21 CFR 73.3127 - Vinyl alcohol/methyl methacrylate-dye reaction products.

Code of Federal Regulations, 2013 CFR

2013-04-01

... coloring effect. (2) As part of the manufacturing process, the lenses containing the color additives are... 21 Food and Drugs 1 2013-04-01 2013-04-01 false Vinyl alcohol/methyl methacrylate-dye reaction products. 73.3127 Section 73.3127 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND...

Formation of furan fatty alkyl esters from their bis-epoxide fatty esters

USDA-ARS?s Scientific Manuscript database

Reactions of epoxidized alkyl soyate with four different alcohols: ethanol, isopropyl alcohol, 2-ethylhexanol, and benzyl alcohol were investigated in the presence of Bronsted acid catalyst. Products not reported in prior studies of similar reactions were found. These were furan fatty acid alkyl est...

Formation of furan fatty alkyl esters from their bis-epoxide fatty esters

USDA-ARS?s Scientific Manuscript database

Reactions of epoxidized alkyl soyate with four different alcohols: ethanol, isopropyl alcohol, 2-ethylhexanol, benzyl alcohol, in the presence of Bronsted acid catalyst, were investigated. Products that were not reported in prior studies of similar reactions were found. These were furan fatty acid a...

A Puzzling Alcohol Dehydration Reaction Solved by GC-MS Analysis

NASA Astrophysics Data System (ADS)

Pelter, Michael W.; Macudzinski, Rebecca M.

1999-06-01

We have adapted the dehydration of 2-methyl-2-propanol to a "puzzle" approach for use in our second-semester chemistry major organic laboratory. The reaction of 2-methyl-2-propanol with ~50% sulfuric acid at 100 °C yields isobutylene, which reacts further by a "puzzling" reaction. By coupling the GC/MS analysis of the product mixture with their knowledge of the mechanism of alcohol dehydration and alkene reactivity, students are able to identify the major products of this reaction.

Interstellar Ices and Radiation-induced Oxidations of Alcohols

NASA Astrophysics Data System (ADS)

Hudson, R. L.; Moore, M. H.

2018-04-01

Infrared spectra of ices containing alcohols that are known or potential interstellar molecules are examined before and after irradiation with 1 MeV protons at ∼20 K. The low-temperature oxidation (hydrogen loss) of six alcohols is followed, and conclusions are drawn based on the results. The formation of reaction products is discussed in terms of the literature on the radiation chemistry of alcohols and a systematic variation in their structures. The results from these new laboratory measurements are then applied to a recent study of propargyl alcohol. Connections are drawn between known interstellar molecules, and several new reaction products in interstellar ices are predicted.

Studying Reaction Intermediates Formed at Graphenic Surfaces

NASA Astrophysics Data System (ADS)

Sarkar, Depanjan; Sen Gupta, Soujit; Narayanan, Rahul; Pradeep, Thalappil

2014-03-01

We report in-situ production and detection of intermediates at graphenic surfaces, especially during alcohol oxidation. Alcohol oxidation to acid occurs on graphene oxide-coated paper surface, driven by an electrical potential, in a paper spray mass spectrometry experiment. As paper spray ionization is a fast process and the time scale matches with the reaction time scale, we were able to detect the intermediate, acetal. This is the first observation of acetal formed in surface oxidation. The process is not limited to alcohols and the reaction has been extended to aldehydes, amines, phosphenes, sugars, etc., where reaction products were detected instantaneously. By combining surface reactions with ambient ionization and mass spectrometry, we show that new insights into chemical reactions become feasible. We suggest that several other chemical transformations may be studied this way. This work opens up a new pathway for different industrially and energetically important reactions using different metal catalysts and modified substrate.

Manganese-Mediated Coupling Reaction of Vinylarenes and Aliphatic Alcohols

PubMed Central

Zhang, Wei; Wang, Nai-Xing; Bai, Cui-Bing; Wang, Yan-Jing; Lan, Xing-Wang; Xing, Yalan; Li, Yi-He; Wen, Jia-Long

2015-01-01

Alcohols and alkenes are the most abundant and commonly used organic building blocks in the large-scale chemical synthesis. Herein, this is the first time to report a novel and operationally simple coupling reaction of vinylarenes and aliphatic alcohols catalyzed by manganese in the presence of TBHP (tert-butyl hydroperoxide). This coupling reaction provides the oxyalkylated products of vinylarenes with good regioselectivity and accomplishes with the principles of step-economies. A possible reaction mechanism has also been proposed. PMID:26470633

Coupling and Reactions of 5-Hydroxyconiferyl Alcohol in Lignin Formation.

PubMed

Elder, Thomas; Berstis, Laura; Beckham, Gregg T; Crowley, Michael F

2016-06-15

The catechol alcohols, caffeyl and 5-hydroxyconiferyl alcohol, may be incorporated into lignin either naturally or through genetic manipulation. Due to the presence of o-OH groups, these compounds form benzodioxanes, a departure from the interunit connections found in lignins derived from the cinnamyl alcohols. In nature, lignins composed of caffeyl and 5-hydroxyconiferyl alcohol are linear homopolymers and, as such, may have properties that make them amenable for use in value-added products, such as lignin-based carbon fibers. In the current work, results from density functional theory calculations for the reactions of 5-hydroxyconiferyl alcohol, taking stereochemistry into account, are reported. Dehydrogenation and quinone methide formation are found to be thermodynamically favored for 5-hydroxyconiferyl alcohol, over coniferyl alcohol. The comparative energetics of the rearomatization reactions suggest that the formation of the benzodioxane linkage is under kinetic control. Ring-opening reactions of the benzodioxane groups show that the bond dissociation enthalpy of the α-O cleavage reaction is lower than that of the β-O reaction. The catechol lignins represent a novel form of the polymer that may offer new opportunities for bioproducts and genetic targets.

Coniferyl alcohol reactivity at the air/water interface.

PubMed

Cathala, Bernard; Aguié-Béghin, Véronique; Douillard, Roger

2004-01-01

In order to investigate the sensitivity of the lignin monomer coupling reactions to the environment physicochemical conditions, coniferyl alcohol (CA) was polymerised at the air/water interface. Characterisation of the interface during the reaction by surface pressure measurement and ellipsometry demonstrates that the reaction occurs near or at the interface. Coupling products were analysed by HPLC and compared to reaction products obtained in the case of polymerisation in solution. Relative proportions of beta-beta and beta-O-4 dehydrodimers were found to increase in air/water interface experiment.

Cocondensation of urea with methylolphenols in acidic conditions

Treesearch

Bunchiro Tomita; Chung-Yun Hse

1992-01-01

The reactions of urea with methylolphenols under acidic conditions were investigated using 2- and 4-hydroxybenzyl alcohol and crude 2,4,6-trimethylophenol as model compounds. The reaction products were analyzed with 13C-NMR spectroscopy and GPC. From the reaction of urea with 4-hydroxybenzyl alcohol, the formations of 4-hydroxybenzylurea,

Copper-catalyzed decarboxylative trifluoromethylation of allylic bromodifluoroacetates.

PubMed

Ambler, Brett R; Altman, Ryan A

2013-11-01

The development of new synthetic fluorination reactions has important implications in medicinal, agricultural, and materials chemistries. Given the prevalence and accessibility of alcohols, methods to convert alcohols to trifluoromethanes are desirable. However, this transformation typically requires four-step processes, specialty chemicals, and/or stoichiometric metals to access the trifluoromethyl-containing product. A two-step copper-catalyzed decarboxylative protocol for converting allylic alcohols to trifluoromethanes is reported. Preliminary mechanistic studies distinguish this reaction from previously reported Cu-mediated reactions.

Biodiesel production by transesterification using immobilized lipase.

PubMed

Narwal, Sunil Kumar; Gupta, Reena

2013-04-01

Biodiesel can be produced by transesterification of vegetable or waste oil catalysed by lipases. Biodiesel is an alternative energy source to conventional fuel. It combines environmental friendliness with biodegradability, low toxicity and renewability. Biodiesel transesterification reactions can be broadly classified into two categories: chemical and enzymatic. The production of biodiesel using the enzymatic route eliminates the reactions catalysed under acid or alkali conditions by yielding product of very high purity. The modification of lipases can improve their stability, activity and tolerance to alcohol. The cost of lipases and the relatively slower reaction rate remain the major obstacles for enzymatic production of biodiesel. However, this problem can be solved by immobilizing the enzyme on a suitable matrix or support, which increases the chances of re-usability. The main factors affecting biodiesel production are composition of fatty acids, catalyst, solvents, molar ratio of alcohol and oil, temperature, water content, type of alcohol and reactor configuration. Optimization of these parameters is necessary to reduce the cost of biodiesel production.

Coupling and Reactions of 5-Hydroxyconiferyl Alcohol in Lignin Formation

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

Elder, Thomas; Berstis, Laura; Beckham, Gregg T.

The catechol alcohols, caffeyl and 5-hydroxyconiferyl alcohol, may be incorporated into lignin either naturally or through genetic manipulation. Due to the presence of o-OH groups, these compounds form benzodioxanes, a departure from the interunit connections found in lignins derived from the cinnamyl alcohols. In nature, lignins composed of caffeyl and 5-hydroxyconiferyl alcohol are linear homopolymers and, as such, may have properties that make them amenable for use in value-added products, such as lignin-based carbon fibers. In the current work, results from density functional theory calculations for the reactions of 5-hydroxyconiferyl alcohol, taking stereochemistry into account, are reported. Dehydrogenation and quinone methide formation are found to be thermodynamically favored for 5-hydroxyconiferyl alcohol, over coniferyl alcohol. The comparative energetics of the rearomatization reactions suggest that the formation of the benzodioxane linkage is under kinetic control. Ring-opening reactions of the benzodioxane groups show that the bond dissociation enthalpy of themore » $$\\alpha$$-O cleavage reaction is lower than that of the $$\\beta$$-O reaction. In conclusion, the catechol lignins represent a novel form of the polymer that may offer new opportunities for bioproducts and genetic targets.« less

Coupling and Reactions of 5-Hydroxyconiferyl Alcohol in Lignin Formation

DOE PAGES

Elder, Thomas; Berstis, Laura; Beckham, Gregg T.; ...

2016-05-28

The catechol alcohols, caffeyl and 5-hydroxyconiferyl alcohol, may be incorporated into lignin either naturally or through genetic manipulation. Due to the presence of o-OH groups, these compounds form benzodioxanes, a departure from the interunit connections found in lignins derived from the cinnamyl alcohols. In nature, lignins composed of caffeyl and 5-hydroxyconiferyl alcohol are linear homopolymers and, as such, may have properties that make them amenable for use in value-added products, such as lignin-based carbon fibers. In the current work, results from density functional theory calculations for the reactions of 5-hydroxyconiferyl alcohol, taking stereochemistry into account, are reported. Dehydrogenation and quinone methide formation are found to be thermodynamically favored for 5-hydroxyconiferyl alcohol, over coniferyl alcohol. The comparative energetics of the rearomatization reactions suggest that the formation of the benzodioxane linkage is under kinetic control. Ring-opening reactions of the benzodioxane groups show that the bond dissociation enthalpy of themore » $$\\alpha$$-O cleavage reaction is lower than that of the $$\\beta$$-O reaction. In conclusion, the catechol lignins represent a novel form of the polymer that may offer new opportunities for bioproducts and genetic targets.« less

Studies on the oxidation reaction of tyrosine (Tyr) with H2O2 catalyzed by horseradish peroxidase (HRP) in alcohol-water medium by spectrofluorimetry and differential spectrophotometry.

PubMed

Tang, Bo; Wang, Yan; Liang, Huiling; Chen, Zhenzhen; He, Xiwen; Shen, Hanxi

2006-03-01

An oxidation reaction of tyrosine (Tyr) with H(2)O(2) catalyzed by horseradish peroxidase (HRP) was studied by spectrofluorimetry and differential spectrophotometry in the alcohol(methanol, ethanol, 1-propanol and isopropanol)-water mutual solubility system. Compared with the enzymatic-catalyzed reaction in the water medium, the fluorescence intensities of the product weakened, even extinguished. Because the addition of alcohols made the conformation of HRP change, the catalytic reaction shifted to the side of polymerization and the polymer (A(n)H(2), n>or=3) exhibited no fluorescence. The four alcohols cannot deactivate HRP. Moreover isopropanol activated HRP remarkably.

Acid-catalyzed ring-opening reactions of a cyclopropanated 3-aza-2-oxabicyclo[2.2.1]hept-5-ene with alcohols.

PubMed

Tait, Katrina; Horvath, Alysia; Blanchard, Nicolas; Tam, William

2017-01-01

The acid-catalyzed ring-opening reactions of a cyclopropanated 3-aza-2-oxabicylic alkene using alcohol nucleophiles were investigated. Although this acid-catalyzed ring-opening reaction did not cleave the cyclopropane unit as planned, this represent the first examples of ring-openings of cyclopropanated 3-aza-2-oxabicyclo[2.2.1]alkenes that lead to the cleavage of the C-O bond instead of the N-O bond. Different acid catalysts were tested and it was found that pyridinium toluenesulfonate in methanol gave the best yields in the ring-opening reactions. The scope of the reaction was successfully expanded to include primary, secondary, and tertiary alcohol nucleophiles. Through X-ray crystallography, the stereochemistry of the product was determined which confirmed an S N 2-like mechanism to form the ring-opened product.

Alcohol-to-acid ratio and substrate concentration affect product structure in chain elongation reactions initiated by unacclimatized inoculum.

PubMed

Liu, Yuhao; Lü, Fan; Shao, Liming; He, Pinjing

2016-10-01

The objective of the study was to investigate whether the ratio of ethanol to acetate affects yield and product structure in chain elongation initiated by unacclimatized mixed cultures. The effect of varying the substrate concentration, while maintaining the same ratio of alcohol to acid, was also investigated. With a high substrate concentration, an alcohol to acid ratio >2:1 provided sufficient electron donor capacity for the chain elongation reaction. With an ethanol to acetate ratio of 3:1 (300mM total carbon), the highest n-caproate concentration (3033±98mg/L) was achieved during the stable phase of the reaction. A lower substrate concentration (150mM total carbon) gave a lower yield of products and led to reduced carbon transformation efficiency compared with other reaction conditions. The use of unacclimatized inoculum in chain elongation can produce significant amounts of odd-carbon-number carboxylates as a result of protein hydrolysis. Copyright © 2016 Elsevier Ltd. All rights reserved.

Ligand-Substitution Reactions of the Tellurium Compound AS-101 in Physiological Aqueous and Alcoholic Solutions.

PubMed

Silberman, Alon; Albeck, Michael; Sredni, Benjamin; Albeck, Amnon

2016-11-07

Since its first crystallization, the aqueous structure of the tellurium-containing experimental drug AS-101 has never been studied. We show that, under the aqueous conditions in which it is administered, AS-101 is subjected to an immediate ligand-substitution reaction with water, yielding a stable hydrolyzed oxide anion product that is identified, for the first time, to be TeOCl 3 - . Studying the structure of AS-101 in propylene glycol (PG), an alcoholic solvent often used for the topical and oral administration of AS-101, revealed the same phenomenon of ligand-substitution reaction between the alcoholic ligands. Upon exposure to water, the PG-substituted product is also hydrolyzed to the same tellurium(IV) oxide form, TeOCl 3 - .

KINETICS OF THE DEHYDROGENATION AND DEHYDRATION OF ISOPROPYL ALCOHOL AND THE DEHYDROGENATION OF TETRALIN ON LANTHANUM OXIDE (in Russian)

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

Tolstopyatova, A.A.; Balandin, A.A.; Yu, C.

1963-10-01

All the relative adsorption coefficients of the dehydrogenation and dehydration products of isopropyl alcohol and dehydrogenation products of tetralin are temperaturedependent. The inhibiting action of the products, propylene, water, and acetone in the isopropyl alcohol reaction and hydrogen in the tetralin reaction diminishes as the temperature is raised. Acetone and water possess a relatively high inhibiting effect. The bond energies of C, H, and 0 with La/sub 2/O/sub 3/ were determined by means of the kinetic method from the activation energies. It was found that Q/sub C-Cat/ < Q/sub H-Cat/ < Q/sub O-Cat/ . (auth)

Regioselective Hydration of an Alkene and Analysis of the Alcohol Product by Remote Access NMR: A Classroom Demonstration

ERIC Educational Resources Information Center

Smith, Maureen E.; Johnson, Sara L.; Masterson, Douglas S.

2013-01-01

A two-part demonstration was conducted in our first-semester organic chemistry course designed to introduce students to the formation of alcohols, regioselective reactions, and analysis of organic products by NMR analysis. This demonstration utilized the oxymercuration-demercuration sequence to prepare an alcohol from an alkene in a Markovnikov…

Indium-catalyzed direct chlorination of alcohols using chlorodimethylsilane-benzil as a selective and mild system.

PubMed

Yasuda, Makoto; Yamasaki, Satoshi; Onishi, Yoshiyuki; Baba, Akio

2004-06-16

The InCl3-catalyzed reaction of alcohols with chlorodimethylsilane (HSiMe2Cl) in the presence of benzil gave the corresponding organic chlorides under mild conditions. Benzil significantly changes the reaction course because the reducing product through dehydroxyhydration was obtained in the absence of benzil. The secondary or tertiary alcohols were effectively chlorinated. The substrates bearing acid-sensitive functional groups were also applied to this system. The highly selective chlorination of the tertiary site was observed in the competitive reaction between tertiary and primary alcohols. The highly coordinated hydrosilane generated from benzil and HSiMe2Cl is an important intermediate.

Surface chemistry of a pine-oil cleaner and other terpene mixtures with ozone on vinyl flooring tiles.

PubMed

Ham, Jason E; Wells, J Raymond

2011-04-01

Indoor environments are dynamic reactors where consumer products (such as cleaning agents, deodorants, and air fresheners) emit volatile organic compounds (VOCs) that can subsequently interact with indoor oxidants such as ozone (O(3)), hydroxyl radicals, and nitrate radicals. Typically, consumer products consist of mixtures of VOCs and semi-VOCs which can react in the gas-phase or on surfaces with these oxidants to generate a variety of oxygenated products. In this study, the reaction of a pine-oil cleaner (POC) with O(3) (100ppb) on a urethane-coated vinyl flooring tile was investigated at 5% and 50% relative humidity. These results were compared to previous α-terpineol+O(3) reactions on glass and vinyl surfaces. Additionally, other terpene and terpene alcohol mixtures were formulated to understand the emission profiles as seen in the POC data. Results showed that the α-terpineol+O(3) reaction products were the prominent species that were also observed in the POC/O(3) surface experiments. Furthermore, α-terpineol+O(3) reactions generate the largest fraction of oxygenated products even in equal mixtures of other terpene alcohols. This finding suggests that the judicial choice of terpene alcohols for inclusion in product formulations may be useful in reducing oxidation product emissions. Published by Elsevier Ltd.

Hydrogenation of carbonyl compounds of relevance to hydrogen storage in alcohols

NASA Astrophysics Data System (ADS)

Suárez, Andrés

2018-02-01

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

Effects of Maillard reaction products in a glucose-glycine alcoholic solution on antioxidative and antimutagenic activities.

PubMed

Ko, Chih-Yuan; Chen, Xiao-Yu; Chang, Wen-Chang; Zeng, Yi-Ming; Lin, Ru-Hai; Zhang, Xiao-Bin; Wu, James Swi-Bea; Shen, Szu-Chuan

2018-04-12

Marinating meat with alcohol, such as wine and beer, is a common culinary practice in cultures worldwide. This study we use a model marination solution comprising 0.2 M glucose-0.2 M glycine buffered to pH 4.3 containing either 0% or 50% ethanol and mimicked the cooking process by heating for 12 h. Antioxidative and antimutagenic characteristics of Maillard reaction products (MRPs) were investigated. Reducing power, antioxidant activity (Fe 2+ chelating ability) and free radical neutralization ability generated from DPPH and ABTS were determined. Ames testing was performed. Results indicate that MRPs from aqueous and alcoholic solution exhibit four antioxidative assays in a dose-dependent manner from 0.16 to 10.00 mg mL -1 . However, MRPs from the alcoholic model was superior. In Ames testing, MRPs from both models are neither toxic nor mutagenic at the test concentrations of 0.63-10.00 mg plate -1 . However, MRPs from the alcoholic model exhibited a higher inhibitory effect on the direct-acting mutagen 4-NQNO compared to the aqueous model. This result is consistent with the observation that MRPs with higher antioxidative capacity exhibit superior antimutagenic activity, suggesting that there are more different products in the alcoholic model. Our results add to the current knowledge about the antioxidative and antimutagenic properties of Maillard reaction products arising when food is cooked in the presence of ethanol. This article is protected by copyright. All rights reserved.

The effect of Maillard reaction products and yeast strain on the synthesis of key higher alcohols and esters in beer fermentations.

PubMed

Dack, Rachael E; Black, Gary W; Koutsidis, Georgios; Usher, St John

2017-10-01

The effect of Maillard reaction products (MRPs), formed during the production of dark malts, on the synthesis of higher alcohols and esters in beer fermentations was investigated by headspace solid-phase microextraction GC-MS. Higher alcohol levels were significantly (p<0.05) higher in dark malt fermentations, while the synthesis of esters was inhibited, due to possible suppression of enzyme activity and/or gene expression linked to ester synthesis. Yeast strain also affected flavour synthesis with Saccharomyces cerevisiae strain A01 producing considerably lower levels of higher alcohols and esters than S288c and L04. S288c produced approximately double the higher alcohol levels and around twenty times more esters compared to L04. Further investigations into malt type-yeast strain interactions in relation to flavour development are required to gain better understanding of flavour synthesis that could assist in the development of new products and reduce R&D costs for the industry. Copyright © 2017 Elsevier Ltd. All rights reserved.

Gold(I)-Catalysed Direct Thioetherifications Using Allylic Alcohols: an Experimental and Computational Study

PubMed Central

Herkert, Lorena; Green, Samantha L J; Barker, Graeme; Johnson, David G; Young, Paul C; Macgregor, Stuart A; Lee, Ai-Lan

2014-01-01

A gold(I)-catalysed direct thioetherification reaction between allylic alcohols and thiols is presented. The reaction is generally highly regioselective (SN2′). This dehydrative allylation procedure is very mild and atom economical, producing only water as the by-product and avoiding any unnecessary waste/steps associated with installing a leaving or activating group on the substrate. Computational studies are presented to gain insight into the mechanism of the reaction. Calculations indicate that the regioselectivity is under equilibrium control and is ultimately dictated by the thermodynamic stability of the products. PMID:25080400

Copper(I)/TEMPO Catalyzed Aerobic Oxidation of Primary Alcohols to Aldehydes with Ambient Air

PubMed Central

Hoover, Jessica M.; Steves, Janelle E.; Stahl, Shannon S.

2012-01-01

This protocol describes a practical laboratory-scale method for aerobic oxidation of primary alcohols to aldehydes, using a chemoselective CuI/TEMPO catalyst system. The catalyst is prepared in situ from commercially available reagents, and the reactions are performed in a common organic solvent (acetonitrile) with ambient air as the oxidant. Three different reaction conditions and three procedures for the isolation and purification of the aldehyde product are presented. The oxidations of eight different alcohols, described here, include representative examples of each reaction condition and purification method. Reaction times vary from 20 min to 24 h, depending on the alcohol, while the purification methods each take about 2 h. The total time necessary for the complete protocol ranges from 3 – 26 h. PMID:22635108

Continuous Catalytic Production of Methyl Acrylates from Unsaturated Alcohols by Gold: The Strong Effect of C=C Unsaturation on Reaction Selectivity

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

Zugic, Branko; Karakalos, Stavros; Stowers, Kara J.

2016-03-04

Here we demonstrate the gas-phase catalytic production of methyl acrylates by oxygen-assisted coupling of methanol with the unsaturated alcohols allyl alcohol and methylallyl alcohol over nanoporous gold (npAu) at atmospheric pressure. Analogous investigations on O-activated Au(110) exhibit the same pattern of reactivity and are used to establish that the competition between methoxy and allyloxy (or methallyloxy) reaction intermediates for adsorption sites, mediated by the reactants themselves, determines the selectivity of reaction. Our results clearly show that the C=C bond substantially increases the binding efficacy of the allyloxy (or methallyloxy), thus requiring extremely high methanol mole fractions (>0.99) in order tomore » achieve comparable surface concentrations of methoxy and produce optimum yields of either methacrylate or methyl methacrylate. Allyloxy and methallyloxy were favored by factors of ~100 and ~450, respectively, vs methoxy. These values are more than 1 order of magnitude greater than those measured for competitive binding of ethoxy and 1-butoxy vs methoxy, demonstrating the strong effect of the carbon–carbon bond unsaturation. The 4.5-fold increase due to the addition of the methyl group in methylallyl alcohol vs allyl alcohol indicates the significant effect of the additional van der Waals interactions between the methyl group and the surface. Gas-phase acidity is also shown to be a good qualitative indicator for the relative binding strength of the alkoxides. This work provides insight into the control of reaction selectivity for coupling reactions and demonstrates the value of fundamental studies on single crystals for establishing key principles governing reaction selectivity. Notably, these oxygen-assisted coupling reactions occur without oxidation of the C=C bond.« less

Continuous Catalytic Production of Methyl Acrylates from Unsaturated Alcohols by Gold: The Strong Effect of C=C Unsaturation on Reaction Selectivity

DOE PAGES

Zugic, Branko; Karakalos, Stavros; Stowers, Kara J.; ...

2016-02-02

We demonstrate the gas-phase catalytic production of methyl acrylates by oxygen-assisted coupling of methanol with the unsaturated alcohols allyl alcohol and methylallyl alcohol over nanoporous gold (npAu) at atmospheric pressure. Analogous investigations on O-activated Au(110) exhibit the same pattern of reactivity and are used to establish that the competition between methoxy and allyloxy (or methallyloxy) reaction intermediates for adsorption sites, mediated by the reactants themselves, determines the selectivity of reaction. These results clearly show that the C=C bond substantially increases the binding efficacy of the allyloxy (or methallyloxy), thus requiring extremely high methanol mole fractions (>0.99) in order to achievemore » comparable surface concentrations of methoxy and produce optimum yields of either methacrylate or methyl methacrylate. Allyloxy and methallyloxy were favored by factors of ~100 and ~450, respectively, vs methoxy. These values are more than 1 order of magnitude greater than those measured for competitive binding of ethoxy and 1-butoxy vs methoxy, demonstrating the strong effect of the carbon–carbon bond unsaturation. The 4.5-fold increase due to the addition of the methyl group in methylallyl alcohol vs allyl alcohol indicates the significant effect of the additional van der Waals interactions between the methyl group and the surface. Gas-phase acidity is also shown to be a good qualitative indicator for the relative binding strength of the alkoxides. This work then provides insight into the control of reaction selectivity for coupling reactions and demonstrates the value of fundamental studies on single crystals for establishing key principles governing reaction selectivity. Notably, these oxygen-assisted coupling reactions occur without oxidation of the C=C bond.« less

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

PubMed

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

2012-01-20

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

Mixed Alcohol Dehydration over Bronsted and Lewis Acidic Catalysts

DOE PAGES

Nash, Connor P.; Ramanathan, Anand; Ruddy, Daniel A.; ...

2015-12-01

Mixed alcohols are attractive oxygenated products of biomass-derived syngas because they may be catalytically converted to a range of hydrocarbon products, including liquid hydrocarbon fuels. Catalytic dehydration to form olefins is a potential first step in the conversion of C 2–C 4 alcohols into longer-chain hydrocarbons. Here, we describe the physical and chemical characterization along with catalytic activity and selectivity of 4 Brønsted and Lewis acidic catalysts for the dehydration of two mixed alcohol feed streams that are representative of products from syngas conversion over K-CoMoS type catalysts (i.e., ethanol, 1-propanol, 1-butanol and 2-methyl-1-propanol). Specifically, a Lewis acidic Zr-incorporated mesoporousmore » silicate (Zr-KIT-6), a commercial Al-containing mesoporous silicate (Al-MCM-41), a commercial microporous aluminosilicate (HZSM-5), and a commercial microporous silicoaluminophosphate (SAPO-34) were tested for mixed alcohol dehydration at 250, 300 and 350 °C. The zeolite materials exhibited high activity (>98% ethanol conversion) at all temperatures while the mesoporous materials only displayed significant activity (>10% ethanol conversion) at or above 300 °C. The turnover frequencies for ethanol dehydration at 300 °C decreased in the following order: HZSM-5 > SAPO-34 > Al-MCM-41 > Zr-KIT-6, suggesting that Brønsted acidic sites are more active than Lewis acidic sites for alcohol dehydration. At 300 °C, SAPO-34 produced the highest yield of olefin products from both a water-free ethanol rich feed stream and a C 3+-alcohol rich feed stream containing water. Post-reaction characterization indicated changes in the Brønsted-to-Lewis acidic site ratios for Zr-KIT-6, Al-MCM-41 and HZSM-5. Ammonia temperature programmed desorption indicated that the acid sites of post-reaction samples could be regenerated following treatment in air. The post-reaction SAPO-34 catalyst contained more aromatic, methylated aromatic and polyaromatic compounds than its zeolite counterpart HZSM-5, while no aromatic compounds were observed on post-reaction Al-MCM-41 or Zr-KIT-6 catalysts. Olefin yield at 300 °C over SAPO-34 (>95%) was comparable to published values for the methanol-to-olefins process, indicating the potential industrial application of mixed alcohol dehydration. Furthermore, the olefin product distribution over SAPO-34 was tunable by the composition of the alcohol feed mixture.« less

Mixed Alcohol Dehydration over Bronsted and Lewis Acidic Catalysts

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

Nash, Connor P.; Ramanathan, Anand; Ruddy, Daniel A.

