ether (PGBE), or ethylene glycol monopropyl ether (EGPE). During cleaning the mean levels in the indoor air were 7.5 mgm(-3) (EGBE), 3.0 mgm(-3) (PGBE), and 3.3 mgm(-3) (EGPE), respectively. The related metabolite levels analysed in the urine of the residents of the rooms at the day of cleaning were 2.4 mgL(-1) for butoxyacetic acid, 0.06 mgL(-1) for 2-butoxypropionic acid, and 2.3 mgL(-1) for n-propoxyacetic acid. Overall, our study indicates that the exposure of the population to glycol ethers is generally low, with the exception of PhAA. Moreover, the results of the cleaning scenarios demonstrate that the use of indoor cleaning agents containing glycol ethers can lead to a detectable internal exposure of residents. Copyright © 2012 Elsevier Ltd. All rights reserved.

Membrane permeability of the human granulocyte to water, dimethyl sulfoxide, glycerol, propylene glycol and ethylene glycol.

PubMed

Vian, Alex M; Higgins, Adam Z

2014-02-01

Granulocytes are currently transfused as soon as possible after collection because they rapidly deteriorate after being removed from the body. This short shelf life complicates the logistics of granulocyte collection, banking, and safety testing. Cryopreservation has the potential to significantly increase shelf life; however, cryopreservation of granulocytes has proven to be difficult. In this study, we investigate the membrane permeability properties of human granulocytes, with the ultimate goal of using membrane transport modeling to facilitate development of improved cryopreservation methods. We first measured the equilibrium volume of human granulocytes in a range of hypo- and hypertonic solutions and fit the resulting data using a Boyle-van't Hoff model. This yielded an isotonic cell volume of 378 μm(3) and an osmotically inactive volume of 165 μm(3). To determine the permeability of the granulocyte membrane to water and cryoprotectant (CPA), cells were injected into well-mixed CPA solution while collecting volume measurements using a Coulter Counter. These experiments were performed at temperatures ranging from 4 to 37°C for exposure to dimethyl sulfoxide, glycerol, ethylene glycol, and propylene glycol. The best-fit water permeability was similar in the presence of all of the CPAs, with an average value at 21°C of 0.18 μmatm(-1)min(-1). The activation energy for water transport ranged from 41 to 61 kJ/mol. The CPA permeability at 21°C was 6.4, 1.0, 8.4, and 4.0 μm/min for dimethyl sulfoxide, glycerol, ethylene glycol, and propylene glycol, respectively, and the activation energy for CPA transport ranged between 59 and 68 kJ/mol. Copyright © 2013 Elsevier Inc. All rights reserved.

TS-1 supported highly dispersed sub-5 nm gold nanoparticles toward direct propylene epoxidation using H2 and O2

NASA Astrophysics Data System (ADS)

Li, Naixu; Chen, Yong; Shen, Quanhao; Yang, Bin; Liu, Ming; Wei, Lingfei; Tian, Wei; Zhou, Jiancheng

2018-05-01

We report a simple and efficient method for the preparation of highly dispersed Au nanoparticles (< 5 nm) on TS-1 substrate. The synthesis relies on the use of NaBH4 as a reductant for rapid Au atom generation, as well as PVA as a capping agent confining the particle size and dispersion. The samples were characterized by N2 physisorption, inductively coupled plasma mass spectrometry, power X-ray diffraction, scanning electron microscopy, transmission electron microscopy, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, CO pulse chemisorption and thermogravimetric analysis. The size of Au particles can be controlled in the range of 3-5 nm. The supported catalyst shows both good activity and selectivity for propylene oxide (PO) generation from direct propylene epoxidation. An optimal performance with PO formation rate of 102.94 gPO h-1 kg-1cat and selectivity of 84.83% is achieved over 2.0 wt% Au/TS-1 catalyst, which is prepared by controlling PVA/Au3+ mass ratio of 1.5/1 and NaBH4/Au3+ mole ratio of 5/1. After 50 h test at 200 °C, no significant decrement of both catalytic activity and PO selectivity can be observed, indicating the excellent thermally stability of the catalyst. Furthermore, a possible reaction mechanism is described on basis of the previous researches and our experimental results.

Conversion of CO2 into cyclic carbonates by a Co(ii) metal-organic framework and the improvement of catalytic activity via nanocrystallization.

PubMed

Ji, Xiao-He; Zhu, Ning-Ning; Ma, Jian-Gong; Cheng, Peng

2018-02-06

The Co(ii) metal-organic framework (MOF) {[Co(μ 3 -L)(H 2 O)]·0.5H 2 O} n (1, H 2 L = thiazolidine 2,4-dicarboxylic acid) with rich Lewis acid sites was used as a catalyst for the conversion of CO 2 and propylene oxide into propylene carbonate with a yield of up to 98% under 50 °C and 1 atm. 1 exhibited excellent reusability, which could be regenerated easily for at least five runs without a decrease in the yield. Importantly, we synthesized two types of nano-crystals (N1 and N2) of 1 with polyvinylpyrrolidone (PVP) and hexadecyltrimethylammonium bromide (CTAB) as surfactants, respectively, and investigated their catalytic properties in comparison with that of 1 in the powder phase. A significant enhancement in both catalytic efficiency and product yield was observed when 1 was nano-crystallized. This is the first investigation about the relationship between the morphology and the catalytic parameters of MOFs. The results showed a strategy for efficiently applying MOFs as catalysts towards CO 2 conversion, which could also be used in other MOF-catalyzed processes.

Nanoscale carbon materials from hydrocarbons pyrolysis: Structure, chemical behavior, utilisation for non-aqueous supercapacitors

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

Savilov, Serguei V., E-mail: savilov@chem.msu.ru; Strokova, Natalia E.; Ivanov, Anton S.

Highlights: • N-doped and regular carbon nanomaterials were obtained by pyrolitic technique. • Dynamic vapor sorption of different solvents reveals smaller S{sub BET} values. • Steric hindrance and specific chemical interactions are the reasons for this. • Nitrogen doping leads to raise of capacitance and coulombic efficiency with non-aqueous N-containing electrolyte. - Abstract: This work systematically studies adsorption properties of carbon nanomaterials that are synthesized through hydrocarbons that is a powerful technique to fabricate different kinds of carbon materials, e.g., nanotubes, nanoshells, onions, including nitrogen substituted. The adsorption properties of the as-synthesized carbons are achieved by low temperature nitrogen adsorptionmore » and organic vapors sorption. Heptane, acetonitrile, water, ethanol, benzene and 1-methylimidazole, which are of great importance for development of supercapacitors, are used as substrates. It is discovered that while nitrogen adsorption reveals a high specific surface area, this parameter for most of organic compounds is rather small depending not only on the size of its molecule but also on chemical interactions for a pair adsorbent–adsorbate. The experimental values of heat of adsorption for carbon and N-substituted structures, when Coulomb cross-coupling of nitrogen atoms in adsorbent and adsorbate takes place, confirms this supposition.« less

Structural and spectroscopic characterization of methyl isocyanate, methyl cyanate, methyl fulminate, and acetonitrile N-oxide using highly correlated ab initio methods.