Mixed alcohols are attractive oxygenated products of biomass-derived syngas because they may be catalytically converted to a range of hydrocarbon products, including liquid hydrocarbon fuels. Catalytic dehydration to form olefins is a potential first step in the conversion of C 2–C 4 alcohols into longer-chain hydrocarbons. Here, we describe the physical and chemical characterization along with catalytic activity and selectivity of 4 Brønsted and Lewis acidic catalysts for the dehydration of two mixed alcohol feed streams that are representative of products from syngas conversion over K-CoMoS type catalysts (i.e., ethanol, 1-propanol, 1-butanol and 2-methyl-1-propanol). Specifically, a Lewis acidic Zr-incorporated mesoporousmore » silicate (Zr-KIT-6), a commercial Al-containing mesoporous silicate (Al-MCM-41), a commercial microporous aluminosilicate (HZSM-5), and a commercial microporous silicoaluminophosphate (SAPO-34) were tested for mixed alcohol dehydration at 250, 300 and 350 °C. The zeolite materials exhibited high activity (>98% ethanol conversion) at all temperatures while the mesoporous materials only displayed significant activity (>10% ethanol conversion) at or above 300 °C. The turnover frequencies for ethanol dehydration at 300 °C decreased in the following order: HZSM-5 > SAPO-34 > Al-MCM-41 > Zr-KIT-6, suggesting that Brønsted acidic sites are more active than Lewis acidic sites for alcohol dehydration. At 300 °C, SAPO-34 produced the highest yield of olefin products from both a water-free ethanol rich feed stream and a C 3+-alcohol rich feed stream containing water. Post-reaction characterization indicated changes in the Brønsted-to-Lewis acidic site ratios for Zr-KIT-6, Al-MCM-41 and HZSM-5. Ammonia temperature programmed desorption indicated that the acid sites of post-reaction samples could be regenerated following treatment in air. The post-reaction SAPO-34 catalyst contained more aromatic, methylated aromatic and polyaromatic compounds than its zeolite counterpart HZSM-5, while no aromatic compounds were observed on post-reaction Al-MCM-41 or Zr-KIT-6 catalysts. Olefin yield at 300 °C over SAPO-34 (>95%) was comparable to published values for the methanol-to-olefins process, indicating the potential industrial application of mixed alcohol dehydration. Furthermore, the olefin product distribution over SAPO-34 was tunable by the composition of the alcohol feed mixture.« less

Tandem Reactions for Streamlining Synthesis

PubMed Central

HUSSAIN, MAHMUD M.; WALSH, PATRICK J.

2009-01-01

CONSPECTUS In 1980 Sharpless and Katsuki introduced the asymmetric epoxidation of prochiral allylic alcohols (the Sharpless-Katsuki Asymmetric Epoxidation), which enabled the rapid synthesis of highly enantioenriched epoxy alcohols. This reaction was a milestone in the development of asymmetric catalysis because it was the first highly enantioselective oxidation reaction. Furthermore, it provided access to enantioenriched allylic alcohols that are now standard starting materials in natural product synthesis. In 1981 Sharpless and coworkers made another seminal contribution by describing the kinetic resolution (KR) of racemic allylic alcohols. This work demonstrated that small-molecule catalysts could compete with enzymatic catalysts in KRs. For these pioneering works, Sharpless was awarded the 2001 Nobel Prize with Knowles and Noyori. Despite these achievements, the Sharpless KR is not an efficient method to prepare epoxy alcohols with high enantiomeric excess (ee). First, the racemic allylic alcohol must be prepared and purified. KR of the racemic allylic alcohol must be stopped at low conversion, because the ee of the product epoxy alcohol decreases as the KR progresses. Thus, better methods to prepare epoxy alcohols containing stereogenic carbinol carbons are needed. This Account summarizes our efforts to develop one-pot methods for the synthesis of various epoxy alcohols and allylic epoxy alcohols with high enantio-, diastereo-, and chemoselectivity. Our laboratory developed titanium-based catalysts for use in the synthesis of epoxy alcohols with tertiary carbinols. The catalysts are involved in the first step, which is an asymmetric alkyl or allyl addition to enones. The resulting intermediates are then subjected to a titanium-directed diastereoselective epoxidation to provide tertiary epoxy alcohols. Similarly, the synthesis of acyclic epoxy alcohols begins with asymmetric additions to enals and subsequent epoxidation. The methods described here enable the synthesis of skeletally diverse epoxy alcohols. PMID:18710197

Synthesis of 1,3,5-triazines via Cu(OAc)2-catalyzed aerobic oxidative coupling of alcohols and amidine hydrochlorides.

PubMed

You, Qing; Wang, Fei; Wu, Chaoting; Shi, Tianchao; Min, Dewen; Chen, Huajun; Zhang, Wu

2015-06-28

Cu(OAc)2 was found to be an efficient catalyst for dehydrogenative synthesis of 1,3,5-triazine derivatives via oxidative coupling reaction of amidine hydrochlorides and alcohols in air. Both aromatic and aliphatic alcohols can be involved in the reaction and thirty-three products were obtained with good to excellent yields. Moreover, the use of a ligand, strong base and organic oxidant is unnecessary.

Reaction and catalyst engineering to exploit kinetically controlled whole-cell multistep biocatalysis for terminal FAME oxyfunctionalization.

PubMed

Schrewe, Manfred; Julsing, Mattijs K; Lange, Kerstin; Czarnotta, Eik; Schmid, Andreas; Bühler, Bruno

2014-09-01

The oxyfunctionalization of unactivated C−H bonds can selectively and efficiently be catalyzed by oxygenase-containing whole-cell biocatalysts. Recombinant Escherichia coli W3110 containing the alkane monooxygenase AlkBGT and the outer membrane protein AlkL from Pseudomonas putida GPo1 have been shown to efficiently catalyze the terminal oxyfunctionalization of renewable fatty acid methyl esters yielding bifunctional products of interest for polymer synthesis. In this study, AlkBGTL-containing E. coli W3110 is shown to catalyze the multistep conversion of dodecanoic acid methyl ester (DAME) via terminal alcohol and aldehyde to the acid, exhibiting Michaelis-Menten-type kinetics for each reaction step. In two-liquid phase biotransformations, the product formation pattern was found to be controlled by DAME availability. Supplying DAME as bulk organic phase led to accumulation of the terminal alcohol as the predominant product. Limiting DAME availability via application of bis(2-ethylhexyl)phthalate (BEHP) as organic carrier solvent enabled almost exclusive acid accumulation. Furthermore, utilization of BEHP enhanced catalyst stability by reducing toxic effects of substrate and products. A further shift towards the overoxidized products was achieved by co-expression of the gene encoding the alcohol dehydrogenase AlkJ, which was shown to catalyze efficient and irreversible alcohol to aldehyde oxidation in vivo. With DAME as organic phase, the aldehyde accumulated as main product using resting cells containing AlkBGT, AlkL, as well as AlkJ. This study highlights the versatility of whole-cell biocatalysis for synthesis of industrially relevant bifunctional building blocks and demonstrates how integrated reaction and catalyst engineering can be implemented to control product formation patterns in biocatalytic multistep reactions. © 2014 Wiley Periodicals, Inc.

A kinetic model for the synthesis of high-molecular-weight alcohols over a sulfided Co-K-Mo/C catalyst

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

Gunturu, A.K.; Kugler, E.L.; Cropley, J.B.

A statistically designed set of experiments was run in a recycle reactor to evaluate the kinetics of the formation of higher-molecular-weight alcohols (higher alcohols) and total hydrocarbon byproducts from synthesis gas (hydrogen and carbon monoxide) in a range of experimental conditions that mirrors the limits of commercial production. The alkali-promoted, C-supported Co-Mo sulfide catalyst that was employed in this study is well known for its sulfur resistance. The reaction was carried out in a gradientless Berty-type recycle reactor. A two-level fractional-factorial set consisting of 16 experiments was performed. Five independent variables were selected for this study, namely, temperature, partial pressuremore » of carbon monoxide, partial pressure of hydrogen, partial pressure of inerts, and methanol concentration in the feed. The major oxygenated products were linear alcohols up to n-butanol, but alcohols of higher carbon number were also detected, and analysis of the liquid product revealed the presence of trace amounts of ethers also. Yields of hydrocarbons were non-negligible. The alcohol product followed an Anderson-Schultz-Flory distribution. From the results of the factorial experiments, a preliminary power-law model was developed, and the statistically significant variables in the rate expression for the production of each alcohol were found. Based on the results of the power-law models, rate expressions of the Langmuir-Hinshelwood type were fitted. The observed kinetics are consistent with the rate-limiting step for the production of each higher alcohol being a surface reaction of the alcohol of next-lower carbon number. All other steps, including CO-insertion, H{sub 2}-cleavage, and hydrogenation steps, do not appear to affect the rate correlations.« less

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.

Characterization of the polymerization of furfuryl alcohol during roasting of coffee.

PubMed

Swasti, Yuliana Reni; Murkovic, Michael

2012-09-01

The polymerization of furfuryl alcohol contributes to the formation of the brown colour in heated foods, in addition to the Maillard and caramelization reactions. During the heating of food, furfuryl alcohol is formed via the degradation of quinic acid or 1,2-enediols. Furfuryl alcohol is a mutagenic compound. In acidic conditions it is able to polymerize and form aliphatic polymers that show a brown colour. Herein we show that furfuryl alcohol polymerizes in a model system by incubating it in 1 M HCl at room temperature. Some of the reaction products are dimers, trimers, tetramers, and pentamers with methylene linkages. The degree of polymerization and the amount of those furfuryl alcohol oligomers increased with increasing reaction time. The results of this model system were used to characterize the polymerization of furfuryl alcohol which is produced during roasting of coffee. The coffee was roasted at 210 °C for 2, 3, 4, 5, and 6 min with a home coffee roaster. Furfuryl alcohol and its dimer were found in roasted coffee after 2 and 3 min of roasting respectively, reaching a maximum amount after 4 min. Perhaps due to further reactions, the dimeric furfuryl alcohol concentration starts to decrease after 4 min. We propose that the polymers of furfuryl alcohol contribute to the brown colour of roasted foods.

Can the epoxides of cinnamyl alcohol and cinnamal show new cases of contact allergy?

PubMed

Hagvall, Lina; Niklasson, Ida B; Luthman, Kristina; Karlberg, Ann-Therese

2018-06-01

Cinnamyl alcohol is considered to be a prohapten and prehapten with cinnamal as the main metabolite. However, many individuals who are allergic to cinnamyl alcohol do not react to cinnamal. Sensitizing epoxides of cinnamyl alcohol and cinnamal have been identified as metabolites and autoxidation products of cinnamyl alcohol. To investigate the clinical relevance of contact allergy to epoxycinnamyl alcohol and epoxycinnamal. Irritative effects of the epoxides were investigated in 12 dermatitis patients. Epoxycinnamyl alcohol and epoxycinnamal were patch tested in 393 and 390 consecutive patients, respectively. In parallel, cinnamyl alcohol and cinnamal were patch tested in 607 and 616 patients, respectively. Both epoxides were irritants, but no more positive reactions were detected than when testing was performed with cinnamyl alcohol and cinnamal. Late allergic reactions to epoxycinnamyl alcohol were observed. In general, patients with late reactions showed doubtful or positive reactions to cinnamal and fragrance mix I at regular patch testing. The investigated epoxides are not important haptens in contact allergy to cinnamon fragrance. The high frequency of fragrance allergy among patients included in the irritancy study showed the difficulty of suspecting fragrance allergy on the basis of history; patch testing broadly with fragrance compounds is therefore important. © 2018 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

Stereoinversion of tertiary alcohols to tertiary-alkyl isonitriles and amines.

PubMed

Pronin, Sergey V; Reiher, Christopher A; Shenvi, Ryan A

2013-09-12

The SN2 reaction (bimolecular nucleophilic substitution) is a well-known chemical transformation that can be used to join two smaller molecules together into a larger molecule or to exchange one functional group for another. The SN2 reaction proceeds in a very predictable manner: substitution occurs with inversion of stereochemistry, resulting from the 'backside attack' of the electrophilic carbon by the nucleophile. A significant limitation of the SN2 reaction is its intolerance for tertiary carbon atoms: whereas primary and secondary alcohols are viable precursor substrates, tertiary alcohols and their derivatives usually either fail to react or produce stereochemical mixtures of products. Here we report the stereochemical inversion of chiral tertiary alcohols with a nitrogenous nucleophile facilitated by a Lewis-acid-catalysed solvolysis. The method is chemoselective against secondary and primary alcohols, thereby complementing the selectivity of the SN2 reaction. Furthermore, this method for carbon-nitrogen bond formation mimics a putative biosynthetic step in the synthesis of marine terpenoids and enables their preparation from the corresponding terrestrial terpenes. We expect that the general attributes of the methodology will allow chiral tertiary alcohols to be considered viable substrates for stereoinversion reactions.

Desaturation reactions catalyzed by soluble methane monooxygenase.

PubMed

Jin, Y; Lipscomb, J D

2001-09-01

Soluble methane monooxygenase (MMO) is shown to be capable of catalyzing desaturation reactions in addition to the usual hydroxylation and epoxidation reactions. Dehydrogenated products are generated from MMO-catalyzed oxidation of certain substrates including ethylbenzene and cyclohexadienes. In the reaction of ethylbenzene, desaturation of ethyl C-H occurred along with the conventional hydroxvlations of ethyl and phenyl C-Hs. As a result, styrene is formed together with ethylphenols and phenylethanols. Similarly, when 1,3- and 1,4-cyclohexadienes were used as substrates, benzene was detected as a product in addition to the corresponding alcohols and epoxides. In all cases, reaction conditions were found to significantly affect the distribution among the different products. This new activity of MMO is postulated to be associated with the chemical properties of the substrates rather than fundamental changes in the nature of the oxygen and C-H activation chemistries. The formation of the desaturated products is rationalized by formation of a substrate cationic intermediate, possibly via a radical precursor. The cationic species is then proposed to partition between recombination (alcohol formation) and elimination (alkene production) pathways. This novel function of MMO indicates close mechanistic kinship between the hydroxylation and desaturation reactions catalyzed by the nonheme diiron clusters.

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.

Iridium-Catalyzed Hydrogen Transfer Reactions

NASA Astrophysics Data System (ADS)

Saidi, Ourida; Williams, Jonathan M. J.

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

Enzymatic network for production of ether amines from alcohols.

PubMed

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

2016-09-01

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

Optimization of 2-ethylhexyl palmitate production using lipozyme RM IM as catalyst in a solvent-free system.

PubMed

Richetti, Aline; Leite, Selma G F; Antunes, Octávio A C; de Souza, Andrea L F; Lerin, Lindomar A; Dallago, Rogério M; Paroul, Natalia; Di Luccio, Marco; Oliveira, J Vladimir; Treichel, Helen; de Oliveira, Débora

2010-04-01

This work reports the application of a lipase in the 2-ethylhexyl palmitate esterification in a solvent-free system with an immobilized lipase (Lipozyme RM IM). A sequential strategy was used applying two experimental designs to optimize the 2-ethylhexyl palmitate production. An empirical model was then built so as to assess the effects of process variables on the reaction conversion. Afterwards, the operating conditions that optimized 2-ethylhexyl palmitate production were established as being acid/alcohol molar ratio 1:3, temperature of 70 degrees C, stirring rate of 150 rpm, 10 wt.% of enzyme, leading to a reaction conversion as high as 95%. From this point, a kinetic study was carried out evaluating the effect of acid:alcohol molar ratio, the enzyme concentration and the temperature on product conversion. The results obtained in this step permit to verify that an excess of alcohol (acid to alcohol molar ratio of 1:6), relatively low enzyme concentration (10 wt.%) and temperature of 70 degrees C, led to conversions next to 100%.

Final report of the addendum to the safety assessment of n-butyl alcohol as used in cosmetics.

PubMed

McLain, Valerie C

2008-01-01

n-Butyl Alcohol is a primary aliphatic alcohol historically used as a solvent in nail care cosmetic products, but new concentration of use data indicate that it also is being used at low concentrations in eye makeup, personal hygiene, and shaving cosmetic products. n-Butyl Alcohol has been generally recognized as safe for use as a flavoring substance in food and appears on the 1982 Food and Drug Administration (FDA) list of inactive ingredients for approved prescription drug products. n-Butyl Alcohol can be absorbed through the skin, lungs, and gastrointestinal tract. n-Butyl Alcohol may be formed by hydrolysis of butyl acetate in the blood, but is rapidly oxidized. The single oral dose LD(50) of n-Butyl Alcohol for rats was 0.79 to 4.36 g/kg. The dermal LD(50) for rabbits was 4.2 g/kg. Inhalation toxicity studies in humans demonstrate sensory irritation of the upper respiratory tract, but only at levels above 3000 mg/m(3). Animal studies demonstrate intoxication, restlessness, ataxia, prostration, and narcosis. Exposures of rats to levels up to 4000 ppm failed to produce hearing defects. High concentrations of n-Butyl Alcohol vapors can be fatal. Ocular irritation was observed for n-Butyl alcohol at 0.005 ml of a 40% solution. The behavioral no-effect dose for n-Butyl Alcohol injected subcutaneously (s.c.) was 120 mg/kg. Fetotoxicity has been demonstrated, but only at maternally toxic levels (1000 mg/kg). No significant behavioral or neurochemical effects were seen in offspring following either maternal or paternal exposure to 3000 or 6000 ppm. n-Butyl Alcohol was not mutagenic in Ames tests, did not induce sister-chromatid exchange or chromosome breakage in chick embryos or Chinese hamster ovary cells, did not induce micronuclei formation in V79 Chinese hamster cells, did not have any chromosome-damaging effects in a mouse micronucleus test, and did not impair chromosome distribution in the course of mitosis. Clinical testing of n-Butyl Alcohol for nonimmunological contact urticaria was negative in 105 subjects. Repeat-insult patch test (RIPT) studies of nail colors and enamels containing 3% n-Butyl Alcohol in one study produced reactions on challenge, but further study linked significant positive reactions to another solvent. In other RIPT studies, only minimal reactions were reported. A photopatch test demonstrated that a nail enamel containing 3% n-Butyl Alcohol resulted in no reactions. Workers complained of ocular irritation, disagreeable odor, slight headache and vertigo, slight irritation of nose and throat, and dermatitis of the fingers and hands when the air concentration of n-Butyl Alcohol was greater than 50 ppm, as compared to an odor threshold in air of 0.83 ppm. The available safety test data were considered adequate to support the safety of n-Butyl Alcohol in all cosmetic product categories in which it is currently used.

PROCESS FOR PRODUCING ALKYL ORTHOPHOSPHORIC ACID EXTRACTANTS

DOEpatents

Grinstead, R.R.

1962-01-23

A process is given for producing superior alkyl orthophosphoric acid extractants for use in solvent extraction methods to recover and purify various metals such as uranium and vanadium. The process comprises slurrying P/sub 2/O/ sub 5/ in a solvent diluent such as kerosene, benzene, isopropyl ether, and the like. An alipbatic alcohol having from nine to seventeen carbon atoms, and w- hcrein ihc OH group is situated inward of the terminal carbon atoms, is added to the slurry while the reaction temperature is mainiained below 60 deg C. The alcohol is added in the mole ratio of about 2 to l, alcohol to P/sub 2/O/sub 5/. A pyrophosphate reaotion product is formed in the slurry-alcohol mixture. Subsequently, the pyrophosphate reaction product is hydrolyzed with dilute mineral acid to produce the desired alkyl orthophosphoric aeid extractant. The extraetant may then be separated and utilized in metal-recovery, solvent- extraction processes. (AEC)

Achmatowicz Reaction and its Application in the Syntheses of Bioactive Molecules

PubMed Central

Ghosh, Arun K.; Brindisi, Margherita

2016-01-01

Substituted pyranones and tetrahydropyrans are structural subunits of many bioactive natural products. Considerable efforts are devoted toward the chemical synthesis of these natural products due to their therapeutic potential as well as low natural abundance. These embedded pyranones and tetrahydropyran structural motifs have been the subject of synthetic interest over the years. While there are methods available for the syntheses of these subunits, there are issues related to regio and stereochemical outcomes, as well as versatility and compatibility of reaction conditions and functional group tolerance. The Achmatowicz reaction, an oxidative ring enlargement of furyl alcohol, was developed in the 1970s. The reaction provides a unique entry to a variety of pyranone derivatives from functionalized furanyl alcohols. These pyranones provide convenient access to substituted tetrahydropyran derivatives. This review outlines general approaches to the synthesis of tetrahydropyrans, covering general mechanistic aspects of the Achmatowicz reaction or rearrangement with an overview of the reagents utilized for the Achmatowicz reaction. The review then focuses on the synthesis of functionalized tetrahydropyrans and pyranones and their applications in the synthesis of natural products and medicinal agents. PMID:28944049

Palladium-Catalyzed Anti-Markovnikov Oxidation of Allylic Amides to Protected β-Amino Aldehydes.

PubMed

Dong, Jia Jia; Harvey, Emma C; Fañanás-Mastral, Martín; Browne, Wesley R; Feringa, Ben L

2014-12-10

A general method for the preparation of N-protected β-amino aldehydes from allylic amines or linear allylic alcohols is described. Here the Pd(II)-catalyzed oxidation of N-protected allylic amines with benzoquinone is achieved in tBuOH under ambient conditions with excellent selectivity toward the anti-Markovnikov aldehyde products and full retention of configuration at the allylic carbon. The method shows a wide substrate scope and is tolerant of a range of protecting groups. Furthermore, β-amino aldehydes can be obtained directly from protected allylic alcohols via palladium-catalyzed autotandem reactions, and the application of this method to the synthesis of β-peptide aldehydes is described. From a mechanistic perspective, we demonstrate that tBuOH acts as a nucleophile in the reaction and that the initially formed tert-butyl ether undergoes spontaneous loss of isobutene to yield the aldehyde product. Furthermore, tBuOH can be used stoichiometrically, thereby broadening the solvent scope of the reaction. Primary and secondary alcohols do not undergo elimination, allowing the isolation of acetals, which subsequently can be hydrolyzed to their corresponding aldehyde products.

Biodiesel production from triolein and short chain alcohols through biocatalysis.

PubMed

Salis, Andrea; Pinna, Marcella; Monduzzi, Maura; Solinas, Vincenzo

2005-09-29

Oleic acid alkyl esters (biodiesel) were synthesised by biocatalysis in solvent-free conditions. Different commercial immobilised lipases, namely Candida antarctica B, Rizhomucor miehei, and Pseudomonas cepacia, were tested towards the reaction between triolein and butanol to produce butyl oleate. Pseudomonas cepacia lipase resulted to be the most active enzyme reaching 100% of conversion after 6h. Different operative conditions such as reaction temperature, water activity, and reagent stoichiometric ratio were investigated and optimised. These conditions were then used to investigate the effect of linear and branched short chain alcohols. Methanol and 2-butanol were the worst alcohols: the former, probably, due to its low miscibility with the oil and the latter because secondary alcohols usually are less reactive than primary alcohols. Conversely, linear and branched primary alcohols with short alkyl chains (C(2)--C(4)) showed high reaction rate and conversion. A mixture of linear and branched short chain alcohols that mimics the residual of ethanol distillation (fusel oil) was successfully used for oleic acid ester synthesis. These compounds are important in biodiesel mixtures since they improve low temperature properties.

Characterization of the products formed by the reaction of trichlorocyanuric acid with 2-propanol.

PubMed

Sandercock, P Mark L; Barnett, Julie S

2009-11-01

We report a recent investigation into the death of a cat that was initially thought to involve intentionally burning the animal via the use of an ignitable liquid. The exposure of the animal to flame was ruled out. Instead, forensic investigation revealed the intentional mixing together of a common outdoor swimming pool chlorinator, trichlorocyanuric acid (TCCA), and 2-propanol (aka, isopropyl alcohol or rubbing alcohol). The reaction of these two chemicals resulted in the formation of cyanuric acid residue, hydrochloric acid, and the evolution of a significant volume of chlorine gas. Further alpha-chlorination side reactions also occurred between 2-propanol and TCCA to produce a variety of chlorinated 2-propanone species that were detected on the submitted evidence. The identification of the products of both the main reaction and the side reactions allowed the authors to determine what chemicals were originally mixed together by the culprit.

Production of fatty acid butyl esters using the low cost naturally immobilized Carica papaya lipase.

PubMed

Su, Erzheng; Wei, Dongzhi

2014-07-09

In this work, the low cost naturally immobilized Carica papaya lipase (CPL) was investigated for production of fatty acid butyl esters (FABE) to fulfill the aim of reducing the lipase cost in the enzymatic butyl-biodiesel process. The CPL showed specificities to different alcohol acyl acceptors. Alcohols with more than three carbon atoms did not have negative effects on the CPL activity. The CPL catalyzed butanolysis for FABE production was systematically investigated. The reaction solvent, alcohol/oil molar ratio, enzyme amount, reaction temperature, and water activity all affected the butanolysis process. Under the optimized conditions, the highest conversion of 96% could be attained in 24 h. These optimal conditions were further applied to CPL catalyzed butanolysis of other vegetable oils. All of them showed very high conversion. The CPL packed-bed reactor was further developed, and could be operated continuously for more than 150 h. All of these results showed that the low cost Carica papaya lipase can be used as a promising lipase for biodiesel production.

Continuous N-alkylation reactions of amino alcohols using γ-Al2O3 and supercritical CO2: unexpected formation of cyclic ureas and urethanes by reaction with CO2.

PubMed

Streng, Emilia S; Lee, Darren S; George, Michael W; Poliakoff, Martyn

2017-01-01

The use of γ-Al 2 O 3 as a heterogeneous catalyst in scCO 2 has been successfully applied to the amination of alcohols for the synthesis of N -alkylated heterocycles. The optimal reaction conditions (temperature and substrate flow rate) were determined using an automated self-optimising reactor, resulting in moderate to high yields of the target products. Carrying out the reaction in scCO 2 was shown to be beneficial, as higher yields were obtained in the presence of CO 2 than in its absence. A surprising discovery is that, in addition to cyclic amines, cyclic ureas and urethanes could be synthesised by incorporation of CO 2 from the supercritical solvent into the product.

Tunable and selective hydrogenation of furfural to furfuryl alcohol and cyclopentanone over Pt supported on biomass-derived porous heteroatom doped carbon.

PubMed

Liu, Xiuyun; Zhang, Bo; Fei, Benhua; Chen, Xiufang; Zhang, Junyi; Mu, Xindong

2017-09-21

The search for and exploitation of efficient catalytic systems for selective conversion of furfural into various high value-added chemicals remains a huge challenge for green synthesis in the chemical industry. Here, novel Pt nanoparticles supported on bamboo shoot-derived porous heteroatom doped carbon materials were designed as highly active catalysts for controlled hydrogenation of furfural in aqueous media. The porous heteroatom doped carbon supported Pt catalysts were endowed with a large surface area with a hierarchical porous structure, a high content of nitrogen and oxygen functionalities, a high dispersion of the Pt nanoparticles, good water dispersibility and reaction stability. Benefiting from these features, the novel Pt catalysts displayed a high activity and controlled tunable selectivity for furfural hydrogenation to produce furfuryl alcohol and cyclopentanone in water. The product selectivity could be easily modulated by controlling the carbonization temperature of the porous heteroatom doped carbon support and the reaction conditions (temperature and H 2 pressure). Under mild conditions (100 °C, 1 MPa H 2 ), furfuryl alcohol was obtained in water with complete conversion of the furfural and an impressive furfuryl alcohol selectivity of >99% in the presence of Pt/NC-BS-500. A higher reaction temperature, in water, favored rearrangement of the furfural (FFA) with Pt/NC-BS-800 as the catalyst, which resulted in a high cyclopentanone yield of >76% at 150 °C and 3 MPa H 2 . The surface properties and pore structure of the heteroatom doped carbon support, adjusted using the carbonization temperature, might determine the interactions between the Pt nanoparticles, carbon support and catalytic reactants in water, which in turn could have led to a good selectivity control. The effect of different reaction temperatures and reaction times on the product selectivity was also explored. Combined with exploration of the distribution of the reaction products, a reaction mechanism for furfural reduction has been proposed.

Cu-catalyzed cross-coupling reactions of epoxides with organoboron compounds.

PubMed

Lu, Xiao-Yu; Yang, Chu-Ting; Liu, Jing-Hui; Zhang, Zheng-Qi; Lu, Xi; Lou, Xin; Xiao, Bin; Fu, Yao

2015-02-11

A copper-catalyzed cross-coupling reaction of epoxides with arylboronates is described. This reaction is not limited to aromatic epoxides, because aliphatic epoxides are also suitable substrates. In addition, N-sulfonyl aziridines can be successfully converted into the products. This reaction provides convenient access to β-phenethyl alcohols, which are valuable synthetic intermediates.

Hydrogenolysis of 5-carbon sugars, sugar alcohols, and methods of making propylene glycol

DOEpatents

Werpy, Todd A [West Richland, WA; Zacher, Alan H [Kennewick, WA; Miller, Dennis J [Okemos, MI

2006-05-02

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.

Rhenium(VII) Catalysis of Prins Cyclization Reactions

PubMed Central

Tadpetch, Kwanruthai; Rychnovsky, Scott D.

2009-01-01

The rhenium(VII) complex O3ReOSiPh3 are particularly effective catalyst for Prins cyclizations using aromatic and α,β-unsaturated aldehydes. The reaction conditions are mild and the highly substituted 4-hydroxy tetrahydropyran products are formed stereoselectively. Rhenium(VII) complexes appear to spontaneously form esters with alcohols and to directly activate electron rich alcohols for solvolysis. Re2O7 and perrhenic acid were equally effective in catalyzing these cyclizations. PMID:18816133

Organic functional group transformations in water at elevated temperature and pressure: Reversibility, reactivity, and mechanisms

NASA Astrophysics Data System (ADS)

Shipp, Jessie; Gould, Ian R.; Herckes, Pierre; Shock, Everett L.; Williams, Lynda B.; Hartnett, Hilairy E.

2013-03-01

Many transformation reactions involving hydrocarbons occur in the presence of H2O in hydrothermal systems and deep sedimentary systems. We investigate these reactions using laboratory-based organic chemistry experiments at high temperature and pressure (300 °C and 100 MPa). Organic functional group transformation reactions using model organic compounds based on cyclohexane with one or two methyl groups provided regio- and stereochemical markers that yield information about reversibility and reaction mechanisms. We found rapidly reversible interconversion between alkanes, alkenes, dienes, alcohols, ketones, and enones. The alkane-to-ketone reactions were not only completely reversible, but also exhibited such extensive reversibility that any of the functional groups along the reaction path (alcohol, ketone, and even the diene) could be used as the reactant and form all the other groups as products. There was also a propensity for these ring-based structures to dehydrogenate; presumably from the alkene, through a diene, to an aromatic ring. The product suites provide strong evidence that water behaved as a reactant and the various functional groups showed differing degrees of reactivity. Mechanistically-revealing products indicated reaction mechanisms that involve carbon-centered cation intermediates. This work therefore demonstrates that a wide range of organic compound types can be generated by abiotic reactions at hydrothermal conditions.

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

Benipal, Neeva; Qi, Ji; Dalian Univ. of Technology, Dalian

Electro-oxidation of alcohol is the key reaction occurring at the anode of a direct alcohol fuel cell (DAFC), in which both reaction kinetics (rate) and selectivity (to deep oxidation products) need improvement to obtain higher power density and fuel utilization for a more efficient DAFC. We recently found that a PdAg bimetallic nanoparticle catalyst is more efficient than Pd for alcohol oxidation: Pd can facilitate deprotonation of alcohol in a base electrolyte, while Ag can promote intermediate aldehyde oxidation and cleavage of C-single bondC bond of C 3 species to C 2 species. Furthermore, a combination of the two activemore » sites (Pd and Ag) with two different functions, can simultaneously improve the reaction rates and deeper oxidation products of alcohols. In this continuing work, Pd, Ag mono, and bimetallic nanoparticles supported on carbon nanotubes (Ag/CNT, Pd/CNT, Pd 1Ag 1/CNT, and Pd 1Ag 3/CNT) were prepared using an aqueous-phase reduction method; they served as working catalysts for studying electrocatalytic oxidation of glycerol in an anion-exchange membrane-based direct glycerol fuel cell. Combined XRD, TEM, and HAADF-STEM analyses performed to fully characterize as-prepared catalysts suggested that they have small particle sizes: 2.0 nm for Pd/CNT, 2.3 nm for PdAg/CNT, 2.4 nm for PdAg 3/CNT, and 13.9 nm for Ag/CNT. XPS further shows that alloying with Ag results in more metal state Pd presented on the surface, and this may be related to their higher direct glycerol fuel cell (DGFC) performances. Single DGFC performance and product analysis results show that PdAg bimetallic nanoparticles can not only improve the glycerol reaction rate so that higher power output can be achieved, but also facilitate deep oxidation of glycerol so that a higher faradaic efficiency and fuel utilization can be achieved along with optimal reaction conditions (increased base-to-fuel ratio). Half-cell electrocatalytic activity measurement and single fuel cell product analysis of different glycerol oxidation intermediates, including C 3: glycerate, tartronate, mesoxalate, and lactate; C 2: glycolate and oxalate, over PdAg/CNT catalyst was further conducted and produced deeper insight into the synergistic effects and reaction pathways of bimetallic PdAg catalysts in glycerol electrocatalytic oxidation.« less

Carbon nanotube supported PdAg nanoparticles for electrocatalytic oxidation of glycerol in anion exchange membrane fuel cells

DOE PAGES

Benipal, Neeva; Qi, Ji; Dalian Univ. of Technology, Dalian; ...

2017-03-10

Electro-oxidation of alcohol is the key reaction occurring at the anode of a direct alcohol fuel cell (DAFC), in which both reaction kinetics (rate) and selectivity (to deep oxidation products) need improvement to obtain higher power density and fuel utilization for a more efficient DAFC. We recently found that a PdAg bimetallic nanoparticle catalyst is more efficient than Pd for alcohol oxidation: Pd can facilitate deprotonation of alcohol in a base electrolyte, while Ag can promote intermediate aldehyde oxidation and cleavage of C-single bondC bond of C 3 species to C 2 species. Furthermore, a combination of the two activemore » sites (Pd and Ag) with two different functions, can simultaneously improve the reaction rates and deeper oxidation products of alcohols. In this continuing work, Pd, Ag mono, and bimetallic nanoparticles supported on carbon nanotubes (Ag/CNT, Pd/CNT, Pd 1Ag 1/CNT, and Pd 1Ag 3/CNT) were prepared using an aqueous-phase reduction method; they served as working catalysts for studying electrocatalytic oxidation of glycerol in an anion-exchange membrane-based direct glycerol fuel cell. Combined XRD, TEM, and HAADF-STEM analyses performed to fully characterize as-prepared catalysts suggested that they have small particle sizes: 2.0 nm for Pd/CNT, 2.3 nm for PdAg/CNT, 2.4 nm for PdAg 3/CNT, and 13.9 nm for Ag/CNT. XPS further shows that alloying with Ag results in more metal state Pd presented on the surface, and this may be related to their higher direct glycerol fuel cell (DGFC) performances. Single DGFC performance and product analysis results show that PdAg bimetallic nanoparticles can not only improve the glycerol reaction rate so that higher power output can be achieved, but also facilitate deep oxidation of glycerol so that a higher faradaic efficiency and fuel utilization can be achieved along with optimal reaction conditions (increased base-to-fuel ratio). Half-cell electrocatalytic activity measurement and single fuel cell product analysis of different glycerol oxidation intermediates, including C 3: glycerate, tartronate, mesoxalate, and lactate; C 2: glycolate and oxalate, over PdAg/CNT catalyst was further conducted and produced deeper insight into the synergistic effects and reaction pathways of bimetallic PdAg catalysts in glycerol electrocatalytic oxidation.« less

Self-sustained enzymatic cascade for the production of 2,5-furandicarboxylic acid from 5-methoxymethylfurfural.

PubMed

Carro, Juan; Fernández-Fueyo, Elena; Fernández-Alonso, Carmen; Cañada, Javier; Ullrich, René; Hofrichter, Martin; Alcalde, Miguel; Ferreira, Patricia; Martínez, Angel T

2018-01-01

2,5-Furandicarboxylic acid is a renewable building block for the production of polyfurandicarboxylates, which are biodegradable polyesters expected to substitute their classical counterparts derived from fossil resources. It may be produced from bio-based 5-hydroxymethylfurfural or 5-methoxymethylfurfural, both obtained by the acidic dehydration of biomass-derived fructose. 5-Methoxymethylfurfural, which is produced in the presence of methanol, generates less by-products and exhibits better storage stability than 5-hydroxymethylfurfural being, therefore, the industrial substrate of choice. In this work, an enzymatic cascade involving three fungal oxidoreductases has been developed for the production of 2,5-furandicarboxylic acid from 5-methoxymethylfurfural. Aryl-alcohol oxidase and unspecific peroxygenase act on 5-methoxymethylfurfural and its partially oxidized derivatives yielding 2,5-furandicarboxylic acid, as well as methanol as a by-product. Methanol oxidase takes advantage of the methanol released for in situ producing H 2 O 2 that, along with that produced by aryl-alcohol oxidase, fuels the peroxygenase reactions. In this way, the enzymatic cascade proceeds independently, with the only input of atmospheric O 2 , to attain a 70% conversion of initial 5-methoxymethylfurfural. The addition of some exogenous methanol to the reaction further improves the yield to attain an almost complete conversion of 5-methoxymethylfurfural into 2,5-furandicarboxylic acid. The synergistic action of aryl-alcohol oxidase and unspecific peroxygenase in the presence of 5-methoxymethylfurfural and O 2 is sufficient for the production of 2,5-furandicarboxylic acid. The addition of methanol oxidase to the enzymatic cascade increases the 2,5-furandicarboxylic acid yields by oxidizing a reaction by-product to fuel the peroxygenase reactions.

Engineering redox homeostasis to develop efficient alcohol-producing microbial cell factories.

PubMed

Zhao, Chunhua; Zhao, Qiuwei; Li, Yin; Zhang, Yanping

2017-06-24

The biosynthetic pathways of most alcohols are linked to intracellular redox homeostasis, which is crucial for life. This crucial balance is primarily controlled by the generation of reducing equivalents, as well as the (reduction)-oxidation metabolic cycle and the thiol redox homeostasis system. As a main oxidation pathway of reducing equivalents, the biosynthesis of most alcohols includes redox reactions, which are dependent on cofactors such as NADH or NADPH. Thus, when engineering alcohol-producing strains, the availability of cofactors and redox homeostasis must be considered. In this review, recent advances on the engineering of cellular redox homeostasis systems to accelerate alcohol biosynthesis are summarized. Recent approaches include improving cofactor availability, manipulating the affinity of redox enzymes to specific cofactors, as well as globally controlling redox reactions, indicating the power of these approaches, and opening a path towards improving the production of a number of different industrially-relevant alcohols in the near future.

Synthesis of terpene and steroid dimers and trimers having cyclobutadienyl-Co and aromatic tethers.

PubMed

Sierra, Miguel A; Torres, M Rosario; Torre, María C de la; Alvaro, Elsa

2007-05-25

The reaction of natural product derived propargylic alcohols with CpCo(CO)2 produces three new types of natural product hybrids having two or three terpene or steroid fragments. The tether joining the natural product subunits is built during the reaction. Type 1 hybrids have two terpene or steroid moieties joined by a CpCo-cyclobutadiene tether, with the two units disposed in a 1,2-arrangement (9, 14, 22). Type 2 hybrids have a Co-cyclopentadienone tether (10). Type 3 has three units of terpene or steroid joined to a benzene ring (11, 12, 15). An unusual Co-mediated beta-carbon elimination pathway of propargylic alcohols leading to ketones (an unknown process in this chemistry) has been observed.

Glycerol triacetate as solvent and acyl donor in the production of isoamyl acetate with Candida antarctica lipase B.

PubMed

Wolfson, Adi; Atyya, Aviad; Dlugy, Christina; Tavor, Dorith

2010-03-01

Glycerol triacetate was successfully used as a green solvent and as the acyl donor in the transesterification of isoamyl alcohol to produce isoamyl acetate using free and immobilized Candida antarctica lipase B. Immobilized lipase was more catalytically active than free lipase and could be easily separated from the reaction mixture by filtration. In addition, it was found that increasing either the reaction temperature or the enzyme to substrate ratio increased the conversion of isoamyl alcohol. Using triacetin as the solvent also enabled the separation of product by simple extraction with petroleum ether and catalyst recycling.

Method to upgrade bio-oils to fuel and bio-crude

DOEpatents

Steele, Philip H; Pittman, Jr., Charles U; Ingram, Jr., Leonard L; Gajjela, Sanjeev; Zhang, Zhijun; Bhattacharya, Priyanka

2013-12-10

This invention relates to a method and device to produce esterified, olefinated/esterified, or thermochemolytic reacted bio-oils as fuels. The olefinated/esterified product may be utilized as a biocrude for input to a refinery, either alone or in combination with petroleum crude oils. The bio-oil esterification reaction is catalyzed by addition of alcohol and acid catalyst. The olefination/esterification reaction is catalyzed by addition of resin acid or other heterogeneous catalyst to catalyze olefins added to previously etherified bio-oil; the olefins and alcohol may also be simultaneously combined and catalyzed by addition of resin acid or other heterogeneous catalyst to produce the olefinated/esterified product.

Site-selective oxidation, amination and epimerization reactions of complex polyols enabled by transfer hydrogenation

NASA Astrophysics Data System (ADS)

Hill, Christopher K.; Hartwig, John F.

2017-12-01

Polyoxygenated hydrocarbons that bear one or more hydroxyl groups comprise a large set of natural and synthetic compounds, often with potent biological activity. In synthetic chemistry, alcohols are important precursors to carbonyl groups, which then can be converted into a wide range of oxygen- or nitrogen-based functionality. Therefore, the selective conversion of a single hydroxyl group in natural products into a ketone would enable the selective introduction of unnatural functionality. However, the methods known to convert a simple alcohol, or even an alcohol in a molecule that contains multiple protected functional groups, are not suitable for selective reactions of complex polyol structures. We present a new ruthenium catalyst with a unique efficacy for the selective oxidation of a single hydroxyl group among many in unprotected polyol natural products. This oxidation enables the introduction of nitrogen-based functional groups into such structures that lack nitrogen atoms and enables a selective alcohol epimerization by stepwise or reversible oxidation and reduction.

[Determination of the alcohol level of alcoholic beverages with the Technicon thermometric autoanalyser].

PubMed

Dupont, P

1978-01-01

Thermometric analyses consists in measuring the enthalpy variations of chemical reaction. The dilution of an hydroalcoholic solution in a aqueous solution of sodium perchlorate is an endothermal reaction, and the variations of temperature within certains limits are functions of the initial alcohol concentration. The variations are collected, amplified and recorded on a diagram. This has been done in the quality control laboratory of our company with a Technicon apparatus to determine the alcoholic strength of spirits at 45 degrees. In industrial use one needs only to compare the height of the peaks corresponding to the product being analysed with the check sample peaks. This quick and precise process, of a great simplicity of utilisation makes it possible to discard the distillation method.

Integrative genomic mining for enzyme function to enable engineering of a non-natural biosynthetic pathway.

PubMed

Mak, Wai Shun; Tran, Stephen; Marcheschi, Ryan; Bertolani, Steve; Thompson, James; Baker, David; Liao, James C; Siegel, Justin B

2015-11-24

The ability to biosynthetically produce chemicals beyond what is commonly found in Nature requires the discovery of novel enzyme function. Here we utilize two approaches to discover enzymes that enable specific production of longer-chain (C5-C8) alcohols from sugar. The first approach combines bioinformatics and molecular modelling to mine sequence databases, resulting in a diverse panel of enzymes capable of catalysing the targeted reaction. The median catalytic efficiency of the computationally selected enzymes is 75-fold greater than a panel of naively selected homologues. This integrative genomic mining approach establishes a unique avenue for enzyme function discovery in the rapidly expanding sequence databases. The second approach uses computational enzyme design to reprogramme specificity. Both approaches result in enzymes with >100-fold increase in specificity for the targeted reaction. When enzymes from either approach are integrated in vivo, longer-chain alcohol production increases over 10-fold and represents >95% of the total alcohol products.

A high-performance liquid chromatography-based radiometric assay for acyl-CoA:alcohol transacylase from jojoba.

PubMed

Garver, W S; Kemp, J D; Kuehn, G D

1992-12-01

Acyl-CoA:alcohol transacylase catalyzes the final step in the biosynthesis of storage liquid wax esters from acyl-CoA fatty acids and fatty alcohols in a limited number of microbes, algae, and Simmondsia chinensis Link (jojoba). An improved and automated method of enzyme assay for this catalyst from cotyledons of jojoba is described. The assay method uses reversed-phase C18 high performance liquid chromatography (HPLC) to separate the labeled C30:1 liquid wax product, [14C]-dodecanyl-octadecenoate, from the unreacted substrate, [14C]octadecenoyl-CoA (oleyl-CoA), and other components produced from enzymes present in the crude homogenate of jojoba cotyledons, including [14C]-octadecenoic acid (oleic acid) and [14C]octadecenol (oleyol). Methods are also described for microscale chemical synthesis in one vessel of 14C-radiolabeled substrates and products for the transacylase. These labeled reagents are required to confirm the HPLC separations of reaction products. The radioactive components are quantitated using an on-line flow-through scintillation detector enabling sensitive and precise analysis of the reaction products.

Hydrogen-driven asymmetric reduction of hydroxyacetone to (R)-1,2-propanediol by Ralstonia eutropha transformant expressing alcohol dehydrogenase from Kluyveromyces lactis.

PubMed

Oda, Takahiro; Oda, Koji; Yamamoto, Hiroaki; Matsuyama, Akinobu; Ishii, Masaharu; Igarashi, Yasuo; Nishihara, Hirofumi

2013-01-10

Conversion of industrial processes to more nature-friendly modes is a crucial subject for achieving sustainable development. Utilization of hydrogen-oxidation reactions by hydrogenase as a driving force of bioprocess reaction can be an environmentally ideal method because the reaction creates no pollutants. We expressed NAD-dependent alcohol dehydrogenase from Kluyveromyces lactis in a hydrogen-oxidizing bacterium: Ralstonia eutropha. This is the first report of hydrogen-driven in vivo coupling reaction of the alcohol dehydrogenase and indigenous soluble NAD-reducing hydrogenase. Asymmetric reduction of hydroxyacetone to (R)-1,2-propanediol, which is a commercial building block for antibacterial agents, was performed using the transformant as the microbial cell catalyst. The two enzymes coupled in vitro in vials without a marked decrease of reactivity during the 20 hr reaction because of the hydrogenase reaction, which generates no by-product that affects enzymes. Alcohol dehydrogenase was expressed functionally in R. eutropha in an activity level equivalent to that of indigenous NAD-reducing hydrogenase under the hydrogenase promoter. The hydrogen-driven in vivo coupling reaction proceeded only by the transformant cell without exogenous addition of a cofactor. The decrease of reaction velocity at higher concentration of hydroxyacetone was markedly reduced by application of an in vivo coupling system. Production of (R)-1,2-propanediol (99.8% e.e.) reached 67.7 g/l in 76 hr with almost a constant rate using a jar fermenter. The reaction velocity under 10% PH2 was almost equivalent to that under 100% hydrogen, indicating the availability of crude hydrogen gas from various sources. The in vivo coupling system enabled cell-recycling as catalysts. Asymmetric reduction of hydroxyacetone by a coupling reaction of the two enzymes continued in both in vitro and in vivo systems in the presence of hydrogen. The in vivo reaction system using R. eutropha transformant expressing heterologous alcohol dehydrogenase showed advantages for practical usage relative to the in vitro coupling system. The results suggest a hopeful perspective of the hydrogen-driven bioprocess as an environmentally outstanding method to achieve industrial green innovation. Hydrogen-oxidizing bacteria can be useful hosts for the development of hydrogen-driven microbial cell factories.

Original Synthesis of Fluorenyl Alcohol Derivatives by Reductive Dehalogenation Initiated by TDAE.

PubMed

Giuglio-Tonolo, Alain Gamal; Terme, Thierry; Vanelle, Patrice

2016-10-24

We report here a novel and easy-to-handle reductive dehalogenation of 9-bromofluorene in the presence of arylaldehydes and dicarbonyl derivatives to give the corresponding fluorenyl alcohol derivatives and Darzens epoxides as by-products in tetrakis(dimethylamino)ethylene (TDAE) reaction conditions. The reaction is believed to proceed via two successive single electron transfers to generate the fluorenyl anion which was able to react with different electrophiles. A mechanistic study was conducted to understand the formation of the epoxide derivatives.

Mild rhodium(iii)-catalyzed intramolecular annulation of benzamides with allylic alcohols to access azepinone derivatives.

PubMed

Peneau, Augustin; Tricart, Quentin; Guillou, Catherine; Chabaud, Laurent

2018-05-23

Azepinone derivatives are important frameworks of several natural products and bioactive compounds. They are synthetized using a Rh(iii)-catalyzed intramolecular annulation of benzamide-tethered allylic alcohols. The reaction requires mild conditions at room temperature and affords diversely substituted azepinones bearing a quaternary carbon.

Allylation of Nitrosobenzene with Pinacol Allylboronates. A Regioselective Complement to Peroxide Oxidation

PubMed Central

Kyne, Robert E.; Ryan, Michael C.; Kliman, Laura T.; Morken, James P.

2010-01-01

Addition of nitrosobenzene to pinacol allylboronates leads to oxidation of the organoboron with concomitant rearrangement of the substrate alkene. This reaction appears to proceed by allylboration of the nitroso group in analogy to carbonyl and imine allylation reactions. Remarkably, the N-O bond is cleaved during the reaction such that simple alcohols are the final reaction product. PMID:20687578

[Alcohol intake--a two-edged sword. Part 1: metabolism and pathogenic effects of alcohol].

PubMed

Ströhle, Alexander; Wolters, Maike; Hahn, Andreas

2012-08-01

From the biomedical point of view alcohol is a Janus-faced dietary component with a dose-dependent effect varying from cardiovascular protection to cytotoxicity. Alcohol is absorbed in the upper gastrointestinal tract by passive diffusion, is quickly distributed throughout body water and is mostly eliminated through oxidation. The enzymatically-catalyzed oxidative degradation to acetaldehyde and further to acetate is primarily localized in the liver. In case of a low blood alcohol concentration (<0.5 per thousand) alcohol is predominantely metabolized by the enzyme aldehyde dehydrogenase; higher blood concentrations (>0.5 per thousand) are increasingly oxidized by the microsomal ethanoloxidizing system (MEOS). Alcohol consumption induces several metabolic reactions as well as acute effects on the central nervous system. Chronic alcohol consumption to some extent irreparably damages nearly every organ with the liver being particularly concerned. There are three stages of alcohol-induced liver disease (fatty liver, alcohol hepatitis, liver cirrhosis) and the liver damages mainly result from reaction products of alcohol degradation (acetaldehyde, NADH and reactive oxygen species). An especially dreaded clinical complication of the alcohol-induced liver disease is the hepatic encephalopathy. Its pathogenesis is a multifactorial and self-perpetuating process with the swelling of astrocytes being a crucial point. Swollen astrocytes induce several reactions such as oxidative/nitrosative stress, impaired signal transduction, protein modifications and a modified gene expression profile. The swelling of astrocytes and the change in neuronal activity are attributed to several neurotoxins, especially ammonia and aromatic amino acids. In alcohol addicted subjects multiple micronutrient deficiencies are common. The status of folic acid, thiamine, pyridoxine and zinc is especially critical.

Highly Chemoselective Reduction of Amides (Primary, Secondary, Tertiary) to Alcohols using SmI2/Amine/H2O under Mild Conditions

PubMed Central

2014-01-01

Highly chemoselective direct reduction of primary, secondary, and tertiary amides to alcohols using SmI2/amine/H2O is reported. The reaction proceeds with C–N bond cleavage in the carbinolamine intermediate, shows excellent functional group tolerance, and delivers the alcohol products in very high yields. The expected C–O cleavage products are not formed under the reaction conditions. The observed reactivity is opposite to the electrophilicity of polar carbonyl groups resulting from the nX → π*C=O (X = O, N) conjugation. Mechanistic studies suggest that coordination of Sm to the carbonyl and then to Lewis basic nitrogen in the tetrahedral intermediate facilitate electron transfer and control the selectivity of the C–N/C–O cleavage. Notably, the method provides direct access to acyl-type radicals from unactivated amides under mild electron transfer conditions. PMID:24460078

SN1 reactions in supercritical carbon dioxide in the presence of alcohols: the role of preferential solvation.

PubMed

Delgado-Abad, Thais; Martínez-Ferrer, Jaime; Acerete, Rafael; Asensio, Gregorio; Mello, Rossella; González-Núñez, María Elena

2016-07-06

Ethanol () inhibits SN1 reactions of alkyl halides in supercritical carbon dioxide (scCO2) and gives no ethers as products. The unexpected behaviour of alcohols in the reaction of alkyl halides with 1,3-dimethoxybenzene () in scCO2 under different conditions is rationalised in terms of Brønsted and Lewis acid-base equilibria of reagents, intermediates, additives and products in a singular solvent characterised by: (i) the strong quadrupole and Lewis acid character of carbon dioxide, which hinders SN2 paths by strongly solvating basic solutes; (ii) the weak Lewis base character of carbon dioxide, which prevents it from behaving as a proton sink; (iii) the compressible nature of scCO2, which enhances the impact of preferential solvation on carbon dioxide availability for the solvent-demanding rate determining step.

Synthesis of cinnamyl alcohol from cinnamaldehyde with Bacillus stearothermophilus alcohol dehydrogenase as the isolated enzyme and in recombinant E. coli cells.

PubMed

Pennacchio, Angela; Rossi, Mosè; Raia, Carlo A

2013-07-01

The synthesis of the aroma chemical cinnamyl alcohol (CMO) by means of enzymatic reduction of cinnamaldehyde (CMA) was investigated using NADH-dependent alcohol dehydrogenase from Bacillus stearothermophilus both as an isolated enzyme, and in recombinant Escherichia coli whole cells. The influence of parameters such as reaction time and cofactor, substrate, co-substrate 2-propanol and biocatalyst concentrations on the bioreduction reaction was investigated and an efficient and sustainable one-phase system developed. The reduction of CMA (0.5 g/L, 3.8 mmol/L) by the isolated enzyme occurred in 3 h at 50 °C with 97% conversion, and yielded high purity CMO (≥98%) with a yield of 88% and a productivity of 50 g/genzyme. The reduction of 12.5 g/L (94 mmol/L) CMA by whole cells in 6 h, at 37 °C and no requirement of external cofactor occurred with 97% conversion, 82% yield of 98% pure alcohol and a productivity of 34 mg/gwet cell weight. The results demonstrate the microbial system as a practical and efficient method for larger-scale synthesis of CMO.

Substrate-Controlled Product Divergence: Conversion of CO2 into Heterocyclic Products.

PubMed

Rintjema, Jeroen; Epping, Roel; Fiorani, Giulia; Martín, Eddy; Escudero-Adán, Eduardo C; Kleij, Arjan W

2016-03-14

Substituted epoxy alcohols and amines allow substrate-controlled conversion of CO2 into a wide range of heterocyclic structures through different mechanistic manifolds. This new approach results in an unusual scope of CO2-derived products by initial activation of CO2 through either the amine or alcohol unit, thus providing nucleophiles for intramolecular epoxy ring opening under mild reaction conditions. Control experiments support the crucial role of the amine/alcohol fragment in this process with the nucleophile-assisted ring-opening step following an SN i pathway, and a 5-exo-tet cyclization, thus leading to heterocyclic scaffolds. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Copper-Catalyzed Oxidative Reaction of β-Keto Sulfones with Alcohols via C-S Bond Cleavage: Reaction Development and Mechanism Study.

PubMed

Du, Bingnan; Wang, Wenmin; Wang, Yang; Qi, Zhenghang; Tian, Jiaqi; Zhou, Jie; Wang, Xiaochen; Han, Jianlin; Ma, Jing; Pan, Yi

2018-02-16

A Cu-catalyzed cascade oxidative radical process of β-keto sulfones with alcohols has been achieved by using oxygen as an oxidant. In this reaction, β-keto sulfones were converted into sulfinate esters under the oxidative conditions via cleavage of C-S bond. Experimental and computational studies demonstrate that a new pathway is involved in this reaction, which proceeds through the formation of the key four-coordinated Cu II intermediate, O-O bond homolysis induced C-S bond cleavage and Cu-catalyzed esterification to form the final products. This reaction provides a new strategy to sulfonate esters and enriches the research content of C-S bond cleavage and transformations. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chlorine atom-initiated low-temperature oxidation of prenol and isoprenol: The effect of C=C double bonds on the peroxy radical chemistry in alcohol oxidation

DOE PAGES

Welz, Oliver; Savee, John D.; Osborn, David L.; ...

2014-07-04

The chlorine atom-initiated oxidation of two unsaturated primary C5 alcohols, prenol (3-methyl-2-buten-1-ol, (CH 3) 2CCHCH 2OH) and isoprenol (3-methyl-3-buten-1-ol, CH 2C(CH 3)CH 2CH 2OH), is studied at 550 K and low pressure (8 Torr). The time- and isomer-resolved formation of products is probed with multiplexed photoionization mass spectrometry (MPIMS) using tunable vacuum ultraviolet ionizing synchrotron radiation. The peroxy radical chemistry of the unsaturated alcohols appears much less rich than that of saturated C4 and C5 alcohols. The main products observed are the corresponding unsaturated aldehydes – prenal (3-methyl-2-butenal) from prenol oxidation and isoprenal (3-methyl-3-butenal) from isoprenol oxidation. No significant productsmore » arising from QOOH chemistry are observed. These results can be qualitatively explained by the formation of resonance stabilized allylic radicals via H-abstraction in the Cl + prenol and Cl + isoprenol initiation reactions. The loss of resonance stabilization upon O 2 addition causes the energies of the intermediate wells, saddle points, and products to increase relative to the energy of the initial radicals and O 2. These energetic shifts make most product channels observed in the peroxy radical chemistry of saturated alcohols inaccessible for these unsaturated alcohols. The experimental findings are underpinned by quantum-chemical calculations for stationary points on the potential energy surfaces for the reactions of the initial radicals with O 2. Under our conditions, the dominant channels in prenol and isoprenol oxidation are the chain-terminating HO 2-forming channels arising from radicals, in which the unpaired electron and the –OH group are on the same carbon atom, with stable prenal and isoprenal co-products, respectively. These results suggest that the presence of C=C double bonds in alcohols will reduce low-temperature reactivity during autoignition.« less

FudC, a protein primarily responsible for furfural detoxification in Corynebacterium glutamicum.