PubMed

Dalbouha, S; Senent, M L; Komiha, N; Domínguez-Gómez, R

2016-09-28

Various astrophysical relevant molecules obeying the empirical formula C 2 H 3 NO are characterized using explicitly correlated coupled cluster methods (CCSD(T)-F12). Rotational and rovibrational parameters are provided for four isomers: methyl isocyanate (CH 3 NCO), methyl cyanate (CH 3 OCN), methyl fulminate (CH 3 ONC), and acetonitrile N-oxide (CH 3 CNO). A CH 3 CON transition state is inspected. A variational procedure is employed to explore the far infrared region because some species present non-rigidity. Second order perturbation theory is used for the determination of anharmonic frequencies, rovibrational constants, and to predict Fermi resonances. Three species, methyl cyanate, methyl fulminate, and CH 3 CON, show a unique methyl torsion hindered by energy barriers. In methyl isocyanate, the methyl group barrier is so low that the internal top can be considered a free rotor. On the other hand, acetonitrile N-oxide presents a linear skeleton, C 3v symmetry, and free internal rotation. Its equilibrium geometry depends strongly on electron correlation. The remaining isomers present a bend skeleton. Divergences between theoretical rotational constants and previous parameters fitted from observed lines for methyl isocyanate are discussed on the basis of the relevant rovibrational interaction and the quasi-linearity of the molecular skeleton.

Structural and spectroscopic characterization of methyl isocyanate, methyl cyanate, methyl fulminate, and acetonitrile N-oxide using highly correlated ab initio methods

NASA Astrophysics Data System (ADS)

Dalbouha, S.; Senent, M. L.; Komiha, N.; Domínguez-Gómez, R.

2016-09-01

Various astrophysical relevant molecules obeying the empirical formula C2H3NO are characterized using explicitly correlated coupled cluster methods (CCSD(T)-F12). Rotational and rovibrational parameters are provided for four isomers: methyl isocyanate (CH3NCO), methyl cyanate (CH3OCN), methyl fulminate (CH3ONC), and acetonitrile N-oxide (CH3CNO). A CH3CON transition state is inspected. A variational procedure is employed to explore the far infrared region because some species present non-rigidity. Second order perturbation theory is used for the determination of anharmonic frequencies, rovibrational constants, and to predict Fermi resonances. Three species, methyl cyanate, methyl fulminate, and CH3CON, show a unique methyl torsion hindered by energy barriers. In methyl isocyanate, the methyl group barrier is so low that the internal top can be considered a free rotor. On the other hand, acetonitrile N-oxide presents a linear skeleton, C3v symmetry, and free internal rotation. Its equilibrium geometry depends strongly on electron correlation. The remaining isomers present a bend skeleton. Divergences between theoretical rotational constants and previous parameters fitted from observed lines for methyl isocyanate are discussed on the basis of the relevant rovibrational interaction and the quasi-linearity of the molecular skeleton.

Vibrational energy transfer between carbon nanotubes and nonaqueous solvents: a molecular dynamics study.

PubMed

Nelson, Tammie R; Chaban, Vitaly V; Prezhdo, Victor V; Prezhdo, Oleg V

2011-05-12

We report molecular dynamics (MD) simulation of energy exchange between single-walled carbon nanotubes (CNTs) and two aprotic solvents, acetonitrile and cyclohexane. Following our earlier study of hydrated CNTs, we find that the time scales and molecular mechanisms of the energy transfer are largely independent of the nature of the surrounding medium, and therefore, should hold for other media including polymer matrices and DNA. The vibrational energy exchange between CNT and solvents exhibits two time-scales. Over half of the energy is transferred in less than one picosecond, indicating that the dominant exchange mechanism is inertial relaxation. It occurs by collisions of solvent molecules with CNT walls, facilitated by the short-range Lennard-Jones interaction. Additional several picoseconds are required for the remainder of the vibrational energy exchange, corresponding to the diffusive relaxation mechanism and involving collective molecular motions. The faster stage of the CNT-solvent energy exchange occurs on the same time-scale, and therefore, competes with the vibrational energy relaxation inside CNTs. The energy exchange time-scales are significantly influenced by the arrangement of solvent molecules inside CNTs. Generally, the effects of confinement on the dynamics can be rationalized by analysis of the solvent structure. For the same CNT diameter, the extent of the confinement effect strongly depends on the size of the solvent molecules. Icelike properties in water seen in small CNTs disappear in CNTs with intermediate diameters. In acetonitrile and cyclohexane, medium size CNTs still show strong confinement effects. Rotational motions of acetonitrile molecules are inhibited, and the cyclohexane density is dramatically decreased. The disbalance between the local temperatures of the inside and outside regions of the solvent equilibrates through a tube-mediated interaction, rather than by a direct coupling between the two solvent subsystems. In all cases

Isomerization and fragmentation of acetonitrile upon interaction with N(4S) atoms: the chemistry of nitrogen in dense molecular clouds

NASA Astrophysics Data System (ADS)

Mencos, Alejandro; Krim, Lahouari

2016-08-01

We experimentally show that the reaction between ground state nitrogen atoms N(4S) and acetonitrile CH3CN can lead to two distinct chemical pathways that are both thermally activated at very low temperatures. First is CH3CN isomerization which produces CH3NC and H2CCNH. Second is CH3CN decomposition which produces HNC and CH3CNH+CN- fragments, with the possible release of H2. Our results reveal that the mobility of N(4S)-atoms is stimulated in the 3-11 K temperature range, and that its subsequent encounter with one acetonitrile molecule is sufficient for the aforementioned reactions to occur without the need for additional energy to be supplied to the CH3CN + N(4S) system. These findings shed more light on the nitrogen chemistry that can possibly take place in dense molecular clouds, which until now was thought to only involve high-energy processes and therefore be unlikely to occur in such cold and dark interstellar regions. The reaction pathways we propose in this study have very important astrochemical implications, as it was shown recently that the atomic nitrogen might be more abundant, in many interstellar icy grain mantles, than previously thought. Also, these reaction pathways can now be considered within dense molecular clouds, and possibly affect the branching ratios for N-bearing molecules computed in astrochemical modelling.

Neutron Scattering Studies of Liquid on or Confined in Nano- and Mesoporous Carbons, Including Carbide-Derived Carbons

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

Wesolowski, David J

2014-07-01

This project involved the synthesis of microporous graphitic-carbon powders with subnanometer average pore size, and very narrow pore size distributions, and the use of these materials in experimental studies of pore-fluid structure and dynamics. Samples of carbide-derived carbon powder, synthesized by extraction of the metal cations from TiC by a high temperature chlorination process, followed by high temperature vacuum annealing, were prepared by Ranjan Dash and his associates at CRADA partner Y-Carbon, Inc. The resulting material had average pore sizes ranging from 5 to 8 . These powders were used in two experiments conducted by researchers involved in the Energymore » Frontier Research Center Directed by David J. Wesolowski at ORNL, the Fluid Interface Reactions, Structures and Transport (FIRST) Center. FIRST-funded researchers at Drexel University collaborated with scientists at the Paul Scherrer Institute, Switzerland, to measure the expansion and contraction of the microporous carbon particles during charging and discharging of supercapactor electrodes composed of these particles (Hantell et al., 2011, Electrochemistry Communications, v. 13, pp. 1221-1224.) in an electrolyte composed of tetraethylammonium tetrafluoroborate dissolved in acetonitrile. In the second experiment, researchers at Oak Ridge National Laboratory and Drexel University conducted quasielastic neutron scattering studies of the diffusional dynamics of water imbibed into the micropores of the same material (Chathoth et al., 2011, EuroPhysics Journal, v. 95, pp. 56001/1-6). These studies helped to establish the role of pores approaching the size of the solvent and dissolved ions in altering diffusional dynamics, ion transport and physical response of conducting substrates to ion desolvation and entry into subnamometer pores.« less

Synthesis of nano-sized hydrogen phosphate-imprinted polymer in acetonitrile/water mixture and its use as a recognition element of hydrogen phosphate selective all-solid state potentiometric electrode.