PubMed

Tsuge, Yota; Kudou, Motonori; Kawaguchi, Hideo; Ishii, Jun; Hasunuma, Tomohisa; Kondo, Akihiko

2016-03-01

Lignocellulosic hydrolysates contain compounds that inhibit microbial growth and fermentation, thereby decreasing the productivity of biofuel and biochemical production. In particular, the heterocyclic aldehyde furfural is one of the most toxic compounds found in these hydrolysates. We previously demonstrated that Corynebacterium glutamicum converts furfural into the less toxic compounds furfuryl alcohol and 2-furoic acid. To date, however, the genes involved in these oxidation and reduction reactions have not been identified in the C. glutamicum genome. Here, we show that Cgl0331 (designated FudC) is mainly responsible for the reduction of furfural into furfuryl alcohol in C. glutamicum. Deletion of the gene encoding FudC markedly diminished the in vivo reduction of furfural to furfuryl alcohol. Purified His-tagged FudC protein from Escherichia coli was also shown to convert furfural into furfuryl alcohol in an in vitro reaction utilizing NADPH, but not NADH, as a cofactor. Kinetic measurements demonstrated that FudC has a high affinity for furfural but has a narrow substrate range for other aldehydes compared to the protein responsible for furfural reduction in E. coli.

Enantiomerically Pure Acetals in Organic Synthesis: Resolutions and Diastereoselective Alkylations of Alpha-Hydroxy Esters

DTIC Science & Technology

1990-01-01

sensitivity of the alkylating agent to the reaction conditions. In either case , a decision was made to use 5-iodo-2- methyl -l-pentene as the alkylating ...agent, and the reaction conditions. In most cases the diastereomeric products of the alkylation were also separated by column chromatography. This...equatorially substituted product. Oxidation of the alcohol to the ketone followed by treatment with an alkyl Grignard reagent gave only the product which

Verification of RDX Photolysis Mechanism

DTIC Science & Technology

1999-11-01

which re-addition of HN02 was proposed to yield a hydroxydiazo intermediate that then decomposed to an alcohol . This sequence is shown for...various organic products such as alcohols , or undergo carbon- nitrogen (C-N) bond cleavage (Noller 1965). This reaction is sufficiently quanti...carbon-centered functional group such as the alcohol shown below, or C-N bond cleavage. 42 CERL TR 99/93 N02 N02 No2 ^Nv. N ’ ( ^| H2

Report on Investigation of Alcohol Combustion Associated Wear in Spark Ignition Engines, Mechanisms and Lubricant Effects.

DTIC Science & Technology

1984-12-01

investigated four - alcohol -containing fuels: pure methanol , pure ethanol, methanol in unleaded gaso- line, and ethanol in unleaded gasoline (gasohol...testing indicated that pure alcohol fuels reduced the buildup of engine .. deposits. Also neat methanol greatly increased engine wear rates at engine...results from reactions between methanol combustion products and the cast-iron cylinder liner, where the presence of liquid methanol in the combustion

The mechanism and thermodynamics of transesterification of acetate-ester enolates in the gas phase

NASA Astrophysics Data System (ADS)

Haas, George W.; Giblin, Daryl E.; Gross, Michael L.

1998-01-01

In solution, base-catalyzed hydrolysis and transesterification of esters are initiated by hydroxide- or alkoxide-ion attack at the carbonyl carbon. At low pressures in the gas phase, however, transesterification proceeds by an attack of the enolate anion of an acetate ester on an alcohol. Fourier transform mass spectrometry (FTMS) indicates that the reaction is the second-order process: -CH2-CO2-R + R'-OH --> - CH2-CO2-R' + R-OH and there is little to no detectable production of either alkoxide anion. Labeling studies show that the product and reactant enolate anion esters undergo exchange of hydrogens located [alpha] to the carbonyl carbon with the deuterium of R'-OD. The extent of the H/D exchange increases with reaction time, pointing to a short-lived intermediate. The alcoholysis reaction rate constants increase with increasing acidity of the primary, straight-chained alkyl alcohols, whereas steric effects associated with branched alcohols cause the rate constants to decrease. Equilibrium constants, which were determined directly from measurements at equilibrium and which were calculated from the forward and reverse rate constants, are near unity and show internal consistency. In the absence of steric effects, the larger enolate is always the favored product at equilibrium. The intermediate for the transesterification reaction, which can be generated at a few tenths of a torr in a tandem mass spectrometer, is tetrahedral, but other adducts that are collisionally stabilized under these conditions are principally loosely bound complexes.

Two types of alcohol dehydrogenase from Perilla can form citral and perillaldehyde.

PubMed

Sato-Masumoto, Naoko; Ito, Michiho

2014-08-01

Studies on the biosynthesis of oil compounds in Perilla will help in understanding regulatory systems of secondary metabolites and in elucidating reaction mechanisms for natural product synthesis. In this study, two types of alcohol dehydrogenases, an aldo-keto reductase (AKR) and a geraniol dehydrogenase (GeDH), which are thought to participate in the biosynthesis of perilla essential oil components, such as citral and perillaldehyde, were isolated from three pure lines of perilla. These enzymes shared high amino acid sequence identity within the genus Perilla, and were expressed regardless of oil type. The overall reaction from geranyl diphosphate to citral was performed in vitro using geraniol synthase and GeDH to form a large proportion of citral and relatively little geraniol as reaction products. The biosynthetic pathway from geranyl diphosphate to citral, the main compound of citral-type perilla essential oil, was established in this study. Copyright © 2014 Elsevier Ltd. All rights reserved.

Method of performing sugar dehydration and catalyst treatment

DOEpatents

Hu, Jianli [Kennewick, WA; Holladay, Johnathan E [Kennewick, WA; Zhang, Xinjie [Burlington, MA; Wang, Yong [Richland, WA

2010-06-01

The invention includes a method of treating a solid acid catalyst. After exposing the catalyst to a mixture containing a sugar alcohol, the catalyst is washed with an organic solvent and is then exposed to a second reaction mixture. The invention includes a process for production of anhydrosugar alcohol. A solid acid catalyst is provided to convert sugar alcohol in a first sample to an anhydrosugar alcohol. The catalyst is then washed with an organic solvent and is subsequently utilized to expose a second sample. The invention includes a method for selective production of an anhydrosugar. A solid acid catalyst is provided within a reactor and anhydrosugar alcohol is formed by flowing a starting sugar alcohol into the reactor. The acid catalyst is then exposed to an organic solvent which allows a greater amount of additional anhydrosugar to be produced than would occur without exposing the acid catalyst to the organic solvent.

Nafion®-catalyzed microwave-assisted Ritter reaction: An atom-economic solvent-free synthesis of amides

EPA Science Inventory

An atom-economic solvent-free synthesis of amides by the Ritter reaction of alcohols and nitriles under microwave irradiation is reported. This green protocol is catalyzed by solid supported Nafion®NR50 with improved efficiency and reduced waste production.

Near-infrared light controlled photocatalytic activity of carbon quantum dots for highly selective oxidation reaction

NASA Astrophysics Data System (ADS)

Li, Haitao; Liu, Ruihua; Lian, Suoyuan; Liu, Yang; Huang, Hui; Kang, Zhenhui

2013-03-01

Selective oxidation of alcohols is a fundamental and significant transformation for the large-scale production of fine chemicals, UV and visible light driven photocatalytic systems for alcohol oxidation have been developed, however, the long wavelength near infrared (NIR) and infrared (IR) light have not yet fully utilized by the present photocatalytic systems. Herein, we reported carbon quantum dots (CQDs) can function as an effective near infrared (NIR) light driven photocatalyst for the selective oxidation of benzyl alcohol to benzaldehyde. Based on the NIR light driven photo-induced electron transfer property and its photocatalytic activity for H2O2 decomposition, this metal-free catalyst could realize the transformation from benzyl alcohol to benzaldehyde with high selectivity (100%) and conversion (92%) under NIR light irradiation. HO&z.rad; is the main active oxygen specie in benzyl alcohol selective oxidative reaction confirmed by terephthalic acid photoluminescence probing assay (TA-PL), selecting toluene as the substrate. Such metal-free photocatalytic system also selectively converts other alcohol substrates to their corresponding aldehydes with high conversion, demonstrating a potential application of accessing traditional alcohol oxidation chemistry.Selective oxidation of alcohols is a fundamental and significant transformation for the large-scale production of fine chemicals, UV and visible light driven photocatalytic systems for alcohol oxidation have been developed, however, the long wavelength near infrared (NIR) and infrared (IR) light have not yet fully utilized by the present photocatalytic systems. Herein, we reported carbon quantum dots (CQDs) can function as an effective near infrared (NIR) light driven photocatalyst for the selective oxidation of benzyl alcohol to benzaldehyde. Based on the NIR light driven photo-induced electron transfer property and its photocatalytic activity for H2O2 decomposition, this metal-free catalyst could realize the transformation from benzyl alcohol to benzaldehyde with high selectivity (100%) and conversion (92%) under NIR light irradiation. HO&z.rad; is the main active oxygen specie in benzyl alcohol selective oxidative reaction confirmed by terephthalic acid photoluminescence probing assay (TA-PL), selecting toluene as the substrate. Such metal-free photocatalytic system also selectively converts other alcohol substrates to their corresponding aldehydes with high conversion, demonstrating a potential application of accessing traditional alcohol oxidation chemistry. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr00092c

Selective Hydrogenolysis of Furfural Derivative 2-Methyltetrahydrofuran into Pentanediol Acetate and Pentanol Acetate over Pd/C and Sc(OTf)3 Cocatalytic System.

PubMed

Zhang, Kun; Li, Xing-Long; Chen, Shi-Yan; Xu, Hua-Jian; Deng, Jin; Fu, Yao

2018-02-22

It is of great significance to convert platform molecules and their derivatives into high value-added alcohols, which have multitudinous applications. This study concerns systematic conversion of 2-methyltetrahydrofuran (MTHF), which is obtained from furfural, into 1-pentanol acetate (PA) and 1,4-pentanediol acetate (PDA). Reaction parameters, such as the Lewis acid species, reaction temperature, and hydrogen pressure, were investigated in detail. 1 H NMR spectroscopy and reaction dynamics study were also conducted to help clarify the reaction mechanism. Results suggested that cleavage of the primary alcohol acetate was less facile than that of the secondary alcohol acetate, with the main product being PA. A PA yield of 91.8 % (150 °C, 3 MPa H 2 , 30 min) was achieved by using Pd/C and Sc(OTf) 3 as a cocatalytic system and an 82 % yield of PDA was achieved (150 °C, 30 min) by using Sc(OTf) 3 catalyst. Simultaneously, the efficient conversion of acetic esters into alcohols by simple saponification was carried out and led to a good yield. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

PubMed

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

2014-01-03

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

Enantiodivergent Hydroboration Reactions of a Racemic Allenylsilane with Diisopinocampheylborane and Curtin-Hammett Controlled Double Asymmetric Crotylboration Reactions of (S)-E-α-phenyldimethylsilyl(ddiisopinocampheyl)-crotylborane

PubMed Central

Chen, Ming; Roush, William R.

2013-01-01

The enantiodivergent hydroboration reactions of racemic allenylsilane (±)-4 with (dIpc)2BH and subsequent crotylboration of achiral aldehydes with the product crotylborane (S)-E-5 at −78 °C provide (E)-δ-silyl-anti-homoallylic alcohols 6 in 71–89% yield and with 93–96% ee. Intriguingly, mismatched double asymmetric crotylboration reactions of enantioenriched chiral aldehydes 20 with (S)-E-5 proceed under Curtin-Hammett control to give anti-3-hydroxylcrotylsilanes 24 as the only products. PMID:24039304

Enantiodivergent hydroboration reactions of a racemic allenylsilane with diisopinocampheylborane and Curtin–Hammett controlled double asymmetric crotylboration reactions of (S)-E-αphenyldimethylsilyl(ddiisopinocampheyl)-crotylborane

PubMed Central

Chen, Ming; Roush, William R.

2013-01-01

The enantiodivergent hydroboration reactions of racemic allenylsilane (±)-4 with (dIpc)2BH and subsequent crotylboration of achiral aldehydes with the product crotylborane (S)-E-5 at −78 °C provide (E)-δ-silyl-anti-homoallylic alcohols 6 in 71–89% yield and with 93–96% ee. Intriguingly, mismatched double asymmetric crotylboration reactions of enantioenriched chiral aldehydes 20 with (S)-E-5 proceed under Curtin–Hammett control to give anti-β-hydroxylcrotylsilanes 24 as the only products. PMID:24068848

Using Gas Phase Reactions of Hexamethylene Triperoxide Diamine (HMTD) to Improve Detection in Mass Spectrometry

NASA Astrophysics Data System (ADS)

Colizza, Kevin; Yevdokimov, Alexander; McLennan, Lindsay; Smith, James L.; Oxley, Jimmie C.

2018-01-01

Our efforts to lower the detection limits of hexamethylene triperoxide diamine (HMTD) have uncovered previously unreported gas-phase reactions of primary and secondary amines with one of the six methylene carbons. The reaction occurs primarily in the atmospheric pressure chemical ionization (APCI) source and is similar to the behavior of alcohols with HMTD [1]. However, unlike alcohols, the amine reaction conserves the hydrogen peroxide on the intact product. Furthermore, with or without amines, HMTD is oxidized to tetramethylene diperoxide diamine dialdehyde (TMDDD) in a temperature-dependent fashion in the APCI source. Synthesized TMDDD forms very strong adducts (not products) to ammonium and amine ions in the electrospray ionization (ESI) source. Attempts to improve HMTD detection by generating TMDDD in the APCI source with post-column addition of amines were not successful. Signal intensity of the solvent related HMTD product in methanol, [HMTD+MeOH2-H2O2]+ (m/z 207.0975), was understandably related to the amount of methanol in the HMTD environment as it elutes into the source. With conditions optimized for this product, the detection of 100 pg on column was accomplished with a robust analysis of 300 pg (1.44 pmol) routinely performed on the Orbitrap mass spectrometers. [Figure not available: see fulltext.

Ene reaction of singlet oxygen, triazolinedione, and nitrosoarene with chiral deuterium-labeled allylic alcohols: the interdependence of diastereoselectivity and regioselectivity discloses mechanistic insights into the hydroxy-group directivity.

PubMed

Adam, Waldemar; Bottke, Nils; Krebs, Oliver; Lykakis, Ioannis; Orfanopoulos, Michael; Stratakis, Manolis

2002-12-04

The ene reaction of singlet oxygen ((1)O(2)), triazolinedione (TAD), and nitrosoarene, specifically 4-nitronitrosobenzene (ArNO), with the tetrasubstituted 1,3-allylically strained, chiral allylic alcohol 3,4-dimethylpent-3-en-2-ol (2) leads to the threo-configured ene products in high diastereoselectivity, a consequence of the hydroxy-group directivity. Hydrogen bonding favors formation of the threo-configured encounter complex threo-EC in the early stage of ene reaction. For the analogous twix deuterium-labeled allylic alcohol Z-2-d(3), a hitherto unrecognized dichotomy between (1)O(2) and the ArNO and TAD enophiles is disclosed in the regioselectivity of the tetrasubstituted alcohol: Whereas for ArNO and TAD, hydrogen bonding with the allylic hydroxy group dictates the regioselectivity (twix selectivity), for (1)O(2), the cis effect dominates (twin/trix selectivity). From the interdependence between the twix/twin regioselectivity and the threo/erythro diastereoselectivity, it has been recognized that the enophile also attacks the allylic alcohol from the erythro pi face without assistance by hydrogen bonding with the allylic hydroxy functionality.

Formation of Alkenes via Degradation of tert-Alkyl Ethers and Alcohols by Aquincola tertiaricarbonis L108 and Methylibium spp. ▿†

PubMed Central

Schäfer, Franziska; Muzica, Liudmila; Schuster, Judith; Treuter, Naemi; Rosell, Mònica; Harms, Hauke; Müller, Roland H.; Rohwerder, Thore

2011-01-01

Bacterial degradation pathways of fuel oxygenates such as methyl tert-butyl and tert-amyl methyl ether (MTBE and TAME, respectively) have already been studied in some detail. However, many of the involved enzymes are still unknown, and possible side reactions have not yet been considered. In Aquincola tertiaricarbonis L108, Methylibium petroleiphilum PM1, and Methylibium sp. strain R8, we have now detected volatile hydrocarbons as by-products of the degradation of the tert-alkyl ether metabolites tert-butyl and tert-amyl alcohol (TBA and TAA, respectively). The alkene isobutene was formed only during TBA catabolism, while the beta and gamma isomers of isoamylene were produced only during TAA conversion. Both tert-alkyl alcohol degradation and alkene production were strictly oxygen dependent. However, the relative contribution of the dehydration reaction to total alcohol conversion increased with decreasing oxygen concentrations. In resting-cell experiments where the headspace oxygen content was adjusted to less than 2%, more than 50% of the TAA was converted to isoamylene. Isobutene formation from TBA was about 20-fold lower, reaching up to 4% alcohol turnover at low oxygen concentrations. It is likely that the putative tert-alkyl alcohol monooxygenase MdpJ, belonging to the Rieske nonheme mononuclear iron enzymes and found in all three strains tested, or an associated enzymatic step catalyzed the unusual elimination reaction. This was also supported by the detection of mdpJK genes in MTBE-degrading and isobutene-emitting enrichment cultures obtained from two treatment ponds operating at Leuna, Germany. The possible use of alkene formation as an easy-to-measure indicator of aerobic fuel oxygenate biodegradation in contaminated aquifers is discussed. PMID:21742915

27 CFR 21.98 - Bone oil (Dipple's oil).

Code of Federal Regulations, 2013 CFR

2013-04-01

... 27 Alcohol, Tobacco Products and Firearms 1 2013-04-01 2013-04-01 false Bone oil (Dipple's oil....98 Bone oil (Dipple's oil). (a) Color. The color shall be a deep brown. (b) Distillation range. When... below 90 °C. (c) Pyrrol reaction. Prepare a 1.0 percent solution of bone oil in 95 percent alcohol...

27 CFR 21.98 - Bone oil (Dipple's oil).

Code of Federal Regulations, 2011 CFR

2011-04-01

... 27 Alcohol, Tobacco Products and Firearms 1 2011-04-01 2011-04-01 false Bone oil (Dipple's oil....98 Bone oil (Dipple's oil). (a) Color. The color shall be a deep brown. (b) Distillation range. When... below 90 °C. (c) Pyrrol reaction. Prepare a 1.0 percent solution of bone oil in 95 percent alcohol...

27 CFR 21.98 - Bone oil (Dipple's oil).

Code of Federal Regulations, 2014 CFR

2014-04-01

... 27 Alcohol, Tobacco Products and Firearms 1 2014-04-01 2014-04-01 false Bone oil (Dipple's oil....98 Bone oil (Dipple's oil). (a) Color. The color shall be a deep brown. (b) Distillation range. When... below 90 °C. (c) Pyrrol reaction. Prepare a 1.0 percent solution of bone oil in 95 percent alcohol...

27 CFR 21.98 - Bone oil (Dipple's oil).

Code of Federal Regulations, 2012 CFR

2012-04-01

... 27 Alcohol, Tobacco Products and Firearms 1 2012-04-01 2012-04-01 false Bone oil (Dipple's oil....98 Bone oil (Dipple's oil). (a) Color. The color shall be a deep brown. (b) Distillation range. When... below 90 °C. (c) Pyrrol reaction. Prepare a 1.0 percent solution of bone oil in 95 percent alcohol...

A study on the quality control of slow burning polyester

NASA Astrophysics Data System (ADS)

Chen, Bin; Wang, Yinglei; Yan, Zhengfeng; Yu, Tao

2018-04-01

In this paper, the influence of the alcohol/acid mole ratio, reaction temperature, warm-up mode, end-capping, vacuity to the quality of slow burning polyester was studied. The hydroxyl value will increase when the alcohol/acid mole ratio increase, but the acid value and molecular weight will decrease. The molecular weight and molecular weight distribution of the polyester consistent with the designed one can be obtained by stepped heating up. Monobasic alcohol end-capping can be used to control the molecular weight effectively and reduce acid value. Stripping process narrow the molecular weight distribution and reduce the hydroxyl value. Decompression is in favor of the decrease of acid value and increase of the reaction speed to get qualified production.

Process for conversion of lignin to reformulated hydrocarbon gasoline

DOEpatents

Shabtai, Joseph S.; Zmierczak, Wlodzimierz W.; Chornet, Esteban

1999-09-28

A process for converting lignin into high-quality reformulated hydrocarbon gasoline compositions in high yields is disclosed. The process is a two-stage, catalytic reaction process that produces a reformulated hydrocarbon gasoline product with a controlled amount of aromatics. In the first stage, a lignin material is subjected to a base-catalyzed depolymerization reaction in the presence of a supercritical alcohol as a reaction medium, to thereby produce a depolymerized lignin product. In the second stage, the depolymerized lignin product is subjected to a sequential two-step hydroprocessing reaction to produce a reformulated hydrocarbon gasoline product. In the first hydroprocessing step, the depolymerized lignin is contacted with a hydrodeoxygenation catalyst to produce a hydrodeoxygenated intermediate product. In the second hydroprocessing step, the hydrodeoxygenated intermediate product is contacted with a hydrocracking/ring hydrogenation catalyst to produce the reformulated hydrocarbon gasoline product which includes various desirable naphthenic and paraffinic compounds.

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

DeTuri, V.F.; Ervin, K.M.

Energy-resolved competitive collision-induced dissociation methods are used to measure the gas-phase acidities of a series of alcohols (methanol, ethanol, 2-propanol, and 2-methyl-2-propanol). The competitive dissociation reactions of fluoride-alcohol, [F{sup {minus}}{center{underscore}dot}HOR], alkoxide-water, [RO{sup {minus}}{center{underscore}dot}HOH], and alkoxide-methanol [RO{+-}{center{underscore}dot}HOCH{sub 3}] proton-bound complexes are studied using a guided ion beam tandem mass spectrometer. The reaction cross sections and product branching fractions to the two proton transfer channels are measured as a function of collision energy. The enthalpy difference between the two product channels is found by modeling the reaction cross sections near threshold using RRKM theory to account for the energy-dependent product branching ratiomore » and kinetic shift. From the enthalpy difference, the alcohol gas-phase acidities are determined relative to the well-known values of HF and H{sub 2}O. The measured gas-phase acidities are {Delta}{sub acid}H{sub 298}(CH{sub 3}OH) = 1599 {+-} 3 kJ/mol, {Delta}{sub acid}H{sub 298}(CH{sub 3}CH{sub 2}OH) = 1586 {+-} 5 kJ/mol, {Delta}{sub acid}H{sub 298}((CH{sub 3}){sub 2}CHOH) = 1576 {+-} 4 kJ/mol, and {Delta}{sub acid}H{sub 298}((CH{sub 3}){sub 3}COH) = 1573 {+-} 3 kJ/mol.« less

Millimeter and Submillimeter Studies of O(^1D) Insertion Reactions to Form Molecules of Astrophysical Interest

NASA Astrophysics Data System (ADS)

Hays, Brian; Wehres, Nadine; Deprince, Bridget Alligood; Roy, Althea A. M.; Laas, Jacob; Widicus Weaver, Susanna L.

2015-06-01

While both the number of detected interstellar molecules and their chemical complexity continue to increase, understanding of the processes leading to their formation is lacking. Our research group combines laboratory spectroscopy, observational astronomy, and astrochemical modeling for an interdisciplinary examination of the chemistry of star and planet formation. This talk will focus on our laboratory studies of O(^1D) insertion reactions with organic molecules to produce molecules of astrophysical interest. By employing these reactions in a supersonic expansion, we are able to produce interstellar organic reaction intermediates that are unstable under terrestrial conditions; we then probe the products using millimeter and submillimeter spectroscopy. We benchmarked this setup using the well-studied O(^1D) + methane reaction to form methanol. After optimizing methanol production, we moved on to study the O(^1D) + ethylene reaction to form vinyl alcohol (CH_2CHOH), and the O(^1D) + methyl amine reaction to form aminomethanol (NH_2CH_2OH). Vinyl alcohol measurements have now been extended up to 450 GHz, and the associated spectral analysis is complete. A possible detection of aminomethanol has also been made, and continued spectral studies and analysis are underway. We will present the results from these experiments and discuss future applications of these molecular and spectroscopic techniques.

Synthesis of polycyclic spiroindolines by highly diastereoselective interrupted Ugi cascade reactions of 3-(2-isocyanoethyl)indoles.

PubMed

Saya, Jordy M; Oppelaar, Barry; Cioc, Răzvan C; van der Heijden, Gydo; Vande Velde, Christophe M L; Orru, Romano V A; Ruijter, Eelco

2016-10-13

We report a highly diastereoselective interrupted Ugi reaction to construct a broad range of structurally congested and stereochemically complex spiroindolines from tryptamine-derived isocyanides. The reaction is facilitated by using fluorinated alcohols (TFE or HFIP) as solvents and tolerates a broad range of amines, aldehydes and 2-isocyanoethylindoles to give polycyclic products in moderate to excellent yields.

Atmospheric reactivity of alcohols, thiols and fluoroalcohols with chlorine atoms

NASA Astrophysics Data System (ADS)

Garzon Ruiz, Andres

Alcohols, thiols and fluoroalcohols are volatile organic compounds (VOCs) which are emitted to the atmosphere from both natural (vegetation, oceans, volcanoes, etc.) and anthropogenic sources (fuels, solvents, wastewater, incinerators, refrigerants, etc.). These pollutants can be eliminated from the troposphere by deposition on the terrestrial surface, direct photolysis or reaction with different tropospheric oxidants. Reactions of VOCs with tropospheric oxidants are involved in the well-known atmospheric phenomenon of photochemical smog or the production of tropospheric ozone. The oxidation of these VOCs in the troposphere is mainly initiated by reaction with OH radicals during the daytime and with NO radicals at night. However, in recent years, the oxidation by chlorine atoms (Cl) has gained great importance in the study of atmospheric reactions because they may exert some influence in the boundary layer, particularly in marine and coastal environments. In general, Cl atoms are much more reactive species than OH and NO; radicals and therefore low concentrations of Cl may compete with OH and NO3 in hydrocarbon oxidation processes. The main source of tropospheric Cl atoms is believed to be the photolysis of chlorine-containing molecules generated by heterogeneous reactions of sea salt aerosols. It has also been proposed that Cl atoms, produced in the photolysis of Cl2 emitted from industrial processes, may enhance hydrocarbon oxidation rates and ozone production in urban environments. In this work, a kinetic, theoretical and mechanistic study of the reaction of several alcohols, thiols, and fluoroalcohols with Cl atoms has been carried out. Pulsed laser photolysis-fluorescence resonance (PLP-RF) technique was used for the kinetic study as a function of temperature and pressure. An environmental chamber-Fourier transform infrared (FTIR) system was also employed in the kinetic studies. Tropospheric lifetimes of these pollutants were estimated using obtained kinetic data. Products of these reactions were determined by FTIR and derivatization with 2,4-dinitrophenylhydrazine and HPLC analysis. Finally, in order to determine the main reaction pathways a theoretical study at QCISD(T)/6-311G**//MP2(Full)(6-311C** level was performed for each reaction.

Erratum to "The mechanism and thermodynamics of transesterification of acetate-ester enolates in the gas phase" : [Int. J. Mass Spectrom. Ion Process. 172 (1998) 25

NASA Astrophysics Data System (ADS)

Haas, George W.; Giblin, Daryl E.; Gross, Michael L.

1998-02-01

In solution, base-catalyzed hydrolysis and transesterification of esters are initiated by hydroxide- or alkoxide-ion attack at the carbonyl carbon. At low pressures in the gas phase, however, transesterification proceeds by an attack of the enolate anion of an acetate ester on an alcohol. Fourier transform mass spectrometry (FTMS) indicates that the reaction is the second-order process: -CH2-CO2-R+R'-OH-->-CH2-CO2-R'+R-OH and there is little to no detectable production of either alkoxide anion. Labeling studies show that the product and reactant enolate anion esters undergo exchange of hydrogens located [alpha] to the carbonyl carbon with the deuterium of R'--OD. The extent of the H/D exchange increases with reaction time, pointing to a short-lived intermediate. The alcoholysis reaction rate constants increase with increasing acidity of the primary, straight-chained alkyl alcohols, whereas steric effects associated with branched alcohols cause the rate constants to decrease. Equilibrium constants, which were determined directly from measurements at equilibrium and which were calculated from the forward and reverse rate constants, are near unity and show internal consistency. In the absence of steric effects, the larger enolate is always the favored product at equilibrium. The intermediate for the transesterification reaction, which can be generated at a few tenths of a torr in a tandem mass spectrometer, is tetrahedral, but other adducts that are collisionally stabilized under these conditions are principally loosely bound complexes.

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

DOEpatents

Crabtree, Robert H.; Brown, Stephen H.

1988-01-01

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

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

DOEpatents

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

1988-02-16

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

Epoxidation of Geraniol: An Advanced Organic Experiment that Illustrates Asymmetric Synthesis

NASA Astrophysics Data System (ADS)

Bradley, Lynn M.; Springer, Joseph W.; Delate, Gregory M.; Goodman, Andrew

1997-11-01

The Sharpless epoxidation reaction is considered one of the most powerful advances in asymmetric organic synthesis (1). It is a classic example of the use of an asymmetric catalyst to provide an enantiomerically enriched mixture of epoxy alcohols. The procedure typically uses titanium(IV) tetraisopropoxide (Ti(OiPr)4) as a catalyst, a peroxide, and dialkyl tartrates to induce asymmetry in the epoxidation reaction of allylic alcohols. The experiment described in this paper illustrates the principle of asymmetric epoxidation and enables students to determine enantiomeric product ratios using chiral shift reagents and NMR spectroscopy.

Secondary benzylation with benzyl alcohols catalyzed by a high-valent heterobimetallic Ir-Sn complex.

PubMed

Podder, Susmita; Choudhury, Joyanta; Roy, Sujit

2007-04-13

A highly efficient secondary benzylation procedure has been demonstrated using a high-valent heterobimetallic complex [Ir2(COD)2(SnCl3)2(Cl)2(mu-Cl)2] 1 as the catalyst in 1,2-dichloroethane to afford the corresponding benzylated products in moderate to excellent yields. The reaction was performed not only with carbon nucleophiles (arenes and heteroarenes) but also with oxygen (alcohol), nitrogen (amide and sulfonamide), and sulfur (thiol) nucleophiles. Mechanistic investigation showed the intermediacy of the ether in this reaction. An electrophilic mechanism is proposed from Hammett correlation.

Catalytic conversion of syngas to mixed alcohols over Zn-Mn promoted Cu-Fe based catalyst

DOE PAGES

Lu, Yongwu; Yu, Fei; Hu, Jin; ...

2012-04-12

Zn-Mn promoted Cu-Fe based catalyst was synthesized by the co-precipitation method. Mixed alcohols synthesis from syngas was studied in a half-inch tubular reactor system after the catalyst was reduced. Zn-Mn promoted Cu-Fe based catalyst was characterized by SEM-EDS, TEM, XRD, and XPS. The liquid phase products (alcohol phase and hydrocarbon phase) were analyzed by GC-MS and the gas phase products were analyzed by GC. The results showed that Zn-Mn promoted Cu-Fe based catalyst had high catalytic activity and high alcohol selectivity. The maximal CO conversion rate was 72%, and the yield of alcohol and hydrocarbons were also very high. Cumore » (111) was the active site for mixed alcohols synthesis, Fe 2C (101) was the active site for olefin and paraffin synthesis. The reaction mechanism of mixed alcohols synthesis from syngas over Zn-Mn promoted Cu-Fe based catalyst was proposed. Here, Zn-Mn promoted Cu-Fe based catalyst can be regarded as a potential candidate for catalytic conversion of biomass-derived syngas to mixed alcohols.« less

A Facile Solvent-Free Cannizzaro Reaction: An Instructional Model for Introductory Organic Chemistry Laboratory

ERIC Educational Resources Information Center

Phonchaiya, Sonthi; Panijpan, Bhinyo; Rajviroongit, Shuleewan; Wright, Tony; Blanchfield, Joanne T.

2009-01-01

Liquid 2-chlorobenzaldehyde was converted, by grinding with potassium hydroxide pellets, into equimolar quantities of solid 2-chlorobenzoic acid and solid 2-chlorobenzyl alcohol in a Cannizzaro reaction. TLC, IR, and NMR experiments, using authentic samples for comparison, confirmed the identity and purity of the two products. Guided-inquiry…

Carbon Isotope Measurements of Experimentally-Derived Hydrothermal Mineral-Catalyzed Organic Products by Pyrolysis-Isotope Ratio Mass Spectrometry

NASA Technical Reports Server (NTRS)

Socki, Richard A.; Fu, Qi; Niles, Paul B.

2011-01-01

We report results of experiments to measure the C isotope composition of mineral catalyzed organic compounds derived from high temperature and high pressure synthesis. These experiments make use of an innovative pyrolysis technique designed to extract and measure C isotopes. To date, our experiments have focused on the pyrolysis and C isotope ratio measurements of low-molecular weight intermediary hydrocarbons (organic acids and alcohols) and serve as a proof of concept for making C and H isotope measurements on more complicated mixtures of solid-phase hydrocarbons and intermediary products produced during high temperature and high pressure synthesis on mineral-catalyzed surfaces. The impetus for this work stems from recently reported observations of methane detected within the Martian atmosphere [1-4], coupled with evidence showing extensive water-rock interaction during Martian history [5-7]. Methane production on Mars could be the result of synthesis by mineral surface-catalyzed reduction of CO2 and/or CO by Fischer-Tropsch Type (FTT) reactions during serpentization reactions [8,9]. Others have conducted experimental studies to show that FTT reactions are plausible mechanisms for low-molecular weight hydrocarbon formation in hydrothermal systems at mid-ocean ridges [10-12]. Further, recent experiments by Fu et al. [13] focus on examining detailed C isotope measurements of hydrocarbons produced by surface-catalyzed mineral reactions. Work described in this paper details the experimental techniques used to measure intermediary organic reaction products (alcohols and organic acids).

Radioactive Phosphorylation of Alcohols to Monitor Biocatalytic Diels-Alder Reactions

PubMed Central

Nierth, Alexander; Jäschke, Andres

2011-01-01

Nature has efficiently adopted phosphorylation for numerous biological key processes, spanning from cell signaling to energy storage and transmission. For the bioorganic chemist the number of possible ways to attach a single phosphate for radioactive labeling is surprisingly small. Here we describe a very simple and fast one-pot synthesis to phosphorylate an alcohol with phosphoric acid using trichloroacetonitrile as activating agent. Using this procedure, we efficiently attached the radioactive phosphorus isotope 32P to an anthracene diene, which is a substrate for the Diels-Alderase ribozyme—an RNA sequence that catalyzes the eponymous reaction. We used the 32P-substrate for the measurement of RNA-catalyzed reaction kinetics of several dye-labeled ribozyme variants for which precise optical activity determination (UV/vis, fluorescence) failed due to interference of the attached dyes. The reaction kinetics were analyzed by thin-layer chromatographic separation of the 32P-labeled reaction components and densitometric analysis of the substrate and product radioactivities, thereby allowing iterative optimization of the dye positions for future single-molecule studies. The phosphorylation strategy with trichloroacetonitrile may be applicable for labeling numerous other compounds that contain alcoholic hydroxyl groups. PMID:21731729

Effects of B group vitamins on reactions of various alpha-hydroxyl-containing organic radicals.

PubMed

Lagutin, P Yu; Shadyro, O I

2005-08-15

Effects of vitamins B1, B2, B6, and pyridoxal phosphate (PPh) on final product formation in radiolysis of aqueous solutions of ethanol, ethylene glycol, alpha-methylglycoside, and maltose were studied. It has been found that vitamin B2 and PPh effectively oxidize R*CHOH species, while suppressing their recombination and fragmentation reactions, thereby increasing the yields of the respective oxidation products. Vitamins B1 and B2 are capable of reducing alcohol radicals to the respective initial molecules, decreasing the yields of the radical transformation products.

Catalytic Conversion of Short-Chain Alcohols on Atomically Dispersed Au and Pd Supported on Nanoscale Metal Oxides

NASA Astrophysics Data System (ADS)

Wang, Chongyang

With the development of technologies for cellulosic biomass conversion to fuels and chemicals, bio-alcohols are among the main alternative feedstocks to fossil fuels. The research pursued in my thesis was the investigation of gold and palladium as catalysts for the application of short aliphatic alcohols to hydrogen generation and value-added chemicals production. Specifically, selective methanol steam reforming and non-oxidative ethanol dehydrogenation to hydrogen and acetaldehyde were investigated in this thesis work. A major aim of the thesis was to develop atomically efficient catalysts with tuned surface chemistry for the desired reactions, using suitable synthesis methods. Methanol steam reforming (SRM) for hydrogen production has recently been investigated on gold catalysts to overcome the drawbacks of copper catalysts (deactivation, pyrophoricity). Previous work at Tufts University has shown that both CeO2 and ZnO are suitable supports for gold. In this thesis, nanoscale composite oxides ZnZrOx were prepared by a carbon hard-template method, which resulted in homogeneous distribution of Zn species in the matrix of ZrO2. Tunable surface chemistry of ZnZrO x was demonstrated by varying the Zn/Zr ratio to suppress the strong Lewis acidity of ZrO2, which leads to undesired production of CO through methanol decomposition. With atomic dispersion of gold, Au/ZnZrO x catalyzes the SRM reaction exclusively via the methanol self-coupling pathway up to 375°C. The activity of Au/ZnZrOx catalysts was compared to Au/TiO2, which is another catalyst system demonstrating atomic dispersion of gold. Similarity in the apparent activation energy of SRM on all the supported gold catalysts studied in this thesis and in the literature further confirms the same single-site Au-Ox-MO centers as active sites for SRM with indirect effects of the supports exploited. With this fundamental understanding of gold-catalyzed C1 alcohol reforming, the Au/ZnZrOx catalyst was evaluated for the dehydrogenation of ethanol. Bare ZnZrOx activate ethanol conversion in the range of 280-300°C and produce undesired ethylene as product of ethanol dehydration, whereas, addition of small amount of gold (<1wt.%) was found to significantly change the product distribution in the low-temperature range (200°C-350°C). As gold passivates the strong Bronsted acid sites of ZrO2 and selectively facilitates the dehydrogenation of ethanol at low-temperature, a wide temperature range was found between the production of acetaldehyde (dehydrogenation products) and ethylene (dehydration product), which can be harnessed for the industrial application. Interestingly, the steam reforming of ethanol did not take place in the low-temperature region, thus the selectivity to acetaldehyde and hydrogen was 100% even in the presence of water. In addition to gold, palladium was also studied in this thesis work on the ZnZrOx composite oxides, and its activity and selectivity were compared to Au/ZnZrOx. Monometallic Pd catalyzes the decomposition of methanol and ethanol, resulting in different product distribution for C 1-C2 alcohol reactions. With ZnZrOx employed as the catalyst support in this thesis work, the finely dispersed ZnO species in ZrO2 were found to alloy with the supported palladium under reduction treatment. Alloying with Zn tunes the chemistry of Pd to catalyze the SRM reaction through the methanol coupling mechanism, shutting off the undesired methanol decomposition pathway. A preliminary study of the Pd/ZnZrO x system for ethanol dehydrogenation also demonstrated the modification of Pd when in the PdZn alloy form. Different from the monometallic Pd catalyst, which primarily catalyzes the C-C bond scission of ethanol, high selectivity to ethanol dehydrogenation products was found on PdZn, over the temperature range of 200-400°C. Formation of the PdZn alloy broadens the application of Pd and potentially other Group VIII metals for selective alcohol conversion reactions. In summary, this thesis work has investigated two noble metals Au and Pd from Group IB and Group VIII, respectively, for methanol and ethanol alcohol reforming reactions employing a novel ZnZrOx composite oxide as a platform catalyst support. Comprehensive study of Au catalyst has deepened our understanding of atomically dispersed Au anchored on various supports through oxygen bonds as the active sites for alcohol reforming reactions, and showed the support effect to be indirect, serving as the carrier and stabilizer of the gold species. For Pd, the Zn species of the composite oxide is necessary to modify the Pd catalyst and the PdZn alloy gives it the desired Au-like properties. Full characterization of the catalysts used here by ICP, XPS, XRD, FTIR and STEM imaging was conducted throughout the thesis to identify the stable species and correlate the catalyst performance with its composition and morphology. Surface acidity titration by isopropanol temperature-programmed desorption/mass spectrometry (IPA-TPD/MS) and pyridine-IR adsorption/desorption was conducted in parallel to temperature-programmed surface reaction (TPSR) studies and products from isothermal steady-state reactions were monitored online by mass spectrometry.

Catalytic Oxidation of Vanillyl Alcohol Using FeMCM-41 Nanoporous Tubular Reactor

NASA Astrophysics Data System (ADS)

Elamathi, P.; Kolli, Murali Krishna; Chandrasekar, G.

Iron containing nanoporous MCM-41 (FeMCM-41) with different Si/Fe ratios of 50, 100 and 150 was synthesized by hydrothermal synthesis process. The materials obtained from hydrothermal synthesis were characterized by various physico chemical techniques such as XRD, N2 adsorption, DR UV-vis, EPR and FTIR spectroscopy. XRD analyses of FeMCM-41 materials confirmed the presence of well-ordered crystalline structure. N2 isotherm of FeMCM-41 materials showed type IV adsorption isotherm. EPR and DR UV-vis analysis of FeMCM-41 samples indicates the presence of high tetrahedral coordination at the Si/Fe ratios of 100 and 150. The catalytic performance of FeMCM-41 nano tubular reactor was tested in the liquid phase oxidation of vanillyl alcohol into vanillin using H2O2 (50wt% in water). The reaction products were analyzed by gas chromatography in DB-5 capillary column with flame ionization detector. The products were confirmed by 1H NMR, 13C NMR and LC-Mass spectroscopy. The maximum conversion of vanillyl alcohol (85%) and selectivity towards vanillin (82%) were observed using the catalyst FeMCM-41(100) in 30min at 60∘C. The influence of reaction temperature, reaction time, reactants molar ratio, Si/Fe ratio and amount of catalyst were investigated.

Influence of thermally processed carbohydrate/amino acid mixtures on the fermentation by Saccharomyces cerevisiae.

PubMed

Tauer, Andreas; Elss, Sandra; Frischmann, Matthias; Tellez, Patricia; Pischetsrieder, Monika

2004-04-07

The production of alcoholic beverages such as Tequila, Mezcal, whiskey, or beer includes the fermentation of a mash containing Maillard reaction products. Because excessive heating of the mash can lead to complications during the following fermentation step, the impact of Maillard products on the metabolism of Saccharomyces cerevisiae was investigated. For this purpose, fermentation was carried out in a model system in the presence and absence of Maillard reaction products and formation of ethanol served as a marker for the progression of fermentation. We found that increasing amounts of Maillard products reduced the formation of ethanol up to 80%. This effect was dependent on the pH value during the Maillard reaction, reaction time, as well as the carbohydrate and amino acid component used for the generation of Maillard reaction products. Another important factor is the pH value during fermentation: The inhibitory effect of Maillard products was not detectable at a pH of 4 and increased with higher pH-values. These findings might be of relevance for the production of above-mentioned beverages.

Spectroscopic Analyses of the Biofuels-Critical Phytochemical Coniferyl Alcohol and Its Enzyme-Catalyzed Oxidation Products

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

Achyuthan, Komandoor; Adams, Paul; Simmons, Blake

2011-07-13

Lignin composition (monolignol types of coniferyl, sinapyl or p-coumaryl alcohol) is causally related to biomass recalcitrance. We describe multiwavelength (220, 228, 240, 250, 260, 290, 295, 300, 310 or 320 nm) absorption spectroscopy of coniferyl alcohol and its laccase- or peroxidase-catalyzed products during real time kinetic, pseudo-kinetic and endpoint analyses, in optical turn on or turn off modes, under acidic or basic conditions. Reactions in microwell plates and 100 mu L volumes demonstrated assay miniaturization and high throughput screening capabilities. Bathochromic and hypsochromic shifts along with hyperchromicity or hypochromicity accompanied enzymatic oxidations by laccase or peroxidase. The limits of detectionmore » and quantitation of coniferyl alcohol averaged 2.4 and 7.1 mu M respectively, with linear trend lines over 3 to 4 orders of magnitude. Coniferyl alcohol oxidation was evident within 10 minutes or with 0.01 mu g/mL laccase and 2 minutes or 0.001 mu g/mL peroxidase. Detection limit improved to 1.0 mu M coniferyl alcohol with Km of 978.7 +/- 150.7 mu M when examined at 260 nm following 30 minutes oxidation with 1.0 mu g/mL laccase. Our assays utilized the intrinsic spectroscopic properties of coniferyl alcohol or its oxidation products for enabling detection, without requiring chemical synthesis or modification of the substrate or product(s). These studies facilitate lignin compositional analyses and augment pretreatment strategies for reducing biomass recalcitrance.« less

Scope and mechanism in palladium-catalyzed isomerizations of highly substituted allylic, homoallylic, and alkenyl alcohols.

PubMed

Larionov, Evgeny; Lin, Luqing; Guénée, Laure; Mazet, Clément

2014-12-03

Herein we report the palladium-catalyzed isomerization of highly substituted allylic alcohols and alkenyl alcohols by means of a single catalytic system. The operationally simple reaction protocol is applicable to a broad range of substrates and displays a wide functional group tolerance, and the products are usually isolated in high chemical yield. Experimental and computational mechanistic investigations provide complementary and converging evidence for a chain-walking process consisting of repeated migratory insertion/β-H elimination sequences. Interestingly, the catalyst does not dissociate from the substrate in the isomerization of allylic alcohols, whereas it disengages during the isomerization of alkenyl alcohols when additional substituents are present on the alkyl chain.

Catalytic asymmetric synthesis of chiral propargylic alcohols for the intramolecular Pauson-Khand cycloaddition.

PubMed

Turlington, Mark; Yue, Yang; Yu, Xiao-Qi; Pu, Lin

2010-10-15

Several methods for the catalytic asymmetric alkyne addition to aldehydes are used to prepare the propargylic alcohol-based chiral en-ynes. Protection of the propargylic alcohols with either an acetyl or a methyl group allows the resulting en-ynes to undergo the intramolecular Pauson-Khand reaction to form the corresponding optically active 5,5- and 5,6-fused bicyclic products with high diastereoselectivity and high enantiomeric purity. In the major product, the propargylic substituent and the bridgehead hydrogen are cis with respect to each other on the fused bicyclic rings. The enantiomeric purity of the propargylic alcohols generated from the asymmetric alkyne addition is maintained in the cycloaddition products. The allylic ethers of the chiral propargylic alcohols are prepared which can also undergo the highly diastereoselective Pauson-Khand cycloaddition with retention of the high enantiomeric purity. This study has shown that the size of the substituents at the propargylic position as well as on the alkyne is important for the diastereoselectivity with the greater bulkiness of the substituents giving higher diastereoselectivity.

Alternative mechanistic explanation for ligand-dependent selectivities in copper-catalyzed N- and O-arylation reactions.

PubMed

Yu, Hai-Zhu; Jiang, Yuan-Ye; Fu, Yao; Liu, Lei

2010-12-29

The ligand-dependent selectivities in Ullmann-type reactions of amino alcohols with iodobenzene by β-diketone- and 1,10-phenanthroline-ligated Cu(I) complexes were recently explained by the single-electron transfer and iodine atom transfer mechanisms (Jones, G. O., Liu, P., Houk, K. N., and Buchwald, S. L. J. Am. Chem. Soc. 2010, 132, 6205.). The present study shows that an alternative, oxidative addition/reductive elimination mechanism may also explain the selectivities. Calculations indicate that a Cu(I) complex with a negatively charged β-diketone ligand is electronically neutral, so that oxidative addition of ArI to a β-diketone-ligated Cu(I) prefers to occur (and occur readily) in the absence of the amino alcohol. Thus, coordination of the amino alcohol in its neutral form can only occur at the Cu(III) stage where N-coordination is favored over O-coordination. The coordination step is the rate-limiting step and the outcome is that N-arylation is favored with the β-diketone ligand. On the other hand, a Cu(I) complex with a neutral 1,10-phenanthroline ligand is positively charged, so that oxidative addition of ArI to a 1,10-phenanthroline-ligated Cu(I) has to get assistance from a deprotonated amino alcohol substrate. This causes oxidative addition to become the rate-limiting step in the 1,10-phenanthroline-mediated reaction. The immediate product of the oxidative addition step is found to undergo facile reductive elimination to provide the arylation product. Because O-coordination of a deprotonated amino alcohol is favored over N-coordination in the oxidative addition transition state, O-arylation is favored with the 1,10-phenanthroline ligand.

Immobilised enzyme microreactor for screening of multi-step bioconversions: characterisation of a de novo transketolase-ω-transaminase pathway to synthesise chiral amino alcohols.

PubMed

Matosevic, S; Lye, G J; Baganz, F

2011-09-20

Complex molecules are synthesised via a number of multi-step reactions in living cells. In this work, we describe the development of a continuous flow immobilized enzyme microreactor platform for use in evaluation of multi-step bioconversion pathways demonstrating a de novo transketolase/ω-transaminase-linked asymmetric amino alcohol synthesis. The prototype dual microreactor is based on the reversible attachment of His₆-tagged enzymes via Ni-NTA linkage to two surface derivatised capillaries connected in series. Kinetic parameters established for the model transketolase (TK)-catalysed conversion of lithium-hydroxypyruvate (Li-HPA) and glycolaldehyde (GA) to L-erythrulose using a continuous flow system with online monitoring of reaction output was in good agreement with kinetic parameters determined for TK in stop-flow mode. By coupling the transketolase catalysed chiral ketone forming reaction with the biocatalytic addition of an amine to the TK product using a transaminase (ω-TAm) it is possible to generate chiral amino alcohols from achiral starting compounds. We demonstrated this in a two-step configuration, where the TK reaction was followed by the ω-TAm-catalysed amination of L-erythrulose to synthesise 2-amino-1,3,4-butanetriol (ABT). Synthesis of the ABT product via the dual reaction and the on-line monitoring of each component provided a full profile of the de novo two-step bioconversion and demonstrated the utility of this microreactor system to provide in vitro multi-step pathway evaluation. Copyright © 2011 Elsevier B.V. All rights reserved.

Preparation of Solid Derivatives by Differential Scanning Calorimetry.

ERIC Educational Resources Information Center

Crandall, E. W.; Pennington, Maxine

1980-01-01

Describes the preparation of selected aldehydes and ketones, alcohols, amines, phenols, haloalkanes, and tertiaryamines by differential scanning calorimetry. Technique is advantageous because formation of the reaction product occurs and the melting point of the product is obtained on the same sample in a short time with no additional purification…

Addition reaction of methyl cinnamate with 2-amino-4- nitrophenol

NASA Astrophysics Data System (ADS)

Suryanti, Venty; Rakhman Wibowo, Fajar; Pranoto; Robingatun Isnaeni, Siti; Ratna Kumala Sari, Meiyanti; Handayani, Sekar

2016-02-01

A novel compound which have one N-H fragment and nitrophenyl group has been designed and synthesized from cinnamaldehyde. The reaction was conducted in 3 step reactions to give the final product. Firstly, cinnamaldehyde was converted into cinnamic acid, which was then esterified with methyl alcohol to obtained methyl cinnamate. The last step was the addition reaction between methyl cinnamate and 2-amino-4-nitrophenol to give a cinnamaldehyde derivative, namely methyl-3-(2-hidroksi-5-nitrophenyl amino)-3- phenylpropanoate.

Design of highly selective ethanol dehydration nanocatalysts for ethylene production.

PubMed

Austin, Natalie; Kostetskyy, Pavlo; Mpourmpakis, Giannis

2018-02-22

Rational design of catalysts for selective conversion of alcohols to olefins is key since product selectivity remains an issue due to competing etherification reactions. Using first principles calculations and chemical rules, we designed novel metal-oxide-protected metal nanoclusters (M 13 X 4 O 12 , with M = Cu, Ag, and Au and X = Al, Ga, and In) exhibiting strong Lewis acid sites on their surface, active for the selective formation of olefins from alcohols. These symmetrical nanocatalysts, due to their curvature, show unfavorable etherification chemistries, while favoring the olefin production. Furthermore, we determined that water removal and regeneration of the nanocatalysts is more feasible compared to the equivalent strong acid sites on solid acids used for alcohol dehydration. Our results demonstrate an exceptional stability of these new nanostructures with the most energetically favorable being Cu-based. Thus, the high selectivity and stability of these in-silico-predicted novel nanoclusters (e.g. Cu 13 Al 4 O 12 ) make them attractive catalysts for the selective dehydration of alcohols to olefins.

Palladium-Catalyzed Telomerization of Butadiene with Polyols: From Mono to Polysaccharides

NASA Astrophysics Data System (ADS)

Bouquillon, Sandrine; Muzart, Jacques; Pinel, Catherine; Rataboul, Franck

The telomerization of butadiene with alcohols is an elegant way to synthesize ethers with minimal environmental impact since this reaction is 100% atom efficient. Besides telomerization of butadiene with methanol and water that is industrially developed, the modification of polyols is still under development. Recently, a series of new substrates has been involved in this reaction, including diols, pure or crude glycerol, protected or unprotected monosaccharides, as well as polysaccharides. This opens up the formation of new products having specific physicochemical properties. We will describe recent advances in this field, focusing on the reaction of renewable products and more specifically on saccharides. The efficient catalytic systems as well as the optimized reaction conditions will be described and some physicochemical properties of the products will be reported.

AAPH-mediated antioxidant reactions of secoisolariciresinol and SDG.

PubMed

Hosseinian, Farah S; Muir, Alister D; Westcott, Neil D; Krol, Ed S

2007-02-21

Secoisolariciresinol (SECO ) is the major lignan found in flaxseed (Linum usitatissimum L.) and is present in a polymer that contains secoisolariciresinol diglucoside (SDG ). SECO, SDG and the polymer are known to have a number of health benefits, including reduction of serum cholesterol levels, delay in the onset of type II diabetes and decreased formation of breast, prostate and colon cancers. The health benefits of SECO and SDG may be partially attributed to their antioxidant properties. To better understand their antioxidant properties, SECO and SDG were oxidized using 2,2'-azobis(2-amidinopropane), an in vitro model of radical scavenging. The major lignan radical-scavenging oxidation products and their formation over time were determined. SDG was converted to four major products, which were the result of a phenoxyl radical intermediate. One of these products, a dimer of SDG, decomposed under the reaction conditions to form two of the other major products, and . SECO was converted to five major products, two of which were also the result of a phenoxyl radical intermediate. The remaining products were the result of an unexpected alkoxyl radical intermediate. The phenol oxidation products were stable under the reaction conditions, whereas two of the alcohol oxidation products decomposed. In general, only one phenol group on the lignans was oxidized, suggesting that the number of phenols per molecule may not predict radical scavenging antioxidant ability of lignans. Finally, SECO is a superior antioxidant to SDG, and it may be that the additional alcohol oxidation pathway contributes to its greater antioxidant ability.

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

PubMed

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

2015-06-01

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

Enzymatic production of monoacylglycerols containing polyunsaturated fatty acids through an efficient glycerolysis system.

PubMed

Yang, Tiankui; Rebsdorf, Morten; Engelrud, Ulrik; Xu, Xuebing

2005-03-09

The aim of the study was to develop an efficient glycerolysis system for the enzymatic production of monoacylglycerols (MAGs) containing polyunsaturated fatty acids. Glycerolysis has been widely applied in industry for the chemical production of food MAGs under high temperature. The enzymatic glycerolysis system at 40-70 degrees C is unfortunately a multiphase system, which leads to the lower reaction efficiency. A tert-butyl alcohol system was developed after careful evaluation and more than 20-fold of the reaction efficiency from this system was obtained compared to the solvent-free system. Novozym 435 was employed as a catalyst in the glycerolysis from the screening. In the batch reaction system with tert-butyl alcohol, temperature higher than 40 degrees C was favored. The glycerol/oil ratio was best in the study with 4.5 while the solvent weight ratio from 1 to 3 had little effect. In general, 60-70% yield can be obtained at 2 h in the stirred tank reactor. The continuous glycerolysis was conducted in a packed bed reactor. MAG yield up to 70% was reached at 30-40 min residence time. The continuous glycerolysis was more sensitive to the amount of tert-butyl alcohol, and in the weight ratio to oil more than 2 was favored. The continuous process was optimized with the assistance of response surface methodology. Optimal conditions for the packed bed reactor after all considerations were recommended as glycerol/oil 4:1 (mol/mol), temperature 40 degrees C, and residence time 45 min. The operation stability study showed that there was no slight reduction of reaction performance at more than 30 days, implying a high feasibility in practical applications.

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

DOEpatents

Crabtree, Robert H.; Brown, Stephen H.

1989-01-01

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

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

DOEpatents

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

1989-10-17

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

To brand or not to brand a product placement? Evidence from a field study of two influence mechanisms of positive portrayals of alcohol in film.

PubMed

Redondo, Ignacio; Russell, Cristel A; Bernal, Jorge

2018-04-01

We propose that branded and non-branded product placements in movies are interpreted differently and that a movie with unbranded alcohol portrayals influences audiences' alcohol-related beliefs and choices indirectly, through the process of narrative transportation, whereas a movie with branded alcohol placements impacts audiences' alcohol beliefs and choices via a more basic social-cognitive process of influence. Ordinary moviegoers (N = 758) attended a showing of The Snows of Kilimanjaro (2011) in a popular theatre in Tacna, Peru. Subjects were randomly assigned to watch the original movie, with branded alcohol portrayals, or a brand-free, control version. Reactions to the movie and alcohol-related beliefs were collected in a survey immediately after the film exposure and real beverage choices were measured. The findings reveal that exposure to unbranded positive portrayals of alcohol produces story-consistent beliefs and alcohol choices through the process of narrative transportation and that exposure to branded positive alcohol portrayals produces direct effects in terms of alcohol expectancies and brand choice, despite lowering narrative transportation. Although viewers disengage more from the characters, and experience lesser enjoyment and perceived realism when exposed to actual brands in a movie, they still hold positive alcohol expectancies and are more likely to select the placed brand, a process consistent with social cognitive theory. The findings suggest caution about the recommended policy of removing branding from alcohol placements, such as in the case with plain packaging in tobacco, and instead call for effective policies to constrain alcohol product placement, as was done with tobacco placements. © 2018 Australasian Professional Society on Alcohol and other Drugs.