PubMed

Alizadeh, Taher; Atayi, Khalil

2018-02-01

Herein, a new recipe is introduced for the preparation of hydrogen phosphate ion-imprinted polymer nanoparticles (nano-IIP) in acetonitrile/water (63.5:36.5) using phosphoric acid as the template. The nano-IIP obtained was used as the recognition element of a carbon paste potentiometric sensor. The IIP electrode showed a Nernstian response to hydrogen phosphate anion; whereas, the non-imprinted polymer (NIP)-based electrode had no considerable sensitivity to the anion. The presence of both methacrylic acid and vinyl pyridine in the IIP structure, as well as optimization of the functional monomers-template proportion, was found to be important to observe the sensing capability of the IIP electrode. The nano-IIP electrode showed a dynamic linear range of 1 × 10 -5 -1 × 10 -1  mol L-1, Nernstian slope of 30.6 ± (0.5) mV decade -1 , response time of 25 seconds, and detection limit of 4.0 × 10 -6  mol L -1 . The utility of the electrodes was checked by potentiometric titration of hydrogen phosphate with La 3+ solution. Copyright © 2017 John Wiley & Sons, Ltd.

Effects of different dosages of propylene glycol in dry cows and cows in early lactation.

PubMed

Maurer, Michaela; Peinhopf, Walter; Gottschalk, Jutta; Einspanier, Almut; Koeller, Gabor; Wittek, Thomas

2017-11-01

In this Research Paper we hypothesised that the temporary insulin resistance seen during the transition period in dairy cows may cause significant differences in the efficacy of PG at different sampling periods and that in some cases this effect will be dose dependent. Eighty four sampling sets were generated by studying 7 multiparous Holstein cows repeatedly at 4 sampling periods of 3 d length (dry cows: days 40, 39 and 38 antepartum; close up cows: days 10, 9 and 8 antepartum; fresh cows: days 3, 4 and 5 post-partum; lactating cows: days 38, 39 and 40 post-partum). On each of these days 3 h after morning feeding propylene glycol was drenched in different dosages of 100, 300 or 500 ml once per day (cross over study). The different doses were applied in an alternating order (Latin square). Blood samples were taken before, every 30 min up to 4 h, after 6 and 12 h after PG application. Following parameters have been measured: insulin, non-esterified fatty acids (NEFA), betahydroxybutyrate (BHB), bilirubin, cholesterol, potassium, aspartate aminotransferase (AST) and glutamate dehydrogenase (GLDH). Revised Quantitative Insulin Sensitivity Check Index (RQUICKI) was calculated. It was found that glucose, insulin, NEFA, BHB, bilirubin and potassium concentrations were influenced differently by the three defined dosages of propylene glycol at four different sampling periods. Whereas RQUICKI, cholesterol, AST and GLDH did not differ between the sampling periods and treatments. The major results of the study are that the effect of PG is dose-dependent and that the effect of PG is depending on the time of application according to calving. It can be concluded that in fresh cows higher dosages are necessary to provoke similar effects in comparison to dry, close up and lactating cows. Although the study did not compare to topdressing of PG from the results it is reasonable to believe that bolus application of a specific PG volume is necessary to provoke the effect.

On the solvation of the phosphocholine headgroup in an aqueous propylene glycol solution

NASA Astrophysics Data System (ADS)

Rhys, Natasha H.; Al-Badri, Mohamed Ali; Ziolek, Robert M.; Gillams, Richard J.; Collins, Louise E.; Lawrence, M. Jayne; Lorenz, Christian D.; McLain, Sylvia E.

2018-04-01

The atomic-scale structure of the phosphocholine (PC) headgroup in 30 mol. % propylene glycol (PG) in an aqueous solution has been investigated using a combination of neutron diffraction with isotopic substitution experiments and computer simulation techniques—molecular dynamics and empirical potential structure refinement. Here, the hydration of the PC headgroup remains largely intact compared with the hydration of this group in a bilayer and in a bulk water solution, with the PG molecules showing limited interactions with the headgroup. When direct PG interactions with PC do occur, they are most likely to coordinate to the 3+N (CH 3 ) motifs. Further, PG does not affect the bulk water structure and the addition of PC does not perturb the PG-solvent interactions. This suggests that the reason why PG is able to penetrate into membranes easily is that it does not form strong-hydrogen bonding or electrostatic interactions with the headgroup allowing it to easily move across the membrane barrier.

Performance Characteristics of Lithium Ion Polymeric Electrolyte Cells

NASA Technical Reports Server (NTRS)

Shen, D.; Nagasubramanian, G.; Huang, C-K.; Surampudi, S.; Halpert, G.

1994-01-01

A series of polyacrylonitrile-based (PAN) electrolytes containing LiAsF6 and a number of solvent mixtures including ethylene carbonate (EC) + propylene carbonate (PC) were prepared, electrochemically evaluated and used as electrolyte in the polymer cells.

Modulation of biogenic amines content by poly(propylene imine) dendrimers in rats.

PubMed

Ciepluch, Karol; Ziemba, Barbara; Janaszewska, Anna; Appelhans, Dietmar; Klajnert, Barbara; Bryszewska, Maria; Fogel, Wiesława Agnieszka

2012-09-01

Biogenic amines and polyamines participate in all vital organism functions, their levels being important function determinants. Studies were performed to check whether repeated administration of poly(propylene imine) (PPI) dendrimers, synthetic macromolecules with diaminobutane core, and peripheral primary amine groups, may influence the endogenous level of amines, as represented by the two of them: spermidine, a natural derivative of diaminobutane, and histamine. The experiment was carried out on Wistar rats. Fourth generation PPI dendrimer, as well as maltotriose-modified fourth generation PPI dendrimers with (a) cationic open sugar shell and (b) neutral dense sugar shell that possess a higher biocompatibility, was used. Applying the combination of column chromatography on Cellex P and spectrofluorimetric assays of o-phthaldialdehyde, the final amine condensation products were employed to analyze tissue spermidine and histamine outside the central nervous system. Furthermore, radioenzymatic assay was used to measure histamine levels in the brain. The obtained results indicate that in some tissues, the endogenous concentrations of histamine and spermidine may be affected by dendrimers depending on their dose and type of dendrimers.

Determination of diflubenzuron and chlorbenzuron in fruits by combining acetonitrile-based extraction with dispersive liquid-liquid microextraction followed by high-performance liquid chromatography.

PubMed

Ruan, Chunqiang; Zhao, Xiang; Liu, Chenglan

2015-09-01

In this study, a simple and low-organic-solvent-consuming method combining an acetonitrile-partitioning extraction procedure followed by "quick, easy, cheap, effective, rugged and safe" cleanup with ionic-liquid-based dispersive liquid-liquid microextraction and high-performance liquid chromatography with diode array detection was developed for the determination of diflubenzuron and chlorbenzuron in grapes and pears. Ionic-liquid-based dispersive liquid-liquid microextraction was performed using the ionic liquid 1-hexyl-3-methylimidazolium hexafluorophosphate as the extractive solvent and acetonitrile extract as the dispersive solvent. The main factors influencing the efficiency of the dispersive liquid-liquid microextraction were evaluated, including the extractive solvent type and volume and the dispersive solvent volume. The validation parameters indicated the suitability of the method for routine analyses of benzoylurea insecticides in a large number of samples. The relative recoveries at three spiked levels ranged between 98.6 and 109.3% with relative standard deviations of less than 5.2%. The limit of detection was 0.005 mg/kg for the two insecticides. The proposed method was successfully used for the rapid determination of diflubenzuron and chlorbenzuron residues in real fruit samples. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Adsorption of water from aqueous acetonitrile on silica-based stationary phases in aqueous normal-phase liquid chromatography.