Thiol dioxygenase turnover yields benzothiazole products from 2-mercaptoaniline and O2-dependent oxidation of primary alcohols.

PubMed

Morrow, William P; Sardar, Sinjinee; Thapa, Pawan; Hossain, Mohammad S; Foss, Frank W; Pierce, Brad S

2017-10-01

Thiol dioxygenases are non-heme mononuclear iron enzymes that catalyze the O 2 -dependent oxidation of free thiols (-SH) to produce the corresponding sulfinic acid (-SO 2 - ). Previous chemical rescue studies identified a putative Fe III -O 2 - intermediate that precedes substrate oxidation in Mus musculus cysteine dioxygenase (Mm CDO). Given that a similar reactive intermediate has been identified in the extradiol dioxygenase 2, 3-HCPD, it is conceivable that these enzymes share other mechanistic features with regard to substrate oxidation. To explore this possibility, enzymatic reactions with Mm CDO (as well as the bacterial 3-mercaptopropionic acid dioxygenase, Av MDO) were performed using a substrate analogue (2-mercaptoaniline, 2ma). This aromatic thiol closely approximates the catecholic substrate of homoprotocatechuate of 2, 3-HPCD while maintaining the 2-carbon thiol-amine separation preferred by Mm CDO. Remarkably, both enzymes exhibit 2ma-gated O 2 -consumption; however, none of the expected products for thiol dioxygenase or intra/extradiol dioxygenase reactions were observed. Instead, benzothiazoles are produced by the condensation of 2ma with aldehydes formed by an off-pathway oxidation of primary alcohols added to aqueous reactions to solubilize the substrate. The observed oxidation of 1º-alcohols in 2ma-reactions is consistent with the formation of a high-valent intermediate similar to what has been reported for cytochrome P450 and mononuclear iron model complexes. Copyright © 2017 Elsevier Inc. All rights reserved.

Na@SiO2-Mediated Addition of Organohalides to Carbonyl Compounds for the Formation of Alcohols and Epoxides

NASA Astrophysics Data System (ADS)

Kapoor, Mohit; Hwu, Jih Ru

2016-11-01

Alcohols and epoxides were generated by the addition of organohalides to carbonyl compounds in the presence of sodium metal impregnated with silica gel (Na@SiO2) in THF at 25 °C through a radical pathway. Under the same conditions, Schiff bases were also successfully converted to the corresponding amines. Furthermore, the reaction of aldehydes with α-haloesters or 4-(chloromethyl)-coumarin with the aid of Na@SiO2 generated trans epoxides. An unprecedented mechanism is proposed for their formation. The advantages associated with these new reactions include: (1) products are obtained in good-to-excellent yields, (2) reactions are completed at room temperatures in a short period of time (<2.0 h), (3) it is unnecessary to perform the reactions under anhydrous conditions, and (4) the entire process requires only simple manipulations.

Direct observation of redox reactions in Candida parapsilosis ATCC 7330 by Confocal microscopic studies.

PubMed

Venkataraman, Sowmyalakshmi; Narayan, Shoba; Chadha, Anju

2016-10-14

Confocal microscopic studies with the resting cells of yeast, Candida parapsilosis ATCC 7330, a reportedly versatile biocatalyst for redox enzyme mediated preparation of optically pure secondary alcohols in high optical purities [enantiomeric excess (ee) up to >99%] and yields, revealed that the yeast cells had large vacuoles under the experimental conditions studied where the redox reaction takes place. A novel fluorescence method was developed using 1-(6-methoxynaphthalen-2-yl)ethanol to track the site of biotransformation within the cells. This alcohol, itself non-fluorescent, gets oxidized to produce a fluorescent ketone, 1-(6-methoxynaphthalen-2-yl)ethanone. Kinetic studies showed that the reaction occurs spontaneously and the products get released out of the cells in less time [5 mins]. The biotransformation was validated using HPLC.

Manganese complex-catalyzed oxidation and oxidative kinetic resolution of secondary alcohols by hydrogen peroxide† †Electronic supplementary information (ESI) available: Tables S1–S4 and additional data: NMR spectra of the products, GC and HPLC chromatograms in the OKR of secondary alcohols, key geometric information for DFT, etc. See DOI: 10.1039/c7sc00891k Click here for additional data file.

PubMed Central

Miao, Chengxia; Li, Xiao-Xi; Lee, Yong-Min; Xia, Chungu; Wang, Yong

2017-01-01

The highly efficient catalytic oxidation and oxidative kinetic resolution (OKR) of secondary alcohols has been achieved using a synthetic manganese catalyst with low loading and hydrogen peroxide as an environmentally benign oxidant in the presence of a small amount of sulfuric acid as an additive. The product yields were high (up to 93%) for alcohol oxidation and the enantioselectivity was excellent (>90% ee) for the OKR of secondary alcohols. Mechanistic studies revealed that alcohol oxidation occurs via hydrogen atom (H-atom) abstraction from an α-CH bond of the alcohol substrate and a two-electron process by an electrophilic Mn–oxo species. Density functional theory calculations revealed the difference in reaction energy barriers for H-atom abstraction from the α-CH bonds of R- and S-enantiomers by a chiral high-valent manganese–oxo complex, supporting the experimental result from the OKR of secondary alcohols. PMID:29163900

Coupled reactions on bioparticles: Stereoselective reduction with cofactor regeneration on PhaC inclusion bodies.

PubMed

Spieler, Valerie; Valldorf, Bernhard; Maaß, Franziska; Kleinschek, Alexander; Hüttenhain, Stefan H; Kolmar, Harald

2016-07-01

Chiral alcohols are important building blocks for specialty chemicals and pharmaceuticals. The production of chiral alcohols from ketones can be carried out stereo selectively with alcohol dehydrogenases (ADHs). To establish a process for cost-effective enzyme immobilization on solid phase for application in ketone reduction, we used an established enzyme pair consisting of ADH from Rhodococcus erythropolis and formate dehydrogenase (FDH) from Candida boidinii for NADH cofactor regeneration and co-immobilized them on modified poly-p-hydroxybutyrate synthase (PhaC)-inclusion bodies that were recombinantly produced in Escherichia coli cells. After separate production of genetically engineered and recombinantly produced enzymes and particles, cell lysates were combined and enzymes endowed with a Kcoil were captured on the surface of the Ecoil presenting particles due to coiled-coil interaction. Enzyme-loaded particles could be easily purified by centrifugation. Total conversion of 4'-chloroacetophenone to (S)-4-chloro-α-methylbenzyl alcohol could be accomplished using enzyme-loaded particles, catalytic amounts of NAD(+) and formate as substrates for FDH. Chiral GC-MS analysis revealed that immobilized ADH retained enantioselectivity with 99 % enantiomeric excess. In conclusion, this strategy may become a cost-effective alternative to coupled reactions using purified enzymes. Copyright © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Kinetics and mechanism of the condensation of pyridoxal hydrochloride with L-tryptophan and D-tryptophan, and the chemical transformation of their products

NASA Astrophysics Data System (ADS)

Pishchugin, F. V.; Tuleberdiev, I. T.

2017-10-01

The kinetics and mechanism of interaction between pyridoxal and L-tryptophan, D-tryptophan, and their derivatives are studied. It is found that condensation reactions proceed via three kinetically distinguishable stages: (1) the rapid intraplanar addition of the NH2 groups of the amino acids to pyridoxal with the formation of amino alcohols; (2) the rotational isomerism of amino alcohol fragments with their subsequent dehydration and the formation of a Schiff base with a specific configuration; (3) the abstraction of α-hydrogen in the product of condensation of pyridoxal with L-tryptophan, or the abstraction of CO2 in the product of condensation of pyridoxal with D-tryptophan with the formation of quinoid structures, hydrolysis of which results in the preparation of pyridoxamine and keto acid or pyridoxal and tryptamine, respectively. Schiff bases resistant to further chemical transformations are formed in the reaction with tryptophan methyl ester.

Synthesis of 1,4-amino alcohols by Grignard reagent addition to THF and N-tosyliminobenzyliodinane.

PubMed

Tejo, Ciputra; See, Yang Feng Anders; Mathiew, Mitch; Chan, Philip Wai Hong

2016-01-21

The synthesis of 1,4-amino alcohols from THF treated with N-tosyliminobenzyliodinane (PhINTs) followed by a Grignard reagent under mild reaction conditions at room temperature is described herein. Various Grignard reagents were shown to be compatible, furnishing the corresponding 4-substituted-N-1,4-tosylamino alcohols in good to excellent yields. A partial or full detosylation of the N-tosyl-1,4-amino alcohol was observed in instances involving a sterically bulky Grignard reagent, leading to the deprotected 1,4-amino alcohol product in moderate to good yields. The synthetic utility of this protocol was demonstrated by the synthesis of a 5-substituted-N-tosyl-1,5-amino alcohol from THP and the conversion of two examples to their corresponding γ-lactam and pyrrolidine adducts.

Study of a specific lignin model: γ-oxidation and how it influences the hydrolysis efficiency of alcohol-aldehyde dehydrogenation copolymers.

PubMed

Bouxin, Florent; Baumberger, Stéphanie; Renault, Jean-Hugues; Dole, Patrice

2011-05-01

Six coniferyl alcohol-coniferaldehyde dehydrogenation copolymers (DHcoPs) were synthesized in order to determine the influence of an increased number of aldehyde functions on hydrolysis. After heterogeneous hydrolysis using acidic Montmorillonite K10 clay, the DHcoPs were thioacidolyzed and analyzed by gel permeation chromatography (GPC). Comparison of the thioacidolyzed products, with and without the hydrolysis step, showed that there was a greater proportion of condensation reaction in the absence of aldehyde. When the coniferaldehyde content in the initial synthetic mixture was more than 30% (w/w), only a low fraction of condensed products was generated during the K10 clay hydrolysis step. This suggests that condensation pathways are mainly due to the alcohol present in the γ-position in the DHcoPs. Investigation of the reactivity and the potential condensation of aldehyde and alcohol monomers under hydrolysis conditions showed the important conversion of coniferyl alcohol and conversely the stability of coniferaldehyde. Copyright © 2011 Elsevier Ltd. All rights reserved.

Enzymatic production of biodiesel from microalgal oil using ethyl acetate as an acyl acceptor.

PubMed

Alavijeh, Razieh Shafiee; Tabandeh, Fatemeh; Tavakoli, Omid; Karkhane, Aliasghar; Shariati, Parvin

2015-01-01

Microalgae have become an important source of biomass for biodiesel production. In enzymatic transesterification reaction, the enzyme activity is decreased in presence of alcohols. The use of different acyl acceptors such as methyl/ethyl acetate is suggested as an alternative and effective way to overcome this problem. In this study, ethyl acetate was used for the first time in the enzymatic production of biodiesel by using microalga, Chlorella vulgaris, as a triglyceride source. Enzymatic conversion of such fatty acids to biodiesel was catalyzed by Novozym 435 as an efficient immobilized lipase which is extensively used in biodiesel production. The best conversion yield of 66.71% was obtained at the ethyl acetate to oil molar ratio of 13:1 and Novozym 435 concentration of 40%, based on the amount of oil, and a time period of 72 h at 40℃. The results showed that ethyl acetate have no adverse effect on lipase activity and the biodiesel amount was not decreased even after seven transesterification cycles, so ethyl acetate has a great potential to be substituted for short-chain alcohols in transesterification reaction.

Suitability of the hydrocarbon-hydroxylating molybdenum-enzyme ethylbenzene dehydrogenase for industrial chiral alcohol production.

PubMed

Tataruch, M; Heider, J; Bryjak, J; Nowak, P; Knack, D; Czerniak, A; Liesiene, J; Szaleniec, M

2014-12-20

The molybdenum/iron-sulfur/heme protein ethylbenzene dehydrogenase (EbDH) was successfully applied to catalyze enantiospecific hydroxylation of alkylaromatic and alkylheterocyclic compounds. The optimization of the synthetic procedure involves use of the enzyme in a crude purification state that saves significant preparation effort and is more stable than purified EbDH without exhibiting unwanted side reactions. Moreover, immobilization of the enzyme on a crystalline cellulose support and changes in reaction conditions were introduced in order to increase the amounts of product formed (anaerobic atmosphere, electrochemical electron acceptor recycling or utilization of ferricyanide as alternative electron acceptor in high concentrations). We report here on an extension of effective enzyme activity from 4h to more than 10 days and final product yields of up to 0.4-0.5g/l, which represent a decent starting point for further optimization. Therefore, we expect that the hydrocarbon-hydroxylation capabilities of EbDH may be developed into a new process of industrial production of chiral alcohols. Copyright © 2014 Elsevier B.V. All rights reserved.

An optimized two-step derivatization method for analyzing diethylene glycol ozonation products using gas chromatography and mass spectrometry.

PubMed

Yu, Ran; Duan, Lei; Jiang, Jingkun; Hao, Jiming

2017-03-01

The ozonation of hydroxyl compounds (e.g., sugars and alcohols) gives a broad range of products such as alcohols, aldehydes, ketones, and carboxylic acids. This study developed and optimized a two-step derivatization procedure for analyzing polar products of aldehydes and carboxylic acids from the ozonation of diethylene glycol (DEG) in a non-aqueous environment using gas chromatography-mass spectrometry. Experiments based on Central Composite Design with response surface methodology were carried out to evaluate the effects of derivatization variables and their interactions on the analysis. The most desirable derivatization conditions were reported, i.e., oximation was performed at room temperature overnight with the o-(2,3,4,5,6-pentafluorobenzyl) hydroxyl amine to analyte molar ratio of 6, silylation reaction temperature of 70°C, reaction duration of 70min, and N,O-bis(trimethylsilyl)-trifluoroacetamide volume of 12.5μL. The applicability of this optimized procedure was verified by analyzing DEG ozonation products in an ultrafine condensation particle counter simulation system. Copyright © 2016. Published by Elsevier B.V.

An experimental and theoretical study of reaction mechanisms between nitriles and hydroxylamine.

PubMed

Vörös, Attila; Mucsi, Zoltán; Baán, Zoltán; Timári, Géza; Hermecz, István; Mizsey, Péter; Finta, Zoltán

2014-10-28

The industrially relevant reaction between nitriles and hydroxylamine yielding amidoximes was studied in different molecular solvents and in ionic liquids. In industry, this procedure is carried out on the ton scale in alcohol solutions and the above transformation produces a significant amount of unexpected amide by-product, depending on the nature of the nitrile, which can cause further analytical and purification issues. Although there were earlier attempts to propose mechanisms for this transformation, the real reaction pathway is still under discussion. A new detailed reaction mechanistic explanation, based on theoretical and experimental proof, is given to augment the former mechanisms, which allowed us to find a more efficient, side-product free procedure. Interpreting the theoretical results obtained, it was shown that the application of specific imidazolium, phosphonium and quaternary ammonium based ionic liquids could decrease simultaneously the reaction time while eliminating the amide side-product, leading to the targeted product selectively. This robust and economic procedure now affords a fast, selective amide free synthesis of amidoximes.

Modified reaction mechanism of aerated n-dodecane liquid flowing over heated metal tubes

NASA Technical Reports Server (NTRS)

Reddy, K. T.; Cernansky, N. P.; Cohen, R. S.

1988-01-01

The degradation mechanism of the n-dodecane was studied using a modified jet fuel thermal oxidation tester containing a sample withdrawal system as a reaction vessel. The reaction products were identified using gas chromatography and mass spectorometry. The soluble products were found to consist mainly of C5-C10 n-alkanes and 1-alkenes, C7-C10 aldehydes, tetrahydrofuran derivatives, dodecanol and dodecanone isomers, dodecyl hydroperoxide (ROOH) decomposition products, and C24 alkane isomers. The data from the experiments agreed with those of Hazlett et al. (1977). It was found that alkyl peroxide radical reactions dominate in the autooxidation temperature regime (at T not above 300 C); the dominant path is for the alkyl peroxyl radical to react bimolecularly with fuel to yield primarily alkyl hydroperoxides. The alkyl peroxide radical also undergoes self-termination and unimolecular isomerization and decomposition reactions, to yield smaller amounts of C12 alcohol plus ketone products and tetrahydrofuran derivatives, respectively.

A facile microwave-assisted Diels-Alder reaction of vinylboronates.

PubMed

Sarotti, Ariel M; Pisano, Pablo L; Pellegrinet, Silvina C

2010-11-21

The Diels-Alder reaction of vinylboronates can be easily performed using microwave irradiation giving excellent yields of the cycloadducts. Pinacol vinylboronate was the reagent of choice due to its stability towards hydrolysis, operational simplicity and yields of Diels-Alder products. To the best of our knowledge, this is the first example of microwave-assisted Diels-Alder reaction of boron-substituted dienophiles. Subsequent in situ oxidation of the cycloadducts with alkaline hydrogen peroxide afforded the alcohols efficiently.

Reactions of hydroxyalkyl radicals with cysteinyl peptides in a nanoESI plume.

PubMed

Stinson, Craig A; Xia, Yu

2014-07-01

In biological systems, carbon-centered small molecule radicals are primarily formed via external radiation or internal radical reactions. These radical species can react with a variety of biomolecules, most notably nucleic acids, the consequence of which has possible links to gene mutation and cancer. Sulfur-containing peptides and proteins are reactive toward a variety of radical species and many of them behave as radical scavengers. In this study, the reactions between alkyl alcohol carbon-centered radicals (e.g., •CH2OH for methanol) and cysteinyl peptides within a nanoelectrospray ionization (nanoESI) plume were explored. The reaction system involved ultraviolet (UV) irradiation of a nanoESI plume using a low pressure mercury lamp consisting of 185 and 254 nm emission bands. The alkyl alcohol was added as solvent into the nanoESI solution and served as the precursor of hydroxyalkyl radicals upon UV irradiation. The hydroxyalkyl radicals subsequently reacted with cysteinyl peptides either containing a disulfide linkage or free thiol, which led to the formation of peptide-S-hydroxyalkyl product. This radical reaction coupled with subsequent MS/MS was shown to have analytical potential by cleaving intrachain disulfide linked peptides prior to CID to enhance sequence information. Tandem mass spectrometry via collision-induced dissociation (CID), stable isotope labeling, and accurate mass measurement were employed to verify the identities of the reaction products.

Reactions of Hydroxyalkyl Radicals with Cysteinyl Peptides in a NanoESI Plume

NASA Astrophysics Data System (ADS)

Stinson, Craig A.; Xia, Yu

2014-07-01

In biological systems, carbon-centered small molecule radicals are primarily formed via external radiation or internal radical reactions. These radical species can react with a variety of biomolecules, most notably nucleic acids, the consequence of which has possible links to gene mutation and cancer. Sulfur-containing peptides and proteins are reactive toward a variety of radical species and many of them behave as radical scavengers. In this study, the reactions between alkyl alcohol carbon-centered radicals (e.g., •CH2OH for methanol) and cysteinyl peptides within a nanoelectrospray ionization (nanoESI) plume were explored. The reaction system involved ultraviolet (UV) irradiation of a nanoESI plume using a low pressure mercury lamp consisting of 185 and 254 nm emission bands. The alkyl alcohol was added as solvent into the nanoESI solution and served as the precursor of hydroxyalkyl radicals upon UV irradiation. The hydroxyalkyl radicals subsequently reacted with cysteinyl peptides either containing a disulfide linkage or free thiol, which led to the formation of peptide- S-hydroxyalkyl product. This radical reaction coupled with subsequent MS/MS was shown to have analytical potential by cleaving intrachain disulfide linked peptides prior to CID to enhance sequence information. Tandem mass spectrometry via collision-induced dissociation (CID), stable isotope labeling, and accurate mass measurement were employed to verify the identities of the reaction products.

Role of solid acid catalysts in bio diesel production.

PubMed

Shivayogimath, C B; Sunita, G; Manoj Kumar, B

2009-07-01

Biodiesel is gaining importance as an alternate source of attractive fuel because of depleting fossil fuel resources. It is produced by trans-esterification, in which oil or fat reacts with a monohydric alcohol in presence of a catalyst. In the present work, trans-esterification of sunflower oil with methanol is carried out by using zirconia supported isopoly and heteropoly tungstates (HPAs) as catalysts. Effects of reaction parameters, such as catalyst types and its concentration, molar ratio of sunflower oil to methanol, reaction temperature and time, have been optimized to get higher conversion of sunflower oil and the product distribution of fatty acid methyl esters (FAME) in the trans-esterfication reaction.

Enzymatic Addition of Alcohols to Terpenes by Squalene Hopene Cyclase Variants.

PubMed

Kühnel, Lisa C; Nestl, Bettina M; Hauer, Bernhard

2017-11-16

Squalene-hopene cyclases (SHCs) catalyze the polycyclization of squalene into a mixture of hopene and hopanol. Recently, amino-acid residues lining the catalytic cavity of the SHC from Alicyclobacillus acidocaldarius were replaced by small and large hydrophobic amino acids. The alteration of leucine 607 to phenylalanine resulted in increased enzymatic activity towards the formation of an intermolecular farnesyl-farnesyl ether product from farnesol. Furthermore, the addition of small-chain alcohols acting as nucleophiles led to the formation of non-natural ether-linked terpenoids and, thus, to significant alteration of the product pattern relative to that obtained with the wild type. It is proposed that the mutation of leucine at position 607 may facilitate premature quenching of the intermediate by small alcohol nucleophiles. This mutagenesis-based study opens the field for further intermolecular bond-forming reactions and the generation of non-natural products. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

PubMed

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

2018-06-23

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

Catalysts for the production of hydrocarbons from carbon monoxide and water

DOEpatents

Sapienza, Richard S.; Slegeir, William A.; Goldberg, Robert I.

1987-04-07

A method of converting low H.sub.2 /CO ratio syngas to carbonaceous products comprising reacting the syngas with water or steam at 200.degree. to 350.degree. C. in the presence of a metal catalyst supported on zinc oxide. Hydrocarbons are produced with a catalyst selected from cobalt, nickel or ruthenium and alcohols are produced with a catalyst selected from palladium, platinium, ruthenium or copper on the zinc oxide support. The ratio of the reactants are such that for alcohols and saturated hydrocarbons: and for olefinic hydrocarbons: where n is the number of carbon atoms in the product and x is the molar amount of water in the reaction mixture.

Visible Light Organic Photoredox-Catalyzed C-H Alkoxylation of Imidazopyridine with Alcohol.

PubMed

Kibriya, Golam; Samanta, Sadhanendu; Jana, Sourav; Mondal, Susmita; Hajra, Alakananda

2017-12-15

The visible light-mediated C-3 alkoxylation of imidazopyridines with alcohols has been achieved using rose bengal as an organic photoredox catalyst at room temperature. Widely abundant air acts as the terminal oxidant that avoids the use of a stoichiometric amount of peroxo compounds. A wide range of functional groups could be tolerated under the reaction conditions to produce C(sp 2 )-H alkoxylated products in high yields.

Changes in cinnamyl alcohol dehydrogenase activities from sugarcane cultivars inoculated with Sporisorium scitamineum sporidia.

PubMed

Santiago, Rocío; Alarcón, Borja; de Armas, Roberto; Vicente, Carlos; Legaz, María Estrella

2012-06-01

This study describes a method for determining cinnamyl alcohol dehydrogenase activity in sugarcane stems using reverse phase (RP) high-performance liquid chromatography to elucidate their possible lignin origin. Activity is assayed using the reverse mode, the oxidation of hydroxycinnamyl alcohols into hydroxycinnamyl aldehydes. Appearance of the reaction products, coniferaldehyde and sinapaldehyde is determined by measuring absorbance at 340 and 345 nm, respectively. Disappearance of substrates, coniferyl alcohol and sinapyl alcohol is measured at 263 and 273 nm, respectively. Isocratic elution with acetonitrile:acetic acid through an RP Mediterranea sea C18 column is performed. As case examples, we have examined two different cultivars of sugarcane; My 5514 is resistant to smut, whereas B 42231 is susceptible to the pathogen. Inoculation of sugarcane stems elicits lignification and produces significant increases of coniferyl alcohol dehydrogenase (CAD) and sinapyl alcohol dehydrogenase (SAD). Production of lignin increases about 29% in the resistant cultivar and only 13% in the susceptible cultivar after inoculation compared to uninoculated plants. Our results show that the resistance of My 5514 to smut is likely derived, at least in part, to a marked increase of lignin concentration by the activation of CAD and SAD. Copyright © Physiologia Plantarum 2012.

Extraction photometric determination of yperite by phthaleins.

PubMed

Halámek, E; Kobliha, Z

1999-01-01

Extraction spectrophotometric determination of sulfidic yperite, based on the reaction with four phthaleins, was developed. The method is technically simpler than the determination of yperites with reagent T-135 (alkaline-aqueous ethanolic thymolphthalein solution) because it does not require heating at 80 degrees C, cooling and acidification of the reaction mixture. Selection of the appropriate phthalein, and particularly optimization of the reagent composition and extraction of the coloured reaction product in chloroform, markedly increased the selectivity of the determination of yperites (HD, HN-3). The reaction is performed in a medium of increased polarity due to the low content of alcohol which enables the reaction to proceed at temperatures of 5-20 degrees C without any marked loss of sensitivity. Using (1)H and (13)C NMR spectroscopy, the reaction products of HD and o-cresolphthalein were identified and an ionic mechanism for the reaction of HD with phthaleins is suggested.

Catalytic conversion of alcohols to hydrocarbons with low benzene content

DOEpatents

Narula, Chaitanya K.; Davison, Brian H.; Keller, Martin

2016-09-06

A method for converting an alcohol to a hydrocarbon fraction having a lowered benzene content, the method comprising: converting said alcohol to a hydrocarbon fraction by contacting said alcohol, under conditions suitable for converting said alcohol to said hydrocarbon fraction, with a metal-loaded zeolite catalyst catalytically active for converting said alcohol to said hydrocarbon fraction, and contacting said hydrocarbon fraction with a benzene alkylation catalyst, under conditions suitable for alkylating benzene, to form alkylated benzene product in said hydrocarbon fraction. Also described is a catalyst composition useful in the method, comprising a mixture of (i) a metal-loaded zeolite catalyst catalytically active for converting said alcohol to said hydrocarbon, and (ii) a benzene alkylation catalyst, in which (i) and (ii) may be in a mixed or separated state. A reactor for housing the catalyst and conducting the reaction is also described.

Catalytic conversion of alcohols to hydrocarbons with low benzene content

DOEpatents

Narula, Chaitanya K.; Davison, Brian H.; Keller, Martin

2016-03-08

A method for converting an alcohol to a hydrocarbon fraction having a lowered benzene content, the method comprising: converting said alcohol to a hydrocarbon fraction by contacting said alcohol, under conditions suitable for converting said alcohol to said hydrocarbon fraction, with a metal-loaded zeolite catalyst catalytically active for converting said alcohol to said hydrocarbon fraction, and contacting said hydrocarbon fraction with a benzene alkylation catalyst, under conditions suitable for alkylating benzene, to form alkylated benzene product in said hydrocarbon fraction. Also described is a catalyst composition useful in the method, comprising a mixture of (i) a metal-loaded zeolite catalyst catalytically active for converting said alcohol to said hydrocarbon, and (ii) a benzene alkylation catalyst, in which (i) and (ii) may be in a mixed or separated state. A reactor for housing the catalyst and conducting the reaction is also described.

Manganese complex-catalyzed oxidation and oxidative kinetic resolution of secondary alcohols by hydrogen peroxide.

PubMed

Miao, Chengxia; Li, Xiao-Xi; Lee, Yong-Min; Xia, Chungu; Wang, Yong; Nam, Wonwoo; Sun, Wei

2017-11-01

The highly efficient catalytic oxidation and oxidative kinetic resolution (OKR) of secondary alcohols has been achieved using a synthetic manganese catalyst with low loading and hydrogen peroxide as an environmentally benign oxidant in the presence of a small amount of sulfuric acid as an additive. The product yields were high (up to 93%) for alcohol oxidation and the enantioselectivity was excellent (>90% ee) for the OKR of secondary alcohols. Mechanistic studies revealed that alcohol oxidation occurs via hydrogen atom (H-atom) abstraction from an α-CH bond of the alcohol substrate and a two-electron process by an electrophilic Mn-oxo species. Density functional theory calculations revealed the difference in reaction energy barriers for H-atom abstraction from the α-CH bonds of R - and S -enantiomers by a chiral high-valent manganese-oxo complex, supporting the experimental result from the OKR of secondary alcohols.

Direct esterification of ammonium salts of carboxylic acids

DOEpatents

Halpern, Yuval [Skokie, IL

2003-06-24

A non-catalytic process for producing esters, the process comprising reacting an ammonium salt of a carboxylic acid with an alcohol and removing ammonia from the reaction mixture. Selectivities for the desired ester product can exceed 95 percent.

Real World of Industrial Chemistry: The SHOP Process: An Example of Industrial Creativity.