PubMed

Soukup, Jan; Jandera, Pavel

2014-12-29

Excess adsorption of water from aqueous acetonitrile mobile phases was investigated on 16 stationary phases using the frontal analysis method and coulometric Karl-Fischer titration. The stationary phases include silica gel and silica-bonded phases with different polarities, octadecyl and cholesterol, phenyl, nitrile, pentafluorophenylpropyl, diol and zwitterionic sulfobetaine and phosphorylcholine ligands bonded on silica, hybrid organic-silica and hydrosilated matrices. Both fully porous and core-shell column types were included. Preferential uptake of water by the columns can be described by Langmuir isotherms. Even though a diffuse rather than a compact adsorbed discrete layer of water on the adsorbent surface can be formed because of the unlimited miscibility of water with acetonitrile, for convenience, the preferentially adsorbed water was expressed in terms of a hypothetical monomolecular water layer equivalent in the inner pores. The uptake of water strongly depends on the polarity and type of the column. Less than one monomolecular water layer equivalent was adsorbed on moderate polar silica hydride-based stationary phases, Ascentis Express F5 and Ascentis Express CN column at the saturation capacity, while on more polar stationary phases, several water layer equivalents were up-taken from the mobile phase. The strongest affinity to water was observed on the ZIC cHILIC stationary phases, where more than nine water layer equivalents were adsorbed onto its surface at its saturation capacity. Columns with bonded hydroxyl and diol ligands show stronger water adsorption in comparison to bare silica. Columns based on hydrosilated silica generally show significantly decreased water uptake in comparison to stationary phases bonded on ordinary silica. Significant correlations were found between the water uptake and the separation selectivity for compounds with strong polarity differences. Copyright © 2014 Elsevier B.V. All rights reserved.

Lithium and sodium ion capacitors with high energy and power densities based on carbons from recycled olive pits

NASA Astrophysics Data System (ADS)

Ajuria, Jon; Redondo, Edurne; Arnaiz, Maria; Mysyk, Roman; Rojo, Teófilo; Goikolea, Eider

2017-08-01

In this work, we are presenting both lithium and sodium ion capacitors (LIC and NIC) entirely based on electrodes designed from recycled olive pit bio-waste derived carbon materials. On the one hand, olive pits were pyrolized to obtain a low specific surface area semigraphitic hard carbon to be used as the ion intercalation (battery-type) negative electrode. On the other hand, the same hard carbon was chemically activated with KOH to obtain a high specific surface area activated carbon that was further used as the ion-adsorption (capacitor-type) positive electrode. Both electrodes were custom-made to be assembled in a hybrid cell to either build a LIC or NIC in the corresponding Li- and Na-based electrolytes. For comparison purposes, a symmetric EDLC supercapacitor cell using the same activated carbon in 1.5 M Et4NBF4/acetonitrile electrolyte was also built. Both LIC and NIC systems demonstrate remarkable energy and power density enhancement over its EDLC counterpart while showing good cycle life. This breakthrough offers the possibility to easily fabricate versatile hybrid ion capacitors, covering a wide variety of applications where different requirements are demanded.

Sorbate-nitrite interactions: acetonitrile oxide as an alkylating agent.

PubMed

Pérez-Prior, M Teresa; Gómez-Bombarelli, Rafael; González-Pérez, Marina; Manso, José A; García-Santos, M Pilar; Calle, Emilio; Casado, Julio

2009-07-01

Because chemical species with DNA-damaging and mutagenic activity are formed in sorbate-nitrite mixtures and because sorbic acid sometimes coexists with nitrite occurring naturally or incorporated as a food additive, the study of sorbate-nitrite interactions is important. Here, the alkylating potential of the products resulting from such interactions was investigated. Drawn were the following conclusions: (i) Acetonitrile oxide (ACNO) is the compound responsible for the alkylating capacity of sorbate-nitrite mixtures; (ii) ACNO alkylates 4-(p-nitrobenzyl)pyridine (NBP), a trap for alkylating agents with nucleophilic characteristics similar to those of DNA bases, forming an adduct (AD; epsilon = 1.4 x 10(4) M(-1) cm(-1); lambda = 519 nm); (iii) the NBP alkylation reaction complies with the rate equation, r = d[AD]/dt = k(alk)(ACNO)[ACNO][NBP]-k(hyd)(AD)[AD], k(alk)(ACNO) being the NBP alkylation rate constant for ACNO and k(hyd)(AD) the rate constant for the adduct hydrolysis reaction; (iv) the small fraction of ACNO forming the adduct with NBP, as well as the small magnitude of the quotient (k(alk) (ACNO)/k(hyd)(ACNO)) as compared with those reported for other alkylating agents, such as some lactones and N-alkyl-N-nitrosoureas, reveals the ACNO effective alkylating capacity to be less significant; (v) the low value of the NBP-ACNO adduct life (defined as the total amount of adduct present along the progression of the NBP alkylation per unit of alkylating agent concentration) points to the high instability of this adduct; and (vi) the obtained results are in accordance with the low carcinogenicity of ACNO.

Progress in Characterizing Thermal Degradation of Ethylene-Propylene Rubber

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

Fifield, Leonard S.; Huang, Qian; Childers, Matthew I.

Ethylene-propylene rubber (EPR) is one of the two most common nuclear cable insulation materials. A large fraction of EPR-insulated cables in use in the nuclear industry were manufactured by The Okonite Company. Okoguard® is the name of the medium voltage thermoset EPR manufactured by The Okonite Company. Okoguard® has been produced with silane-treated clay filler and the characteristic pink color since the 1970’s. EPR is complex material that undergoes simultaneous reactions during thermal aging including oxidative and thermal cleavage and oxidative and thermal crosslinking. This reaction complexity makes precise EPR service life prediction from accelerated aging using approaches designed formore » single discreet reactions such as the Arrhenius approach problematic. Performance data and activation energies for EPR aged at conditions closer to service conditions will improve EPR lifetime prediction. In this report pink Okoguard® EPR insulation material has been thermally aged at elevated temperatures. A variety of characterization techniques have been employed to track material changes with aging. It was noted that EPR aged significant departure in aging behavior seemed to occur at accelerated aging temperatures between 140°C and 150°C at around 20 days of exposure. This may be due to alternative degradation mechanisms being accessed at this higher temperature and reinforces the need to perform accelerated aging for Okoguard® EPR service life prediction at temperatures below 150°C.« less

The influence of alcohol, propylene glycol and 1,2-pentanediol on the permeability of hydrophilic model drug through excised pig skin.

PubMed

Duracher, Lucie; Blasco, Laurent; Hubaud, Jean-Claude; Vian, Laurence; Marti-Mestres, Gilberte

2009-06-05

Alcohol and glycol including 1,2-pentanediol, a new product in this field, were examined for their transdermal penetration enhancing in vitro properties using pig skin and caffeine as a model drug. In order to investigate a possible influence of these compounds, we followed diffusion from an aqueous solution with caffeine followed by a series of different vehicles, their compositions were: (1) in water as a control; (2) in propylene glycol/ethanol/water (25:25:48; v/v/v); (3) in 1,2-pentanediol/water (2.5:95.5, v/v); (4) in 1,2-pentanediol/water (5:93, v/v); in propylene glycol/water (5:93; v/v); and in ethanol/water (5:93; v/v). The stratum corneum/vehicle partition coefficients (K(m)), maximum flux (J), enhancement factor (EF), 24-h receptor concentration (Q(24h)) were determined and compared to control values (caffeine in water). Permeation was also expressed in percentage of the applied dose absorbed in the different compartments. In all test models, caffeine was released and penetrated into pig skin. The 1,2-pentanediol was presented as the most effective enhancer; with a low proportion of this compound (only 5%), caffeine penetrated the skin quicker and in a greater extent. While this compound showed promise as penetration enhancer, further study was required to determine its effectiveness with others drugs and its irritation potential.

The electronic spectra and the structures of the individual copper(II) chloride and bromide complexes in acetonitrile according to steady-state absorption spectroscopy and DFT/TD-DFT calculations

NASA Astrophysics Data System (ADS)

Olshin, Pavel K.; Myasnikova, Olesya S.; Kashina, Maria V.; Gorbunov, Artem O.; Bogachev, Nikita A.; Kompanets, Viktor O.; Chekalin, Sergey V.; Pulkin, Sergey A.; Kochemirovsky, Vladimir A.; Skripkin, Mikhail Yu.; Mereshchenko, Andrey S.

2018-03-01

The results of spectrophotometric study and quantum chemical calculations for copper(II) chloro- and bromocomplexes in acetonitrile are reported. Electronic spectra of the individual copper(II) halide complexes were obtained in a wide spectral range 200-2200 nm. Stability constants of the individual copper(II) halide complexes in acetonitrile were calculated: log β1 = 8.5, log β2 = 15.6, log β3 = 22.5, log β4 = 25.7 for [CuCln]2-n and log β1 = 17.0, log β2 = 24.6, log β3 = 28.1, log β4 = 30.4 for [CuBrn]2-n. Structures of the studied complexes were optimized and electronic spectra were simulated using DFT and TD-DFT methodologies, respectively. According to the calculations, the more is the number of halide ligands the less is coordination number of copper ion.

Short-term organic carbon migration from polymeric materials in contact with chlorinated drinking water.

PubMed

Mao, Guannan; Wang, Yingying; Hammes, Frederik

2018-02-01

Polymeric materials are widely used in drinking water distribution systems. These materials could release organic carbon that supports bacterial growth. To date, the available migration assays for polymeric materials have not included the potential influence of chlorination on organic carbon migration behavior. Hence, we established a migration and growth potential protocol specifically for analysis of carbon migration from materials in contact with chlorinated drinking water. Four different materials were tested, including ethylene propylene dienemethylene (EPDM), poly-ethylene (PEX b and PEX c) and poly-butylene (PB). Chlorine consumption rates decreased gradually over time for EPDM, PEXc and PB. In contrast, no free chlorine was detected for PEXb at any time during the 7 migration cycles. Total organic carbon (TOC) and assimilable organic carbon (AOC) was evaluated in both chlorinated and non-chlorinated migrations. TOC concentrations for EPDM and PEXb in chlorinated migrations were significantly higher than non-chlorinated migrations. The AOC results showed pronounced differences among tested materials. AOC concentrations from chlorinated migration waters of EPDM and PB were higher compared to non-chlorinated migrations, whereas the opposite trend was observed for PEXb and PEXc. There was also a considerable difference between tested materials with regards to bacterial growth potential. The results revealed that the materials exposed to chlorine-influenced migration still exhibited a strong biofilm formation potential. The overall results suggested that the choice in material would make a considerable difference in chlorine consumption and carbon migration behavior in drinking water distribution systems. Copyright © 2017 Elsevier B.V. All rights reserved.

Ionic association and solvation in solutions of magnesium and nickel perchlorates in acetonitrile

NASA Astrophysics Data System (ADS)

Kalugin, O. N.; Agieienko, V. N.; Otroshko, N. A.; Moroz, V. V.

2009-02-01

The paper presents the conductometric data on solutions of Mg(ClO4)2 and Ni(ClO4)2 in acetonitrile over the temperature ranges 5-55°C for Mg(ClO4)2 and 25-75°C for Ni(ClO4)2. The extended Lee-Wheaton equation for unsymmetrical electrolytes was used to determine the limiting equivalent conductivities of the Mg2+, Ni2+, and ClO{4/-} ions and first-step ionic association constants with the formation of [KtClO4]+ ion pairs. Lower ionic association constants for Ni(ClO4)2 compared with Mg(ClO4)2 were a consequence of stronger non-Coulomb repulsion in the formation of [KtClO4]+ ion pairs because of the formation of a firmer solvation shell by the nickel compared with magnesium cation. The structure-dynamic parameter of ionic solvation was estimated. It was found that spatial-time correlations in the nearest environment of ions increased in the series ClO{4/-} > Mg2+ > Ni2+.

Electrical conductivity and dielectric relaxation of 2-(antipyrin-4-ylhydrazono)-2-(4-nitrophenyl)acetonitrile

NASA Astrophysics Data System (ADS)

El-Menyawy, E. M.; Zedan, I. T.; Nawar, H. H.

2014-03-01

The electrical and dielectric properties of the synthesized 2-(antipyrin-4-ylhydrazono)-2-(4-nitrophenyl)acetonitrile (AHNA) have been studied. The direct and alternating current (DC and AC) conductivities and complex dielectric constant were investigated in temperature range 303-403 K. The AC conductivity and dielectric properties of AHNA were investigated over frequency range 100 Hz-5 MHz. From DC and AC measurements, electrical conduction is found to be a thermally activated process. The frequency-dependent AC conductivity obeys Jonscher's universal power law in which the frequency exponent decreases with increasing temperature. The correlated barrier hopping (CBH) is the predominant model for describing the charge carrier transport in which the electrical parameters are evaluated. The activation energy is found to decrease with increasing frequency. The behaviors of dielectric and dielectric loss are discussed in terms of a polarization mechanism. The dielectric loss shows frequency power law from which the maximum barrier height is determined as 0.19 eV in terms of the Guintini model.

The Effect of Ethylene and Propylene Pulses on Respiration, Ripening Advancement, Ethylene-Forming Enzyme, and 1-Aminocyclopropane-1-carboxylic Acid Synthase Activity in Avocado Fruit 12

PubMed Central

Starrett, David A.; Laties, George G.

1991-01-01

When early-season avocado fruit (Persea americana Mill. cv Hass) were treated with ethylene or propylene for 24 hours immediately on picking, the time to the onset of the respiratory climacteric, i.e. the lag period, remained unchanged compared with that in untreated fruit. When fruit were pulsed 24 hours after picking, on the other hand, the lag period was shortened. In both cases, however, a 24 hour ethylene or propylene pulse induced a transient increase in respiration, called the pulse-peak, unaccompanied by ethylene production (IL Eaks [1980] Am Soc Hortic Sci 105: 744-747). The pulse also caused a sharp rise in ethylene-forming enzyme activity in both cases, without any increase in the low level of 1-aminocyclopropane-1-carboxylic acid synthase activity. Thus, the shortening of the lag period by an ethylene pulse is not due to an effect of ethylene on either of the two key enzymes in ethylene biosynthesis. A comparison of two-dimensional polyacrylamide gel electrophoresis polypeptide profiles of in vitro translation products of poly(A+) mRNA from control and ethylene-pulsed fruit showed both up- and down-regulation in response to ethylene pulsing of a number of genes expressed during the ripening syndrome. It is proposed that the pulse-peak or its underlying events reflect an intrinsic element in the ripening process that in late-season or continuously ethylene-treated fruit may be subsumed in the overall climacteric response. A computerized system that allows continuous readout of multiple samples has established that the continued presentation of exogeneous ethylene or propylene to preclimacteric fruit elicits a dual respiration response comprising the merged pulse-peak and climacteric peak in series. The sequential removal of cores from a single fruit has proven an unsatisfactory sampling procedure inasmuch as coring induces wound ethylene, evokes a positive respiration response, and advances ripening. PMID:16668073

Interactive transport of guanidinylated poly(propylene imine)-based dendrimers through liposomal and cellular membranes.