ERIC Educational Resources Information Center

Reuben, Bryan; Wittcoff, Harold

1988-01-01

Discusses the Shell Higher Olefins Process (SHOP) in the manufacture of primary C11-C15 fatty alcohols. Offers examples and explanations of the four-step process. Gives uses for reaction products. (ML)

Tuning the catalytic CO hydrogenation to straight- and long-chain aldehydes/alcohols and olefins/paraffins

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

Xiang, Yizhi; Kruse, Norbert

Here, the catalytic CO hydrogenation is one of the most versatile large-scale chemical syntheses leading to variable chemical feedstock. While traditionally mainly methanol and long-chain hydrocarbons are produced by CO hydrogenation, here we show that the same reaction can be tuned to produce long-chain n-aldehydes, 1-alcohols and olefins, as well as n-paraffins over potassium-promoted CoMn catalysts. The sum selectivity of aldehydes and alcohols is usually >50 wt% whereof up to ~97% can be n-aldehydes. While the product slate contains ~60% n-aldehydes at /p CO=0.5, a 65/35% slate of paraffins/alcohols is obtained at a ratio of 9. A linear Anderson–Schulz–Flory behaviour,more » independent of the /p CO ratio, is found for the sum of C 4+ products. We advocate a synergistic interaction between a Mn 5O 8 oxide and a bulk Co 2C phase, promoted by the presence of potassium, to be responsible for the unique product spectra in our studies.« less

Tuning the catalytic CO hydrogenation to straight- and long-chain aldehydes/alcohols and olefins/paraffins

DOE PAGES

Xiang, Yizhi; Kruse, Norbert

2016-10-06

Here, the catalytic CO hydrogenation is one of the most versatile large-scale chemical syntheses leading to variable chemical feedstock. While traditionally mainly methanol and long-chain hydrocarbons are produced by CO hydrogenation, here we show that the same reaction can be tuned to produce long-chain n-aldehydes, 1-alcohols and olefins, as well as n-paraffins over potassium-promoted CoMn catalysts. The sum selectivity of aldehydes and alcohols is usually >50 wt% whereof up to ~97% can be n-aldehydes. While the product slate contains ~60% n-aldehydes at /p CO=0.5, a 65/35% slate of paraffins/alcohols is obtained at a ratio of 9. A linear Anderson–Schulz–Flory behaviour,more » independent of the /p CO ratio, is found for the sum of C 4+ products. We advocate a synergistic interaction between a Mn 5O 8 oxide and a bulk Co 2C phase, promoted by the presence of potassium, to be responsible for the unique product spectra in our studies.« less

Regio- and Stereospecific Formation of Protected Allylic Alcohols via Zirconium-Mediated SN2' Substitution of Allylic Chlorides

PubMed Central

Fox, Richard J.; Lalic, Gojko; Bergman, Robert G.

2008-01-01

A new, highly regio- and stereospecific SN2' substitution reaction between a zirconium oxo complex and allylic chloride has been achieved. The resulting allylic alcohol or TBS-protected allylic ether products were isolated in good to excellent yields with a wide range of E-allylic chlorides. A mechanism for the SN2' allylic substitution consistent with kinetic, stereochemical and secondary isotope effect studies was proposed. PMID:17973391

Mechanistic studies on covalent assemblies of metal-mediated hemi-aminal ethers† †Electronic supplementary information (ESI) available. CCDC 1018457. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c4sc02495h Click here for additional data file. Click here for additional data file. Click here for additional data file.

PubMed Central

Jo, Hyun Hwa; Edupuganti, Ramakrishna; You, Lei; Dalby, Kevin N.

2015-01-01

The use of reversible covalent bonding in a four-component assembly incorporating chiral alcohols was recently reported to give a method for determining the enantiomeric excess of the alcohols via CD spectroscopy. Experiments that probe the mechanism of this assembly, which consists of 2-formylpyridine (2-PA), dipicolylamine (DPA), Zn(ii) and alcohols to yield zinc complexes of tren-like ligands, are presented. The studies focus upon the mechanism of conversion of a hemi-aminal (1) to a hemi-aminal ether (3), thereby incorporating the fourth component. It was found that molecular sieves along with 3 to 4 equivalents of alcohol are required to drive the conversion of 1 to 3. Attempts to isolate an intermediate in this reaction via addition of strong Lewis acids led to the discovery of a five-membered ring pyridinium salt (5), but upon exposure to Zn(ii) and alcohols gave different products to the assembly. This was interpreted to support the intermediacy of an iminium species. Kinetic studies reveal that the conversion of 1 to 3 is zero-order in alcohol in large excesses of alcohol, supporting rate-determining formation of an intermediate prior to reaction with alcohol. Further, the magnitudes of the rate constants for interconversion of 1 and 3 are similar, supporting the notion that there are similar rate-determining steps (rds) for the forward and reverse reactions. Hammett plots show that the rds involves creation of a negative charge (interpreted as the loss of positive charge), supporting the notion that the decomplexation of Zn(ii) from the assemblies to generate apo-forms of 1 and 3 is rate-determining. The individual mechanistic conclusions are combined to create a qualitative reaction coordinate diagram for the interconversion of 1 and 3. PMID:25530834

Green Synthesis of a Fluorescent Natural Product

ERIC Educational Resources Information Center

Young, Douglas M.; Welker, Jacob J. C.; Doxsee, Kenneth M.

2011-01-01

Synthesis of 4-methylumbelliferone via the acid-catalyzed Pechmann condensation introduces students to several types of organic reactions: transesterification, electrophilic aromatic substitution, and alcohol dehydration. Performed with a recyclable, solid catalyst and under solvent-free conditions, the experiment illustrates many of the…

Catalytic Nucleophilic Glyoxylation of Aldehydes

PubMed Central

Steward, Kimberly M.; Johnson, Jeffrey S.

2010-01-01

β-Silyloxy-α-ketoesters are prepared through a cyanide-catalyzed benzoin-type reaction with silyl glyoxylates and aldehydes. The products undergo a dynamic kinetic resolution to provide enantioenriched orthogonally protected alcohols and can be converted to the corresponding β-silyloxy-α-aminoesters. PMID:20481613

Directing reaction pathways by catalyst active-site selection using self-assembled monolayers.

PubMed

Pang, Simon H; Schoenbaum, Carolyn A; Schwartz, Daniel K; Medlin, J Will

2013-01-01

One key route for controlling reaction selectivity in heterogeneous catalysis is to prepare catalysts that exhibit only specific types of sites required for desired product formation. Here we show that alkanethiolate self-assembled monolayers with varying surface densities can be used to tune selectivity to desired hydrogenation and hydrodeoxygenation products during the reaction of furfural on supported palladium catalysts. Vibrational spectroscopic studies demonstrate that the selectivity improvement is achieved by controlling the availability of specific sites for the hydrogenation of furfural on supported palladium catalysts through the selection of an appropriate alkanethiolate. Increasing self-assembled monolayer density by controlling the steric bulk of the organic tail ligand restricts adsorption on terrace sites and dramatically increases selectivity to desired products furfuryl alcohol and methylfuran. This technique of active-site selection simultaneously serves both to enhance selectivity and provide insight into the reaction mechanism.

Insulating Materials Comprising Polysilazane, Methods of Forming Such Insulating Materials, and Precursor Formulations Comprising Polysilazane

NASA Technical Reports Server (NTRS)

Larson, Robert S. (Inventor); Fuller, Michael E. (Inventor)

2013-01-01

Methods of forming an insulating material comprising combining a polysilazane, a cross-linking compound, and a gas-generating compound to form a reaction mixture, and curing the reaction mixture to form a modified polysilazane. The gas-generating compound may be water, an alcohol, an amine, or combinations thereof. The cross-linking compound may be an isocyanate, an epoxy resin, or combinations thereof. The insulating material may include a matrix comprising one of a reaction product of a polysilazane and an isocyanate and a reaction product of a polysilazane and an epoxy resin. The matrix also comprises a plurality of interconnected pores produced from one of reaction of the polysilazane and the isocyanate and from reaction of the polysilazane and the epoxy resin. A precursor formulation that comprises a polysilazane, a cross-linking compound, and a gas-generating compound is also disclosed.

Microwave assisted alkali-catalyzed transesterification of Pongamia pinnata seed oil for biodiesel production.

PubMed

Kumar, Ritesh; Kumar, G Ravi; Chandrashekar, N

2011-06-01

In this study, microwave assisted transesterification of Pongamia pinnata seed oil was carried out for the production of biodiesel. The experiments were carried out using methanol and two alkali catalysts i.e., sodium hydroxide (NaOH) and potassium hydroxide (KOH). The experiments were carried out at 6:1 alcohol/oil molar ratio and 60°C reaction temperature. The effect of catalyst concentration and reaction time on the yield and quality of biodiesel was studied. The result of the study suggested that 0.5% sodium hydroxide and 1.0% potassium hydroxide catalyst concentration were optimum for biodiesel production from P. pinnata oil under microwave heating. There was a significant reduction in reaction time for microwave induced transesterification as compared to conventional heating. Copyright © 2011 Elsevier Ltd. All rights reserved.

Catalytic total hydrodeoxygenation of biomass-derived polyfunctionalized substrates to alkanes.

PubMed

Nakagawa, Yoshinao; Liu, Sibao; Tamura, Masazumi; Tomishige, Keiichi

2015-04-13

The total hydrodeoxygenation of carbohydrate-derived molecules to alkanes, a key reaction in the production of biofuel, was reviewed from the aspect of catalysis. Noble metals (or Ni) and acid are the main components of the catalysts, and group 6 or 7 metals such as Re are sometimes added as modifiers of the noble metal. The main reaction route is acid-catalyzed dehydration plus metal-catalyzed hydrogenation, and in some systems metal-catalyzed direct CO dissociation is involved. The appropriate active metal, acid strength, and reaction conditions depend strongly on the reactivity of the substrate. Reactions that use Pt or Pd catalysts supported on Nb-based acids or relatively weak acids are suitable for furanic substrates. Carbohydrates themselves and sugar alcohols undergo CC dissociation easily. The systems that use metal-catalyzed direct CO dissociations can give a higher yield of the corresponding alkane from carbohydrates and sugar alcohols. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Efficient conversion of polyamides to ω-hydroxyalkanoic acids: a new method for chemical recycling of waste plastics.

PubMed

Kamimura, Akio; Ikeda, Kosuke; Suzuki, Shuzo; Kato, Kazunari; Akinari, Yugo; Sugimoto, Tsunemi; Kashiwagi, Kohichi; Kaiso, Kouji; Matsumoto, Hiroshi; Yoshimoto, Makoto

2014-09-01

An efficient transformation of polyamides to ω-hydroxy alkanoic acids was achieved. Treatment of nylon-12 with supercritical MeOH in the presence of glycolic acid gave methyl ω-hydroxydodecanoate in 85% yield and the alcohol/alkene selectivity in the product was enhanced to up to 9.5:1. The use of (18)O-enriched acetic acid for the reaction successfully introduced an (18)O atom at the alcoholic OH group in the product. This strategy may provide a new and economical solution for the chemical recycling of waste plastics. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bond formations by intermolecular and intramolecular trappings of acylketenes and their applications in natural product synthesis†

PubMed Central

Reber, Keith P.; Tilley, S. David

2011-01-01

The reactive intermediates known as acylketenes exhibit a rich chemistry and have been extensively utilized for many types of inter- and intramolecular bond-forming reactions within the field of organic synthesis. Characteristic reactions of acylketenes include cycloadditions, carbon–carbon bond-forming reactions, and nucleophilic capture with alcohols or amines to give β-keto acid derivatives. In particular, the intramolecular capture of acylketene intermediates with pendant nucleophiles represents a powerful method for forming both medium-sized rings and macrocycles, often in high yield. This tutorial review examines the history, generation, and reactivity of acylketenes with a special focus on their applications in the synthesis of natural products. PMID:19847338

Autonomously Propelled Motors for Value-Added Product Synthesis and Purification.

PubMed

Srivastava, Sarvesh K; Schmidt, Oliver G

2016-06-27

A proof-of-concept design for autonomous, self-propelling motors towards value-added product synthesis and separation is presented. The hybrid motor design consists of two distinct functional blocks. The first, a sodium borohydride (NaBH4 ) granule, serves both as a reaction prerequisite for the reduction of vanillin and also as a localized solid-state fuel in the reaction mixture. The second capping functional block consisting of a graphene-polymer composite serves as a hydrophobic matrix to attract the reaction product vanillyl alcohol (VA), resulting in facile separation of this edible value-added product. These autonomously propelled motors were fabricated at a length scale down to 400 μm, and once introduced in the reaction environment showed rapid bubble-propulsion followed by high-purity separation of the reaction product (VA) by the virtue of the graphene-polymer cap acting as a mesoporous sponge. The concept has excellent potential towards the synthesis/isolation of industrially important compounds, affinity-based product separation, pollutant remediation (such as heavy metal chelation/adsorption), as well as localized fuel-gradients as an alternative to external fuel dependency. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Copper(I)-catalyzed aryl bromides to form intermolecular and intramolecular carbon-oxygen bonds.

PubMed

Niu, Jiajia; Guo, Pengran; Kang, Juntao; Li, Zhigang; Xu, Jingwei; Hu, Shaojing

2009-07-17

A highly efficient Cu-catalyzed C-O bond-forming reaction of alcohol and aryl bromides has been developed. This transformation was realized through the use of copper(I) iodide as a catalyst, 8-hydroxyquinoline as a ligand, and K(3)PO(4) as a base. A variety of functionalized substrates were found to react under these reaction conditions to provide products in good to excellent yields.

Origin of the selectivity in the gold-mediated oxidation of benzyl alcohol

NASA Astrophysics Data System (ADS)

Rodríguez-Reyes, Juan Carlos F.; Friend, Cynthia M.; Madix, Robert J.

2012-08-01

Benzyl alcohol has received substantial attention as a probe molecule to test the selectivity and efficiency of novel metallic gold catalysts. Herein, the mechanisms of benzyl alcohol oxidation on a gold surface covered with atomic oxygen are elucidated; the results show direct correspondence to the reaction on gold-based catalysts. The selective, partial oxidation of benzyl alcohol to benzaldehyde is achieved with low oxygen surface concentrations and takes place through dehydrogenation of the alcohol to form benzaldehyde via a benzyloxy (C6H5-CH2O) intermediate. While in this case atomic oxygen plays solely a dehydrogenating role, at higher concentrations it leads to the formation of intermediates from benzaldehyde, producing benzoic acid and CO2. Facile ester (benzyl benzoate) formation also occurs at low oxygen concentrations, which indicates that benzoic acid is not a precursor of further oxidation of the ester; instead, the ester is produced by the coupling of adsorbed benzyloxy and benzaldehyde. Key to the high selectivity seen at low oxygen concentrations is the fact that the production of the aldehyde (and esters) is kinetically favored over the production of benzoic acid.

Organic reactions catalyzed by methylrhenium trioxide: Reactions of ethyl diazoacetate and organic azides

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

Zhu, Z.; Espenson, J.H.

1996-10-16

Methylrhenium trioxide (CH{sub 3}ReO{sub 3} or MTO) catalyzes several classes of reactions of ethyl diazoacetate, EDA. It is the first high valent oxo complex for carbene transfer. Under mild conditions and in the absence of other substrates, EDA was converted to a 9:1 mixture of diethyl maleate and diethyl fumarate. In the presence of alcohols, {alpha}-alkoxy ethyl acetates were obtained in good yield. The yields dropped for the larger and more branched alcohols, the balance of material being diethyl maleate and fumarate. An electron-donating group in the para position of phenols favors the formation of {alpha}-phenoxy ethyl acetates. The usemore » of EDA to form {alpha}-thio ethyl acetates and N-substituted glycine ethyl esters, on the other hand, is hardly affected by the size or structure of the parent thiol or amine, with all of these reactions proceeding in high yield. MTO-catalyzed cycloaddition reactions occur between EDA and aromatic imines, olefins, and carbonyl compounds. Three-membered ring products are formed: aziridines, cyclopropanes, and epoxides, respectively. The reactions favor the formation of trans products, and provide a convenient route for the preparation of aziridines. Intermediate carbenoid and nitrenoid species have been proposed. In the presence of an oxygen source such as an epoxide, ethyl diazoacetate and azibenzil are converted to an oxalic acid monoethyl ester and to benzil; at the same time the epoxide was converted to an olefin. 75 refs., 1 fig., 7 tabs.« less

Cu-catalyzed aerobic oxidative cyclizations of 3-N-hydroxyamino-1,2-propadienes with alcohols, thiols, and amines to form α-O-, S-, and N-substituted 4-methylquinoline derivatives.

PubMed

Sharma, Pankaj; Liu, Rai-Shung

2015-03-16

A one-pot, two-step synthesis of α-O-, S-, and N-substituted 4-methylquinoline derivatives through Cu-catalyzed aerobic oxidations of N-hydroxyaminoallenes with alcohols, thiols, and amines is described. This reaction sequence involves an initial oxidation of N-hydroxyaminoallenes with NuH (Nu = OH, OR, NHR, and SR) to form 3-substituted 2-en-1-ones, followed by Brønsted acid catalyzed intramolecular cyclizations of the resulting products. Our mechanistic analysis suggests that the reactions proceed through a radical-type mechanism rather than a typical nitrone-intermediate route. The utility of this new Cu-catalyzed reaction is shown by its applicability to the synthesis of several 2-amino-4-methylquinoline derivatives, which are known to be key precursors to several bioactive molecules. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Transformations of C2-C4 alcohols on the surface of a copper catalyst

NASA Astrophysics Data System (ADS)

Magaeva, A. A.; Lyamina, G. V.; Sudakova, N. N.; Shilyaeva, L. P.; Vodyankina, O. V.

2007-10-01

The interaction of monoatomic alcohols C2-C4 with the surface of a copper catalyst preliminarily oxidized under various conditions was studied by the temperature-programmed reaction method to determine the detailed mechanism of partial oxidation. The conditions of oxygen preadsorption on the surface of copper for the preparation of the desired products were determined. The selective formation of carbonyl compounds was shown to occur at the boundary between reduced and oxidized copper surface regions. The role played by Cu2O was the deep oxidation of alcohols to CO2. Alcohols with branched hydrocarbon structures experienced parallel partial oxidation and dehydrogenation, which was related to the high stability of intermediate keto-type compounds.

Radical Nature of C-Lignin

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

Berstis, Laura; Elder, Thomas; Crowley, Michael

The recently discovered lignin composed of caffeoyl alcohol monolignols or C-lignin is particularly intriguing given its homogeneous, linear polymeric structure and exclusive benzodioxane linkage between monomers. By virtue of this simplified chemistry, the potential emerges for improved valorization strategies with C-lignin relative to other natural heterogeneous lignins. To better understand caffeoyl alcohol polymers, we characterize the thermodynamics of the radical recombination dimerization reactions forming the benzodioxane linkage and the bond dissociation into radical monolignol products. These properties are also predicted for the cross-coupling of caffeoyl alcohol with the natural monolignols, coniferyl alcohol, sinapyl alcohol, and p-coumaryl alcohol, in anticipation of polymers potentially enabled by genetic modification. The average BDEs for the C-lignin benzodioxanemore » $$\\alpha$$- and β-bonds are 56.5 and 63.4 kcal/mol, respectively, with similar enthalpies for heterodimers. The BDE of the $$\\alpha$$-bond within the benzodioxane linkage is consistently greater than that of the β-bond in all dimers of each stereochemical arrangement, explained by the ability the $$\\alpha$$-carbon radical generated to delocalize onto the adjacent phenyl ring. Relative thermodynamics of the heterodimers demonstrates that the substituents on the phenyl ring directly neighboring the bond coupling the monolignols more strongly impact the dimer bond strengths and product stability, compared to the substituents present on the terminal phenyl ring. Enthalpy comparisons furthermore demonstrate that the erythro stereochemical configurations of the benzodioxane bond are slightly less thermodynamically stable than the threo configurations. The overall differences in strength of bonds and reaction enthalpies between stereoisomers are generally found to be insignificant, supporting that postcoupling rearomatization is under kinetic control. Projecting the lowest-energy stereoisomer internal coordinates to longer polymer C-lignin strands highlights how significantly the stereochemical outcomes in polymerization may impact the macromolecular structure and in turn material and chemical properties. Lastly, through these comparisons of geometry, bond strengths, and reaction enthalpies, we shed light on the distinctive properties of C-lignin's radical recombination and decomposition chemistry, and its potential as a natural lignin solution for biorefinery feedstocks and unique materials science applications.« less

Radical Nature of C-Lignin

DOE PAGES

Berstis, Laura; Elder, Thomas; Crowley, Michael; ...

2016-05-17

The recently discovered lignin composed of caffeoyl alcohol monolignols or C-lignin is particularly intriguing given its homogeneous, linear polymeric structure and exclusive benzodioxane linkage between monomers. By virtue of this simplified chemistry, the potential emerges for improved valorization strategies with C-lignin relative to other natural heterogeneous lignins. To better understand caffeoyl alcohol polymers, we characterize the thermodynamics of the radical recombination dimerization reactions forming the benzodioxane linkage and the bond dissociation into radical monolignol products. These properties are also predicted for the cross-coupling of caffeoyl alcohol with the natural monolignols, coniferyl alcohol, sinapyl alcohol, and p-coumaryl alcohol, in anticipation of polymers potentially enabled by genetic modification. The average BDEs for the C-lignin benzodioxanemore » $$\\alpha$$- and β-bonds are 56.5 and 63.4 kcal/mol, respectively, with similar enthalpies for heterodimers. The BDE of the $$\\alpha$$-bond within the benzodioxane linkage is consistently greater than that of the β-bond in all dimers of each stereochemical arrangement, explained by the ability the $$\\alpha$$-carbon radical generated to delocalize onto the adjacent phenyl ring. Relative thermodynamics of the heterodimers demonstrates that the substituents on the phenyl ring directly neighboring the bond coupling the monolignols more strongly impact the dimer bond strengths and product stability, compared to the substituents present on the terminal phenyl ring. Enthalpy comparisons furthermore demonstrate that the erythro stereochemical configurations of the benzodioxane bond are slightly less thermodynamically stable than the threo configurations. The overall differences in strength of bonds and reaction enthalpies between stereoisomers are generally found to be insignificant, supporting that postcoupling rearomatization is under kinetic control. Projecting the lowest-energy stereoisomer internal coordinates to longer polymer C-lignin strands highlights how significantly the stereochemical outcomes in polymerization may impact the macromolecular structure and in turn material and chemical properties. Lastly, through these comparisons of geometry, bond strengths, and reaction enthalpies, we shed light on the distinctive properties of C-lignin's radical recombination and decomposition chemistry, and its potential as a natural lignin solution for biorefinery feedstocks and unique materials science applications.« less

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

DOEpatents

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

1984-05-08

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

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

DOEpatents

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

1984-01-01

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

Endogenous ethanol affects biopolyester molecular weight in recombinant Escherichia coli.

PubMed

Hiroe, Ayaka; Hyakutake, Manami; Thomson, Nicholas M; Sivaniah, Easan; Tsuge, Takeharu

2013-11-15

In biopolyester synthesis, polyhydroxyalkanoate (PHA) synthase (PhaC) catalyzes the polymerization of PHA in bacterial cells, followed by a chain transfer (CT) reaction in which the PHA polymer chain is transferred from PhaC to a CT agent. Accordingly, the frequency of CT reaction determines PHA molecular weight. Previous studies have shown that exogenous alcohols are effective CT agents. This study aimed to clarify the effect of endogenous ethanol as a CT agent for poly[(R)-3-hydroxybutyrate] [P(3HB)] synthesis in recombinant Escherichia coli, by comparing with that of exogenous ethanol. Ethanol supplementation to the culture medium reduced P(3HB) molecular weights by up to 56% due to ethanol-induced CT reaction. NMR analysis of P(3HB) polymers purified from the culture supplemented with (13)C-labeled ethanol showed the formation of a covalent bond between ethanol and P(3HB) chain at the carboxyl end. Cultivation without ethanol supplementation resulted in the reduction of P(3HB) molecular weight with increasing host-produced ethanol depending on culture aeration. On the other hand, production in recombinant BW25113(ΔadhE), an alcohol dehydrogenase deletion strain, resulted in a 77% increase in molecular weight. Analysis of five E. coli strains revealed that the estimated number of CT reactions was correlated with ethanol production. These results demonstrate that host-produced ethanol acts as an equally effective CT agent as exogenous ethanol, and the control of ethanol production is important to regulate the PHA molecular weight.

One-Pot Multicomponent Coupling Methods for the Synthesis of Diastereo- and Enantioenriched (Z)-Trisubstituted Allylic Alcohols

PubMed Central

Kerrigan, Michael H.; Jeon, Sang-Jin; Chen, Young K.; Salvi, Luca; Carroll, Patrick J.; Walsh, Patrick J.

2009-01-01

(Z)-Trisubstituted allylic alcohols are widespread structural motifs in natural products and biologically active compounds but are difficult to directly prepare. Introduced herein is a general one-pot multicomponent coupling method for the synthesis of (Z)-α,α,β-trisubstituted allylic alcohols. (Z)-Trisubstituted vinylzinc reagents are formed in situ by initial hydroboration of 1-bromo-1-alkynes. Addition of dialkylzinc reagents induces a 1,2-metallate rearrangement that is followed by a boron-to-zinc transmetallation. The resulting vinylzinc reagents add to a variety of prochiral aldehydes to produce racemic (Z)-trisubstituted allylic alcohols. When enantioenriched aldehyde substrates are employed (Z)-trisubstituted allylic alcohols are isolated with high dr (>20:1 in many cases). For example, vinylation of enantioenriched benzyl protected α- and β-hydroxy propanal derivatives furnished the expected anti-Felkin addition products via chelation control. Surprisingly, silyl protected α-hydroxy aldehydes also afford anti-Felkin addition products. A protocol for the catalytic asymmetric addition of (Z)-trisubstituted vinylzinc reagents to prochiral aldehydes with a (−)-MIB-based catalyst has also been developed. Several additives were investigated as inhibitors of the Lewis acidic alkylzinc halide byproducts, which promote the background reaction to form the racemate. α-Ethyl and α-cyclohexyl (Z)-trisubstituted allylic alcohols can now be synthesized with excellent levels of enantioselectivity in the presence of diamine inhibitors. PMID:19476375

5-hydroxymethylfurfural conversion by fungal aryl-alcohol oxidase and unspecific peroxygenase.

PubMed

Carro, Juan; Ferreira, Patricia; Rodríguez, Leonor; Prieto, Alicia; Serrano, Ana; Balcells, Beatriz; Ardá, Ana; Jiménez-Barbero, Jesús; Gutiérrez, Ana; Ullrich, René; Hofrichter, Martin; Martínez, Angel T

2015-08-01

Oxidative conversion of 5-hydroxymethylfurfural (HMF) is of biotechnological interest for the production of renewable (lignocellulose-based) platform chemicals, such as 2,5-furandicarboxylic acid (FDCA). To the best of our knowledge, the ability of fungal aryl-alcohol oxidase (AAO) to oxidize HMF is reported here for the first time, resulting in almost complete conversion into 2,5-formylfurancarboxylic acid (FFCA) in a few hours. The reaction starts with alcohol oxidation, yielding 2,5-diformylfuran (DFF), which is rapidly converted into FFCA by carbonyl oxidation, most probably without leaving the enzyme active site. This agrees with the similar catalytic efficiencies of the enzyme with respect to oxidization of HMF and DFF, and its very low activity on 2,5-hydroxymethylfurancarboxylic acid (which was not detected by GC-MS). However, AAO was found to be unable to directly oxidize the carbonyl group in FFCA, and only modest amounts of FDCA are formed from HMF (most probably by chemical oxidation of FFCA by the H2 O2 previously generated by AAO). As aldehyde oxidation by AAO proceeds via the corresponding geminal diols (aldehyde hydrates), the various carbonyl oxidation rates may be related to the low degree of hydration of FFCA compared with DFF. The conversion of HMF was completed by introducing a fungal unspecific heme peroxygenase that uses the H2 O2 generated by AAO to transform FFCA into FDCA, albeit more slowly than the previous AAO reactions. By adding this peroxygenase when FFCA production by AAO has been completed, transformation of HMF into FDCA may be achieved in a reaction cascade in which O2 is the only co-substrate required, and water is the only by-product formed. © 2014 The Authors. FEBS Journal published by John Wiley & Sons Ltd on behalf of FEBS.

An ultrasound-assisted system for the optimization of biodiesel production from chicken fat oil using a genetic algorithm and response surface methodology.

PubMed

Fayyazi, E; Ghobadian, B; Najafi, G; Hosseinzadeh, B; Mamat, R; Hosseinzadeh, J

2015-09-01

Biodiesel is a green (clean), renewable energy source and is an alternative for diesel fuel. Biodiesel can be produced from vegetable oil, animal fat and waste cooking oil or fat. Fats and oils react with alcohol to produce methyl ester, which is generally known as biodiesel. Because vegetable oil and animal fat wastes are cheaper, the tendency to produce biodiesel from these materials is increasing. In this research, the effect of some parameters such as the alcohol-to-oil molar ratio (4:1, 6:1, 8:1), the catalyst concentration (0.75%, 1% and 1.25% w/w) and the time for the transesterification reaction using ultrasonication on the rate of the fatty acids-to-methyl ester (biodiesel) conversion percentage have been studied (3, 6 and 9 min). In biodiesel production from chicken fat, when increasing the catalyst concentration up to 1%, the oil-to-biodiesel conversion percentage was first increased and then decreased. Upon increasing the molar ratio from 4:1 to 6:1 and then to 8:1, the oil-to-biodiesel conversion percentage increased by 21.9% and then 22.8%, respectively. The optimal point is determined by response surface methodology (RSM) and genetic algorithms (GAs). The biodiesel production from chicken fat by ultrasonic waves with a 1% w/w catalyst percentage, 7:1 alcohol-to-oil molar ratio and 9 min reaction time was equal to 94.8%. For biodiesel that was produced by ultrasonic waves under a similar conversion percentage condition compared to the conventional method, the reaction time was decreased by approximately 87.5%. The time reduction for the ultrasonic method compared to the conventional method makes the ultrasonic method superior. Copyright © 2015. Published by Elsevier B.V.