PubMed

Tsogas, Ioannis; Sideratou, Zili; Tsiourvas, Dimitris; Theodossiou, Theodossis A; Paleos, Constantinos M

2007-10-15

The ability of guanidinylated poly(propylene imine) dendrimers to translocate across lipid bilayers was assessed by employing either a model phosphate-bearing liposomal membrane system or A549 human lung carcinoma cells. Two dendrimer generations, differing in the number of surface guanidinium groups, were employed, while surface acetylation or the use of spacers affected the binding of the guanidinium group to the phosphate moiety and finally the transport efficiency. Following adhesion of dendrimers with liposomes, fusion or transport occurred. Transport through the liposomal bilayer was observed at low guanidinium/phosphate molar ratios, and was enhanced when the bilayer was in the liquid-crystalline phase. For effective transport through the liposomal membrane, an optimum balance between the binding strength and the degree of hydrophobicity of the guanidinylated dendrimer is required. In experiments performed in vitro with cells, efficient penetration and internalization in subcellular organelles and cytosol was observed.

Synthesis and the crystal and molecular structure of the germanium(IV) complex with propylene-1,3-diaminetetraacetic acid [Ge(Pdta)

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

Sergienko, V. S., E-mail: sergienko@igic.ras.ru; Martsinko, E. E.; Seifullina, I. I.

2015-09-15

The germanium(IV) complex with propylene-1,3-diaminetetraacetic acid (H{sub 4}Pdta) is studied by elemental analysis, X-ray diffraction, thermogravimetry, and IR spectroscopy. The X-ray diffraction study reveals two crystallographically independent [Ge(Pdta)] molecules of similar structure. Both Ge atoms are octahedrally coordinated by four O atoms and two N atoms (at the cis positions) of the hexadentate pentachelate Pdta{sup 4–} ligand. An extended system of weak C—H···O hydrogen bonds connects complex molecules into a supramolecular 3D framework.

Synthesis and the crystal and molecular structure of the germanium(IV) complex with propylene-1,3-diaminetetraacetic acid [Ge( Pdta)

NASA Astrophysics Data System (ADS)

Sergienko, V. S.; Martsinko, E. E.; Seifullina, I. I.; Churakov, A. V.; Chebanenko, E. A.

2015-09-01

The germanium(IV) complex with propylene-1,3-diaminetetraacetic acid (H4 Pdta) is studied by elemental analysis, X-ray diffraction, thermogravimetry, and IR spectroscopy. The X-ray diffraction study reveals two crystallographically independent [Ge( Pdta)] molecules of similar structure. Both Ge atoms are octahedrally coordinated by four O atoms and two N atoms (at the cis positions) of the hexadentate pentachelate Pdta 4- ligand. An extended system of weak С—Н···О hydrogen bonds connects complex molecules into a supramolecular 3D framework.

Carbon nanotubes and graphene modified screen-printed carbon electrodes as sensitive sensors for the determination of phytochelatins in plants using liquid chromatography with amperometric detection.

PubMed

Dago, Àngela; Navarro, Javier; Ariño, Cristina; Díaz-Cruz, José Manuel; Esteban, Miquel

2015-08-28

Nanomaterials are of great interest for the development of electrochemical sensors. Multi-walled carbon nanotubes and graphene were used to modify the working electrode surface of different screen-printed carbon electrodes (SPCE) with the aim of improving the sensitivity of the SPCE and comparing it with the conventional glassy carbon electrode. To assay the usability of these sensors, a HPLC methodology with amperometric detection was developed to analyze several phytochelatins in plants of Hordeum vulgare and Glycine max treated with Hg(II) or Cd(II) giving detection limits in the low μmolL(-1) range. Phytochelatins are low molecular weight peptides with the general structure γ-(Glu-Cys)n-Gly (n=2-5) which are synthesized in plants in the presence of heavy metal ions. These compounds can chelate heavy metal ions by the formation of complexes which, are transported to the vacuoles, where the toxicity is not threatening. For this reason phytochelatins are essential in the detoxification of heavy metal ions in plants. The developed HPLC method uses a mobile phase of 1% of formic acid in water with KNO3 or NaCl (pH=2.00) and 1% of formic acid in acetonitrile. Electrochemical detection at different carbon-based electrodes was used. Among the sensors tested, the conventional glassy carbon electrode offers the best sensitivity although modification improves the sensitivity of the SPCE. Glutathione and several isoforms of phytochelatin two were found in plant extracts of both studied species. Copyright © 2015 Elsevier B.V. All rights reserved.

Experimental Investigation of the Thermophysical Properties of TiO2/Propylene Glycol-Water Nanofluids for Heat-Transfer Applications

NASA Astrophysics Data System (ADS)

Leena, M.; Srinivasan, S.

2018-05-01

Nanofluids have been prepared by dispersing TiO2 nanoparticles in 70:30% (by weight) water-propylene glycol mixture. The thermal conductivity and viscosity were found experimentally at various temperatures with the volume concentrations 0.1-0.8%. The results indicate that the thermal conductivity of the nanofluids increases with the volume concentration and temperature. Similarly, the viscosity of the nanofluids increases with the volume concentration but decreases with increase in the temperature. Correlations have been proposed for estimating the thermal conductivity and viscosity of the nanofluids. The potential heat transfer benefits of their use in laminar and turbulent flow conditions has been explained.

[Determination of ethylene glycol in biological fluids--propylene glycol interferences].

PubMed

Gomółka, Ewa; Cudzich-Czop, Sylwia; Sulka, Adrianna

2013-01-01

Many laboratories in Poland do not use gas chromatography (GC) method for determination of ethylene glycol (EG) and methanol in blood of poisoned patients, they use non specific spectrophotometry methods. One of the interfering substances is propylene glycol (PG)--compound present in many medical and cosmetic products: drops, air freshens, disinfectants, electronic cigarettes and others. In Laboratory of Analytical Toxicology and Drug Monitoring in Krakow determination of EG is made by GC method. The method enables to distinguish and make resolution of (EG) and (PG) in biological samples. In the years 2011-2012 in several serum samples from diagnosed patients PG was present in concentration from several to higher than 100 mg/dL. The aim of the study was to estimate PG interferences of serum EG determination by spectrophotometry method. Serum samples containing PG and EG were used in the study. The samples were analyzed by two methods: GC and spectrophotometry. Results of serum samples spiked with PG with no EG analysed by spectrophotometry method were improper ("false positive"). The results were correlated to PG concentration in samples. Calculated cross-reactivity of PG in the method was 42%. Positive results of EG measured by spectrophotometry method must be confirmed by reference GC method. Spectrophotometry method shouldn't be used for diagnostics and monitoring of patients poisoned by EG.

Three-dimensional spectroscopy of vibrational energy in liquids: nitromethane and acetonitrile.

PubMed

Sun, Yuxiao; Pein, Brandt C; Dlott, Dana D

2013-12-12

We introduce a novel type of three-dimensional (3D) spectroscopy to study vibrational energy transfer, where an IR pulse tunable through the CH-stretching and CD-stretching regions was used to create parent vibrational excitations in liquids and a visible probe pulse was used to generate both Stokes and anti-Stokes Raman spectra as a function of delay time. The Raman spectra determine how much vibrational excitation was present in each probed state. The three dimensions are the wavenumber of the pumped state, the wavenumber of the probed state, and the time interval. The technique was used to study nitromethane (NM) and acetonitrile (ACN) and their deuterated analogues at ambient temperature. The 3D spectra were quite complicated. Three types of artifacts due to nonlinear light scattering were observed. Along the diagonal were two fundamental CH-stretch (or CD-stretch) transitions and several weaker combination bands or overtone transitions. Because Raman spectroscopy allows us to simultaneously probe a wide wavenumber region, for every diagonal peak, there were ∼10 off-diagonal peaks. The cross-peaks at shorter delay times reveal the nature of the initial excitation by showing which lower-wavenumber excitations were produced along with the pumped CH-stretch or CD-stretch. The longer-time spectra characterized vibrational energy relaxation processes, and showed how daughter vibrations were generated by different parent excitations.

Poly(ethylene oxide monomethyl ether)- block-poly(propylene succinate) Nanoparticles: Synthesis and Characterization, Enzymatic and Cellular Degradation, Micellar Solubilization of Paclitaxel, and in Vitro and in Vivo Evaluation.

PubMed

Jäger, Alessandro; Jäger, Eliézer; Syrová, Zdeňka; Mazel, Tomas; Kováčik, Lubomír; Raška, Ivan; Höcherl, Anita; Kučka, Jan; Konefal, Rafal; Humajova, Jana; Poučková, Pavla; Štěpánek, Petr; Hrubý, Martin

2018-04-11

Polyester-based nanostructures are widely studied as drug-delivery systems due to their biocompatibility and biodegradability. They are already used in the clinic. In this work, we describe a new and simple biodegradable and biocompatible system as the Food and Drug Administration approved polyesters (poly-ε-caprolactone, polylactic acid, and poly(lactic- co-glycolic acid)) for the delivery of the anticancer drug paclitaxel (PTX) as a model drug. A hydrophobic polyester, poly(propylene succinate) (PPS), was prepared from a nontoxic alcohol (propylene glycol) and monomer from the Krebs's cycle (succinic acid) in two steps via esterification and melt polycondensation. Furthermore, their amphiphilic block copolyester, poly(ethylene oxide monomethyl ether)- block-poly(propylene succinate) (mPEO- b-PPS), was prepared by three steps via esterification followed by melt polycondensation and the addition of mPEO to the PPS macromolecules. Analysis of the in vitro cellular behavior of the prepared nanoparticle carriers (NPs) (enzymatic degradation, uptake, localization, and fluorescence resonance energy-transfer pair degradation studies) was performed by fluorescence studies. PTX was loaded to the NPs of variable sizes (30, 70, and 150 nm), and their in vitro release was evaluated in different cell models and compared with commercial PTX formulations. The mPEO- b-PPS copolymer analysis displays glass transition temperature < body temperature < melting temperature, lower toxicity (including the toxicity of their degradation products), drug solubilization efficacy, stability against spontaneous hydrolysis during transport in bloodstream, and simultaneous enzymatic degradability after uptake into the cells. The detailed cytotoxicity in vitro and in vivo tumor efficacy studies have shown the superior efficacy of the NPs compared with PTX and PTX commercial formulations.

Enhanced performance of dicationic ionic liquid electrolytes by organic solvents.

PubMed

Li, Song; Zhang, Pengfei; Fulvio Pasquale, F; Hillesheim Patrick, C; Feng, Guang; Dai, Sheng; Cummings Peter, T

2014-07-16

The use of dicationic ionic liquid (DIL) electrolytes in supercapacitors is impeded by the slow dynamics of DILs, whereas the addition of organic solvents into DIL electrolytes improves ion transport and then enhances the power density of supercapacitors. In this work, the influences of organic solvents on the conductivity of DILs and the electrical double layer (EDL) of DIL-based supercapacitors are investigated using classical molecular dynamics simulation. Two types of organic solvents, acetonitrile (ACN) and propylene carbonate (PC), were used to explore the effects of different organic solvents on the EDL structure and capacitance of DIL/organic solvent-based supercapacitors. Firstly, it was found that the conductivity of DIL electrolytes was greatly enhanced in the presence of the organic solvent ACN. Secondly, a stronger adsorption of PC on graphite results in different EDL structures formed by DIL/ACN and DIL/PC electrolytes. The expulsion of co-ions from EDLs was observed in DIL/organic solvent electrolytes rather than neat DILs and this feature is more evident in DIL/PC. Furthermore, the bell-shaped differential capacitance-electric potential curve was not essentially changed by the presence of organic solvents. Comparing DIL/organic solvent electrolytes with neat DILs, the capacitance is slightly increased by organic solvents, which is in agreement with experimental observation.

21 CFR 184.1666 - Propylene glycol.

Code of Federal Regulations, 2014 CFR

2014-04-01

... chlorinated water to form the chlorohydrin which is converted to the glycol by treatment with sodium carbonate solution. It is also prepared by heating glyercol with sodium hydroxide. (b) The ingredient meets the...

21 CFR 184.1666 - Propylene glycol.

Code of Federal Regulations, 2013 CFR

2013-04-01

... glycol by treatment with sodium carbonate solution. It is also prepared by heating glyercol with sodium hydroxide. (b) The ingredient meets the specifications of the Food Chemicals Codex, 3d Ed. (1981), p. 255...

21 CFR 184.1666 - Propylene glycol.

Code of Federal Regulations, 2012 CFR

2012-04-01

... glycol by treatment with sodium carbonate solution. It is also prepared by heating glyercol with sodium hydroxide. (b) The ingredient meets the specifications of the Food Chemicals Codex, 3d Ed. (1981), p. 255...

An Electrochemical and Spectroelectrochemical Study of Substituted Alkylidene Cyclopropabenzenes: 1-(Diphenylmethylene)Cyclopropabenzene in the First Anodic and Cathodic Voltammetric Waves in Acetonitrile.

DTIC Science & Technology

1986-07-30

extracts were washed with water , dried with magnesium sulfate. and N 3 concentrated to an orange oil under reduced pressure. This oil was then passed...prepared from the metathesis of sodium tetrafluoroborate and tetra-n-butylammonium hydrogen sulfate. The crude product was washed with ice water , dissolved...stored in a vacuum oven at 75°C for 24h before use. Acetonitrile was HPLC grade (Baker Chemicals, 0.001% nominal water content) and was used as received

Silane cross-linkable ethylene-propylene elastomer compositions prepared by reactive processing

NASA Astrophysics Data System (ADS)

Kozawa, Eiji; Nakajima, Yasuo; Kim, Jae Kyung

2015-05-01

Thermoplastic Elastomers (TPEs) have received attention as the alternative materials of EPDM due to an advantage for mass production. In recent years, by the progress of polymerization technology, Ethylene-propylene Elastomer (EP), one of the TPEs, is beginning to be applied to many products because of its good properties as rubber. However, as much as a complete replacement for EPDM, it is not provided with sufficient properties. In such circumstance, we found that EP's performance properties can be further enhanced via chemical modification such as cross-linking. The advent of a newer technique, involving the grafting of organo-functional silane onto the polymer chain in the reaction extrusion process is more attractive due to various industrial advantages. Although the functionalization of the EP by silane grafting through reactive processing is very useful, the silane grafting process of EP has a difficulty. It is most likely a consequence of the nature of the PP chain scission (β-scission), which is the dominant reaction in PP when subjected to free radicals at elevated temperature during processing. Therefore, the objective of our current work is to investigate a reactive extrusion process for the silane cross-linkable EP while minimizing the degradation, as well as evaluate the properties of the modified polymer.

Effect of phase symmetry on the NMR spectrum of acetonitrile oriented in a uniaxial-biaxial-uniaxial phase

NASA Astrophysics Data System (ADS)

Deepak, H. S. Vinay; Yelamaggad, C. V.; Khetrapal, C. L.; Ramanathan, K. V.

2016-09-01

We report here the measurement of the Csbnd H and the Hsbnd H dipolar couplings of the methyl group of acetonitrile oriented in the biaxial liquid crystal potassium laurate/1-decanol/water system. These parameters show large variations when measured as a function of temperature. The variations follow the symmetry of the phase as the liquid crystal goes through the sequence of uniaxial - biaxial - uniaxial phases and show a close correspondence to the phase changes that occur in the liquid crystalline solvent coinciding with the onset of biaxiality. The Hsbnd Csbnd H bond angle calculated after incorporating vibrational corrections to the dipolar couplings is discussed in terms of contributions in the case of the biaxial liquid crystal arising from vibration-rotation interaction effects.

75 FR 57412 - Approval and Promulgation of Implementation Plans Alabama: Volatile Organic Compounds

Federal Register 2010, 2011, 2012, 2013, 2014

2010-09-21

...] Approval and Promulgation of Implementation Plans Alabama: Volatile Organic Compounds AGENCY: Environmental... compounds'' (VOCs) found at Alabama Administrative Code section 335-3-1-.02(gggg). Specifically, the revision would add two compounds (propylene carbonate and dimethyl carbonate) to the list of those excluded...

Physical Properties and Cellular Responses to Crosslinkable Poly(Propylene Fumarate)/Hydroxyapatite Nanocomposites

PubMed Central

Lee, Kee-Won; Wang, Shanfeng; Yaszemski, Michael J.; Lu, Lichun

2008-01-01

A series of crosslinkable nanocomposites has been developed using hydroxyapatite (HA) nanoparticles and poly(propylene fumarate) (PPF). PPF/HA nanocomposites with four different weight fractions of HA nanoparticles have been characterized in terms of thermal and mechanical properties. To assess surface chemistry of crosslinked PPF/HA nanocomposites, their hydrophilicity and capability of adsorbing proteins have been determined using static contact angle measurement and MicroBCA protein assay kit after incubation with 10% fetal bovine serum (FBS), respectively. In vitro cell studies have been performed using MC3T3-E1 mouse pre-osteoblast cells to investigate the ability of PPF/HA nanocomposites to support cell attachment, spreading, and proliferation after 1, 4, and 7 days. By adding HA nanoparticles to PPF, the mechanical properties of crosslinked PPF/HA nanocomposites have not been increased due to the initially high modulus of crosslinked PPF. However, hydrophilicity and serum protein adsorption on the surface of nanocomposites have been significantly increased, resulting in enhanced cell attachment, spreading, and proliferation after 4 days of cell seeding. These results indicate that crosslinkable PPF/HA nanocomposites are useful for hard tissue replacement because of excellent mechanical strength and osteoconductivity. PMID:18403013

Eflect of Relative Humidity on the Bactericidal Activity of Propylene Oxide Vapor1

PubMed Central

Himmelfarb, Philip; El-Bisi, Hamed M.; Read, R. B.; Litsky, Warren

1962-01-01

Because of the low toxicity of its breakdown product, propylene oxide (PO) vapor will play an increasingly important role in the preservation of foods. It is therefore necessary that the diversified variables which influence effectiveness of PO treatment be thoroughly investigated and understood prior to advocating its general use in industry. Accordingly, the present study was undertaken to determine the effect of relative humidity (RH) upon the bactericidal activity of PO sterilant atmospheres. Death rates were established at increasing RH values of < 1, 52, 65, 80, and 98% and under constant conditions of concentration, pressure, and temperature. Test bacterial populations were preconditioned to corresponding moisture levels. Results indicate that gram-positive cocci were relatively insensitive to PO vapor at dry conditions but became progressively less resistant with the increase in RH up to a maximum of 65 to 70%. Lactic acid bacteria and gram-negative rods were much more sensitive at dry conditions, showing much less dependency upon water vapor. Bacillus subtilis spores elicited the highest degree of resistance but the death rate substantially increased with the increase in RH. PMID:13954626

Spectrophotometric study on the proton transfer reaction between 2-amino-4-methylpyridine with 2,6-dichloro-4-nitrophenol in methanol, acetonitrile and the binary mixture 50% methanol + 50% acetonitrile

NASA Astrophysics Data System (ADS)

Al-Ahmary, Khairia M.; Habeeb, Moustafa M.; Al-Obidan, Areej H.

2016-02-01

Proton transfer reaction between 2-amino-4-methylpyridine (2AMP) as the proton acceptor with 2,6-dichloro-4-nitrophenol (DCNP) as the proton donor has been investigated spectrophotometrically in methanol (MeOH), acetonitrile (AN) and a binary mixture composed of 50% MeOH and 50% AN (AN-Me). The composition of the complex has been investigated utilizing Job's and photometric titration methods to be 1:1. Minimum-maximum absorbance equation has been applied to estimate the formation constant of the proton transfer reaction (KPT) where it reached high values in the investigated solvent confirming its high stability. The formation constant recorded higher value in AN compared with MeOH and mixture of AN-Me. Based on the formation of stable proton transfer complex, a sensitive spectrophotometric method was suggested for quantitative determination of 2AMP. The Lambert-Beer's law was obeyed in the concentration range 0.5-8 μg mL- 1 with small values of limits of detection and quantification. The solid complex between 2AMP with DCNP has been synthesized and characterized by elemental analysis to be 1:1 in concordant with the molecular stoichiometry in solution. Further analysis of the solid complex was carried out using infrared and 1H NMR spectroscopy.

Solvation of fluoro-acetonitrile in water by 2D-IR spectroscopy: A combined experimental-computational study

NASA Astrophysics Data System (ADS)

Cazade, Pierre-André; Tran, Halina; Bereau, Tristan; Das, Akshaya K.; Kläsi, Felix; Hamm, Peter; Meuwly, Markus

2015-06-01

The solvent dynamics around fluorinated acetonitrile is characterized by 2-dimensional infrared spectroscopy and atomistic simulations. The lineshape of the linear infrared spectrum is better captured by semiempirical (density functional tight binding) mixed quantum mechanical/molecular mechanics simulations, whereas force field simulations with multipolar interactions yield lineshapes that are significantly too narrow. For the solvent dynamics, a relatively slow time scale of 2 ps is found from the experiments and supported by the mixed quantum mechanical/molecular mechanics simulations. With multipolar force fields fitted to the available thermodynamical data, the time scale is considerably faster—on the 0.5 ps time scale. The simulations provide evidence for a well established CF-HOH hydrogen bond (population of 25%) which is found from the radial distribution function g(r) from both, force field and quantum mechanics/molecular mechanics simulations.

ALMA Spectroscopy of Titan's Atmosphere: First Detections of Vinyl Cyanide and Acetonitrile Isotopologues

NASA Astrophysics Data System (ADS)

Cordiner, Martin; Y Palmer, Maureen; Nixon, Conor A.; Charnley, Steven B.; Mumma, Michael J.; Irwin, Pat G. J.; Teanby, Nick A.; Kisiel, Zbigniew; Serigano, Joseph

2015-11-01

Studies of Titan's atmospheric chemistry provide a unique opportunity to explore the origin and evolution of complex organic matter in primitive planetary atmospheres. The Atacama Large Millimeter/submillimeter Array (ALMA) is a powerful new telescope, well suited to the study of molecular emission from Titan's stratosphere and mesosphere. Here we present early results from our ongoing study to exploit the large volume of Titan data taken using ALMA in Early Science Mode (during the period 2012-2014). Combining data from multiple ALMA Band 6 observations, we obtained high-resolution mm-wave spectra with unprecedented sensitivity, enabling the first detection of vinyl cyanide (C2H3CN) in Titan's atmosphere. Initial estimates indicate a mesospheric abundance ratio with respect to ethyl cyanide (C2H5CN) of [C2H3CN]/[C2H5CN] = 0.31. In addition, we report the first detections on Titan of the 13C and 15N-substituted isotopologues of acetonitrile (13CH3CN and CH3C15N). Radiative transfer models and possible chemical formation pathways for these molecules will be discussed.