Stereoselective oxidation of aliphatic diols and reduction of hydroxy-ketones with galactitol dehydrogenase from Rhodobacter sphaeroides D.

PubMed

Kohring, G W; Wiehr, P; Jeworski, M; Giffhorn, F

2003-01-01

From the Rhodobacter sphaeroides mutant D a galactitol dehydrogenase (GDH) was isolated and characterized in an earlier investigation (1). The enzyme expressed activity with a wide spread substrate spectrum, like sugars, sugar alcohols, secondary alcohols or the corresponding ketones and it can be used for the production of the rare sugar L-tagatose by regioselective oxidation of galactitol (2). This study focuses on the preparation of optically pure aliphatic diols by oxidation of one enantiomer or stereospecific reduction of keto-alcohols and diketones. The oxidation of 1,2-propanediol, 1,2-butanediol, 1,2-pentanediol and 1,2-hexanediol occurred highly specific with the S-enantiomer leaving the R-enantiomer of the diols in the reaction vessel. Also (S)-1,2,6-hexanetriol was oxidized by GDH to 1,6-dihydroxy-2-hexanone. The Km values of these reactions decreased with increasing length of the carbon chain. Reduction of hydroxyacetone or 1-hydroxy-2-butanone resulted in an excess of 93% (S)-1,2-propanediol and more than 98% of (S)-1,2-butanediol, respectively. The diketone 2,3-hexanedione was only reduced to (2R,3S)-2,3-hexanediol, one of the possible four configurations. The wide substrate spectrum on one hand and the selectivity in the reaction on the other hand make GDH a very interesting enzyme for the production of optically pure building blocks in the chemical synthesis of bioactive compounds.

Covalent Surface Modification of Silicon Oxides with Alcohols in Polar Aprotic Solvents.

PubMed

Lee, Austin W H; Gates, Byron D

2017-09-05

Alcohol-based monolayers were successfully formed on the surfaces of silicon oxides through reactions performed in polar aprotic solvents. Monolayers prepared from alcohol-based reagents have been previously introduced as an alternative approach to covalently modify the surfaces of silicon oxides. These reagents are readily available, widely distributed, and are minimally susceptible to side reactions with ambient moisture. A limitation of using alcohol-based compounds is that previous reactions required relatively high temperatures in neat solutions, which can degrade some alcohol compounds or could lead to other unwanted side reactions during the formation of the monolayers. To overcome these challenges, we investigate the condensation reaction of alcohols on silicon oxides carried out in polar aprotic solvents. In particular, propylene carbonate has been identified as a polar aprotic solvent that is relatively nontoxic, readily accessible, and can facilitate the formation of alcohol-based monolayers. We have successfully demonstrated this approach for tuning the surface chemistry of silicon oxide surfaces with a variety of alcohol containing compounds. The strategy introduced in this research can be utilized to create silicon oxide surfaces with hydrophobic, oleophobic, or charged functionalities.

Comparative metabolism of the pyrethroids bifenthrin and deltamethrin in the bulb mite Rhizoglyphus robini

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

Ruzo, L.O.; Cohen, E.; Capua, S.

The fate of {sup 14}C-radiolabeled bifenthrin and deltamethrin was studied in the mite, Rhizoglyphus robini. Administered either by ingestion or by contact, both pyrethroids were efficiently metabolized, but deltamethrin was degraded to a much greater extent. The identified metabolites arise from a combination of ester cleavage, oxidation, and conjugation reactions. With {sup 14}C-acid- and {sup 14}C-alcohol-labeled bifenthrin, the free metabolites detected were the 4{prime}-hydroxy derivative of the ester, the primary ester cleavage products, the acid, and its 4{prime}-hydroxy derivative from the alcohol moiety, as well as several unidentified metabolites. Using {sup 14}C-alcohol-labeled deltamethrin, 3-phenoxybenzoic acid and its 4{prime}-hydroxylated product andmore » several unknown metabolites were detected. Conjugates comprised the bulk of total pyrethroid metabolites. In addition to ester cleavage products, the 4{prime}-hydroxylated bifenthrin was also identified. For the first time in invertebrates, a conjugated pyrethroid ester was observed.« less

Structural and Affinity Determinants in the Interaction between Alcohol Acyltransferase from F. x ananassa and Several Alcohol Substrates: A Computational Study

PubMed Central

Herrera, Raúl; Caballero, Julio; Alzate-Morales, Jans H.

2016-01-01

Aroma and flavor are important factors of fruit quality and consumer preference. The specific pattern of aroma is generated during ripening by the accumulation of volatiles compounds, which are mainly esters. Alcohol acyltransferase (AAT) (EC 2.3.1.84) catalyzes the esterification reaction of aliphatic and aromatic alcohols and acyl-CoA into esters in fruits and flowers. In Fragaria x ananassa, there are different volatiles compounds that are obtained from different alcohol precursors, where octanol and hexanol are the most abundant during fruit ripening. At present, there is not structural evidence about the mechanism used by the AAT to synthesize esters. Experimental data attribute the kinetic role of this enzyme to 2 amino acidic residues in a highly conserved motif (HXXXD) that is located in the middle of the protein. With the aim to understand the molecular and energetic aspects of volatiles compound production from F. x ananassa, we first studied the binding modes of a series of alcohols, and also different acyl-CoA substrates, in a molecular model of alcohol acyltransferase from Fragaria x ananassa (SAAT) using molecular docking. Afterwards, the dynamical behavior of both substrates, docked within the SAAT binding site, was studied using routine molecular dynamics (MD) simulations. In addition, in order to correlate the experimental and theoretical data obtained in our laboratories, binding free energy calculations were performed; which previous results suggested that octanol, followed by hexanol, presented the best affinity for SAAT. Finally, and concerning the SAAT molecular reaction mechanism, it is suggested from molecular dynamics simulations that the reaction mechanism may proceed through the formation of a ternary complex, in where the Histidine residue at the HXXXD motif deprotonates the alcohol substrates. Then, a nucleophilic attack occurs from alcohol charged oxygen atom to the carbon atom at carbonyl group of the acyl CoA. This mechanism is in agreement with previous results, obtained in our group, in alcohol acyltransferase from Vasconcellea pubescens (VpAAT1). PMID:27078149

Evaluation of synthesized cross linked polyvinyl alcohol as potential disintegrant.

PubMed

Patel, Ashok R; Vavia, Pradeep R

2010-01-01

The present study deals with evaluation of crosslinked poly vinyl alcohol (PVA) as a potential disintegrant. Crosslinking of PVA was carried out using glutaraldehyde as a crosslinker, in presence of acidic conditions. The crosslinking reaction was optimized for a) polymer: crosslinker ratio; b) temperature requirement and c) reaction duration. Certain physical parameters of the disintegrant (including sedimentation volume, hydration capacity, specific surface area and bulk and tap density) were determined and compared to the known disintegrants. Characterization was carried out using FT-IR, DSC, XRD, SEM and Photo microscopy studies. The developed excipient was also studied for acute toxicity in rats and found to be safe for oral use. Disintegration property of formed product was compared to known disintegrant (Ac-Di-Sol) and it was found to give better results. The disintegration mechanism of developed disintegrant was postulated based on results obtained from various physical evaluations including: Study of effect of disintegrant concentration, fillers, and hardness, mode of incorporation and method of granulation on disintegration activity. By changing the condition parameters of well known crosslinking reaction of PVA, we obtained a crosslinked product which had excellent disintegration activity, good flow and optimal tableting properties.

CuO nanoparticles catalyzed C-N, C-O, and C-S cross-coupling reactions: scope and mechanism.

PubMed

Jammi, Suribabu; Sakthivel, Sekarpandi; Rout, Laxmidhar; Mukherjee, Tathagata; Mandal, Santu; Mitra, Raja; Saha, Prasenjit; Punniyamurthy, Tharmalingam

2009-03-06

CuO nanoparticles have been studied for C-N, C-O, and C-S bond formations via cross-coupling reactions of nitrogen, oxygen, and sulfur nucleophiles with aryl halides. Amides, amines, imidazoles, phenols, alcohols and thiols undergo reactions with aryl iodides in the presence of a base such as KOH, Cs(2)CO(3), and K(2)CO(3) at moderate temperature. The procedure is simple, general, ligand-free, and efficient to afford the cross-coupled products in high yield.

Immobilization of Pichia pastoris cells containing alcohol oxidase activity

PubMed Central

Maleknia, S; Ahmadi, H; Norouzian, D

2011-01-01

Background and Objectives The attempts were made to describe the development of a whole cell immobilization of P. pastoris by entrapping the cells in polyacrylamide gel beads. The alcohol oxidase activity of the whole cell Pichia pastoris was evaluated in comparison with yeast biomass production. Materials and Methods Methylotrophic yeast P. pastoris was obtained from Collection of Standard Microorganisms, Department of Bacterial Vaccines, Pasteur Institute of Iran (CSMPI). Stock culture was maintained on YPD agar plates. Alcohol oxidase was strongly induced by addition of 0.5% methanol as the carbon source. The cells were harvested by centrifugation then permeabilized. Finally the cells were immobilized in polyacrylamide gel beads. The activity of alcohol oxidase was determined by method of Tane et al. Results At the end of the logarithmic phase of cell culture, the alcohol oxidase activity of the whole cell P. Pastoris reached the highest level. In comparison, the alcohol oxidase activity was measured in an immobilized P. pastoris when entrapped in polyacrylamide gel beads. The alcohol oxidase activity of cells was induced by addition of 0.5% methanol as the carbon source. The cells were permeabilized by cetyltrimethylammonium bromide (CTAB) and immobilized. CTAB was also found to increase the gel permeability. Alcohol oxidase activity of immobilized cells was then quantitated by ABTS/POD spectrophotometric method at OD 420. There was a 14% increase in alcohol oxidase activity in immobilized cells as compared with free cells. By addition of 2-butanol as a substrate, the relative activity of alcohol oxidase was significantly higher as compared with other substrates added to the reaction media. Conclusion Immobilization of cells could eliminate lengthy and expensive procedures of enzyme separation and purification, protect and stabilize enzyme activity, and perform easy separation of the enzyme from the reaction media. PMID:22530090

Mechanism of alcohol-enhanced lucigenin chemiluminescence in alkaline solution.

PubMed

Chi, Quan; Chen, Wanying; He, Zhike

2015-11-01

The chemiluminescence (CL) of lucigenin (Luc(2+)) can be enhanced by different alcohols in alkaline solution. The effect of different fatty alcohols on the CL of lucigenin was related to the carbon chain length and the number of hydroxyl groups. Glycerol provides the greatest enhancement. UV/Vis absorption spectra and fluorescence spectra showed that N-methylacridone (NMA) was produced in the CL reaction in the presence of different alcohols. The peak of the CL spectrum was located at 470 nm in all cases, indicating that the luminophore was always the excited-state NMA. The quenching of lucigenin CL by superoxide dismutase (SOD) and the electron spin resonance (ESR) results with the spin trap of 5,5-dimethyl-1-pyrroline N-oxide (DMPO) demonstrated that superoxide anions (O2 (•-)) were generated from dissolved oxygen in the CL reaction and that glycerol and dihydroxyacetone (DHA) can promote O2 (•-) production by the reduction of dissolved oxygen in alkaline solution. It was assumed that the enhancement provided by different alcohols was related to the solvent effect and reducing capacity. Glycerol and DHA can also reduce Luc(2+) into lucigenin cation radicals (Luc(•+) ), which react with O2 (•-) to produce CL, and glycerol can slowly transform into DHA, which is oxidized quickly in alkaline solution. Copyright © 2015 John Wiley & Sons, Ltd.

Catalysts for the production of hydrocarbons from carbon monoxide and water

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

Sapienza, Richard S.; Slegeir, William A.; Goldberg, Robert I.

1987-01-01

A method of converting low H.sub.2 /CO ratio syngas to carbonaceous products comprising reacting the syngas with water or steam at 200.degree. to 350.degree. C. in the presence of a metal catalyst supported on zinc oxide. Hydrocarbons are produced with a catalyst selected from cobalt, nickel or ruthenium and alcohols are produced with a catalyst selected from palladium, platinium, ruthenium or copper on the zinc oxide support. The ratio of the reactants are such that for alcohols and saturated hydrocarbons: (2n+1).gtoreq.x.gtoreq.O and for olefinic hydrocarbons: 2n.gtoreq.x.gtoreq.O where n is the number of carbon atoms in the product and x ismore » the molar amount of water in the reaction mixture.« less

Controlling hydrogenation activity and selectivity of bimetallic surfaces and catalysts

NASA Astrophysics Data System (ADS)

Murillo, Luis E.

Studies of bimetallic systems are of great interest in catalysis due to the novel properties that they often show in comparison with the parent metals. The goals of this dissertation are: (1) to expand the studies of self-hydrogenation and hydrogenation reactions on bimetallic surfaces under ultra high vacuum conditions (UHV) using different hydrocarbon as probe molecules; (2) to attempt to correlate the surface science findings with supported catalyst studies under more realistic conditions; and (3) to investigate the competitive hydrogenation of C=C versus C=O bonds on Pt(111) modified by different 3d transition metals. Hydrogenation studies using temperature programmed desorption (TPD) on Ni/Pt(111) bimetallic surfaces have demonstrated an enhancement in the low temperature hydrogenation activity relative to that of clean Pt(111). This novel hydrogenation pathway can be achieved under UHV conditions by controlling the structures of the bimetallic surfaces. A low temperature hydrogenation activity of 1-hexene and 1-butene has been observed on a Pt-Ni-Pt(111) subsurface structure, where Ni atoms are mainly present on the second layer of the Pt(111) single crystal. These results are in agreement with previous studies of self-hydrogenation and hydrogenation of cyclohexene. However, a much higher dehydrogenation activity is observed in the reaction of cyclohexene to produce benzene, demonstrating that the hydrocarbon structure has an effect on the reaction pathways. On the other hand, self-hydrogenation of 1-butene is not observed on the Pt-Ni-Pt(111) surface, indicating that the chain length (or molecular weight) has a significant effect on the selfhydrogenation activity. The gas phase reaction of cyclohexene on Ni/Pt supported on alumina catalysts has also shown a higher self-hydrogenation activity in comparison with the same reaction performed on supported monometallic catalysts. The effects of metal loading and impregnation sequence of the metal precursors are also discussed. Chemisorption, TPD, FTIR using a batch reactor for the self-hydrogenation of cyclohexene and CO adsorbed on the bimetallic surfaces were carried out to correlate surface science findings with experiments on supported bimetallic catalysts. To expand the studies on the effect of bimetallic structures on hydrogenation reactions, molecules with multiple functional groups such as alpha,beta-unsaturated aldehydes were also investigated. Studies of selective hydrogenation of a,ss-unsaturated aldehydes toward the desired unsaturated alcohols are of interest for the production of fine chemicals and pharmaceuticals. In these compounds, competitive hydrogenation of the C=C and C=O bonds occurs. TPD and HREELS experiments of acrolein (CH2=CH-CH=O) on Pt-based bimetallic surfaces are performed to investigate their effects on the hydrogenation activity of the C-O bond. The production of the desired unsaturated alcohol, allyl alcohol, has been observed for the first time on Pt-Ni-Pt(111) under UHV conditions. However, the propionaldehyde yield is five times higher than the allyl alcohol yield. Thus, a preferential isomerization reaction of allyl alcohol to propionaldehyde is very likely to occur on the Pt-Ni-Pt(111) surface as observed on the desorption studies of allyl alcohol on this surface. The hydrogenation of acrolein is also carried out under UHV conditions on other 3d-transition metal/Pt(111) surfaces such as Co/Pt(111), Fe/Pt(111), and Cu/Pt(111). So far, the highest activity and allyl alcohol yield are found on the Pt-Ni-Pt(111) surface with pre-adsorbed hydrogen.

A selected ion flow tube study of the reactions of H3O+, NO+ and O2+ with some oxygenated biogenic volatile organic compounds

NASA Astrophysics Data System (ADS)

Amelynck, C.; Schoon, N.; Kuppens, T.; Bultinck, P.; Arijs, E.

2005-12-01

The rate constants and product ion distributions of the reactions of H3O+, NO+ and O2+ with 2-methyl-3-buten-2-ol, cis-3-hexen-1-ol, cis-3-hexenyl acetate, 1,8-cineole, 6-methyl-5-hepten-2-one, camphor and linalool have been determined at 150 Pa and 297 K using a selected ion flow tube (SIFT). All reactions were found to proceed at a rate close to the collision rate, calculated with the Su and Chesnavich model, using the polarizability and electric dipole moment of the compounds derived from B3LYP/aug-cc-pVDZ quantum chemical calculations. Additionally the product ion distributions of the reactions of these three ions with the terpenoid alcohols nerol and geraniol have been obtained.

Mathematical modeling of methyl ester concentration distribution in a continuous membrane tubular reactor and comparison with conventional tubular reactor

NASA Astrophysics Data System (ADS)

Talaghat, M. R.; Jokar, S. M.; Modarres, E.

2017-10-01

The reduction of fossil fuel resources and environmental issues made researchers find alternative fuels include biodiesels. One of the most widely used methods for production of biodiesel on a commercial scale is transesterification method. In this work, the biodiesel production by a transesterification method was modeled. Sodium hydroxide was considered as a catalyst to produce biodiesel from canola oil and methanol in a continuous tubular ceramic membranes reactor. As the Biodiesel production reaction from triglycerides is an equilibrium reaction, the reaction rate constants depend on temperature and related linearly to catalyst concentration. By using the mass balance for a membrane tubular reactor and considering the variation of raw materials and products concentration with time, the set of governing equations were solved by numerical methods. The results clearly show the superiority of membrane reactor than conventional tubular reactors. Afterward, the influences of molar ratio of alcohol to oil, weight percentage of the catalyst, and residence time on the performance of biodiesel production reactor were investigated.

Transesterification reaction of the fat originated from solid waste of the leather industry.

PubMed

Işler, Asli; Sundu, Serap; Tüter, Melek; Karaosmanoğlu, Filiz

2010-12-01

The leather industry is an industry which generates a large amount of solid and liquid wastes. Most of the solid wastes originate from the pre-tanning processes while half of it comes from the fleshing step. Raw fleshing wastes which mainly consist of protein and fat have almost no recovery option and the disposal is costly. This study outlines the possibility of using the fleshing waste as an oil source for transesterification reaction. The effect of oil/alcohol molar ratio, the amount of catalyst and temperature on ester production was individually investigated and optimum reaction conditions were determined. The fuel properties of the ester product were also studied according to the EN 14214 standard. Cold filter plugging point and oxidation stability have to be improved in order to use the ester product as an alternative fuel candidate. Besides, this product can be used as a feedstock in lubricant production or cosmetic industry. Copyright © 2010 Elsevier Ltd. All rights reserved.

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

Disselkamp, Robert S.; Denslow, Kayte M.; Hart, Todd R.

We have studied the effect of cavitating ultrasound on the heterogeneous aqueous hydrogenation of cis-2-buten-1-ol (C4 olefin) and cis-2-penten-1-ol (C5 olefin) on Pd-black to form the trans-olefins (trans-2-buten-1-ol and trans-2-penten-1-ol) and saturated alcohols (1-butanol and 1-pentanol, respectively). Silent (and magnetically stirred) experiments served as control experiments. As described in an earlier publication by our group, we have added an inert dopant, 1-propanol, in the reaction mixture to ensure the rapid onset of cavitation in the ultrasound-assisted reactions that can lead to altered selectivity compared to silent reaction systems [R.S. Disselkamp, Ya-Huei Chin, C.H.F. Peden, J. Catal. 227 (2004) 552]. Themore » motivation for this study is to examine whether cavitating ultrasound can reduce the [trans-olefin/saturated alcohol] molar ratio during the course of the reaction. This could have practical application in that it may offer an alternative processing methodology of synthesizing healthier edible seed oils by reducing trans-fat content.We have observed that cavitating ultrasound results in a [(trans-olefin/saturated alcohol)ultrasound/(trans-olefin/saturated alcohol)silent] ratio quantity less than 0.5 at the reaction mid-point for both the C4 and C5 olefin systems. This indicates that ultrasound reduces trans-olefin production compared to the silent control experiment. Furthermore, there is an added 30% reduction for the C5 versus C4 olefin compounds again at reaction mid-point. We attribute differences in the ratio quantity as a moment of inertia effect. In principle, the C4 versus C5 olefins has a {approx}52% increase in moment of inertia about C2 C3 double bond slowing isomerization. Since seed oils are C18 multiple cis-olefins and have a moment of inertia even greater than our C5 olefin here, our study suggests that even a greater reduction in trans-olefin content may occur for partial hydrogenation of C18 seed oils.« less

Investigating the nature of palladium chain-walking in the enantioselective redox-relay Heck reaction of alkenyl alcohols.

PubMed

Hilton, Margaret J; Xu, Li-Ping; Norrby, Per-Ola; Wu, Yun-Dong; Wiest, Olaf; Sigman, Matthew S

2014-12-19

The mechanism of the redox-relay Heck reaction was investigated using deuterium-labeled substrates. Results support a pathway through a low energy palladium-alkyl intermediate that immediately precedes product formation, ruling out a tautomerization mechanism. DFT calculations of the relevant transition structures at the M06/LAN2DZ+f/6-31+G* level of theory show that the former pathway is favored by 5.8 kcal/mol. Palladium chain-walking toward the alcohol, following successive β-hydride eliminations and migratory insertions, is also supported in this study. The stereochemistry of deuterium labels is determined, lending support that the catalyst remains bound to the substrate during the relay process and that both cis- and trans-alkenes form from β-hydride elimination.

Observation of CO2 and solvent adduct ions during negative mode electrospray ionization Fourier transform ion cyclotron resonance mass spectrometric analysis of monohydric alcohols.

PubMed

Zhou, Xibin; Zhang, Yahe; Zhao, Suoqi; Hsu, Chang Samuel; Shi, Quan

2013-12-15

Monohydric alcohols are common in natural products, bio-oils, and medicine. We have found that monohydric alcohols can form O3 (ions containing three oxygen atoms) and O4 adduct ions in negative electrospray ionization (ESI) Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS), which would significantly affect the composition analysis of alcohols, especially in a complex mixture. It is necessary to study the reaction pathways and the method to eliminate or reduce the 'artifact' adducts. Octadecanol, cholesterol, squalanol and two complex monohydric alcohol mixtures were selected as model compounds. These samples were subjected to negative ion ESI FT-ICR MS analysis. The composition and formation mechanism of adducts were studied by the ultrahigh-resolution accurate mass measurement for elemental composition, along with the MS(2) isolation and collision-induced dissociation (CID) experiments for structural determination. The reaction pathway of O3 adduct formation is the coupling of a monohydric alcohol ion with a CO2 to form a stable O3 ionic species by likely a covalent bond (source of CO2 is not clear). The O4 species are formed by O3 ionic species adducted with an alcohol molecule of the solvent, such as methanol or ethanol, by likely a hydrogen bond. These adduct ions could be eliminated or reduced by increasing collision energy. However, excessive collision energy would fragment monohydric alcohol ions. The formation mechanisms of O3 and O4 adducts from monohydric alcohols in negative ion ESI FT-ICR MS were proposed. The solvent adduction effects can be eliminated or reduced by optimizing the collision energy of CID in FT-ICR MS. Copyright © 2013 John Wiley & Sons, Ltd.

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.

Automated Discovery of New Chemical Reactions and Accurate Calculation of Their Rates

DTIC Science & Technology

2015-06-02

formation of organic acids in reactions of the Criegee intermediate with aldehydes and ketones . Phys. Chem. Chem. Phys. 2013, 15, 16841-16852. [39...dioxolan-3-ol – our second case study - we confirmed that fragmentation of the cyclic peroxide leads to two possible pairs of acid and aldehyde products...Rate Prediction via Group Additivity, Part 2: H-Abstraction from Alkenes, Alkynes, Alcohols, Aldehydes , and Acids by H Atoms. J. Phys. Chem. A 2001, 105

In situ FTIR studies on the oxidation of isopropyl alcohol over SnO2 as a function of temperature up to 600 °C and a comparison to the analogous plasma-driven process.

PubMed

Christensen, P A; Mashhadani, Z T A W; Md Ali, Abd Halim Bin

2018-04-04

This paper reports the application of in situ reflectance Fourier Transform InfraRed spectroscopy to the study of the thermal and plasma driven reaction of IsoPropyl Alcohol (IPA) at SnO2-coated Macor, the latter a ceramic material comprised of the oxides of Al, Mg and Si. The data so obtained were compared to those obtained using uncoated Macor. When uncoated Macor was employed, no reaction of the IPA was observed up to 600 °C in the thermal experiments, whereas a number of products were observed in the plasma-driven experiments. The results obtained using coated Macor were somewhat different, with no reaction taking place in the plasma-driven experiments, whilst significant reaction took place in the thermally-driven process. In the latter experiments, the chemistry was observed to show four distinct temperature regions, with electron injection into the conduction band of the SnO2 playing a significant role, culminating in the production of CO2. The data were interpreted in terms of a model in which physisorbed IPA was converted to two forms of isopropoxide: this was converted to acetone and acetaldehyde via adsorbed enolate. The data clearly support the catalytic activity of Macor in the plasma-driven conversion of IPA.

Catalyst for producing lower alcohols

DOEpatents

Rathke, Jerome W.; Klingler, Robert J.; Heiberger, John J.

1987-01-01

A process and system for the production of the lower alcohols such as methanol, ethanol and propanol involves the reaction of carbon monoxide and water in the presence of a lead salt and an alkali metal formate catalyst combination. The lead salt is present as solid particles such as lead titanate, lead molybdate, lead vanadate, lead zirconate, lead tantalate and lead silicates coated or in slurry within molten alkali metal formate. The reactants, carbon monoxide and steam are provided in gas form at relatively low pressures below 100 atmospheres and at temperatures of 200-400.degree. C. The resulted lower alcohols can be separated into boiling point fractions and recovered from the excess reactants by distillation.

What Can the Brain Teach Us about Winemaking? An fMRI Study of Alcohol Level Preferences

PubMed Central

Frost, Ram; Quiñones, Ileana; Veldhuizen, Maria; Alava, Jose-Iñaki; Small, Dana; Carreiras, Manuel

2015-01-01

Over the last few decades, wine makers have been producing wines with a higher alcohol content, assuming that they are more appreciated by consumers. To test this hypothesis, we used functional magnetic imaging to compare reactions of human subjects to different types of wine, focusing on brain regions critical for flavor processing and food reward. Participants were presented with carefully matched pairs of high- and low-alcohol content red wines, without informing them of any of the wine attributes. Contrary to expectation, significantly greater activation was found for low-alcohol than for high-alcohol content wines in brain regions that are sensitive to taste intensity, including the insula as well as the cerebellum. Wines were closely matched for all physical attributes except for alcohol content, thus we interpret the preferential response to the low-alcohol content wines as arising from top-down modulation due to the low alcohol content wines inducing greater attentional exploration of aromas and flavours. The findings raise intriguing possibilities for objectively testing hypotheses regarding methods of producing a highly complex product such as wine. PMID:25785844

What can the brain teach us about winemaking? An fMRI study of alcohol level preferences.

PubMed

Frost, Ram; Quiñones, Ileana; Veldhuizen, Maria; Alava, Jose-Iñaki; Small, Dana; Carreiras, Manuel

2015-01-01

Over the last few decades, wine makers have been producing wines with a higher alcohol content, assuming that they are more appreciated by consumers. To test this hypothesis, we used functional magnetic imaging to compare reactions of human subjects to different types of wine, focusing on brain regions critical for flavor processing and food reward. Participants were presented with carefully matched pairs of high- and low-alcohol content red wines, without informing them of any of the wine attributes. Contrary to expectation, significantly greater activation was found for low-alcohol than for high-alcohol content wines in brain regions that are sensitive to taste intensity, including the insula as well as the cerebellum. Wines were closely matched for all physical attributes except for alcohol content, thus we interpret the preferential response to the low-alcohol content wines as arising from top-down modulation due to the low alcohol content wines inducing greater attentional exploration of aromas and flavours. The findings raise intriguing possibilities for objectively testing hypotheses regarding methods of producing a highly complex product such as wine.

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

PubMed

Yılmaz, Durmuşhan; Şahin, Engin; Dertli, Enes

2017-11-01

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

Methods for transfer a saliva based alcohol content test to a dermal patch

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

Silks, III, Louis A.

Detection and quantitation of ethanol which is highly sensitive, specific, and efficient has been a commercial target for sometime. Clearly analytical methods are useful such as gas and liquid chromatography, mass spectrometry, and NMR spectroscopy. However, those methods are best used in the laboratory and a less useful for detection and quantitation of ethanol in the field. Enzymes have been employed for the detection and quantitation of EtOH. Enzymes are proteins that perform a particular task in a bio-catalytic way. Most of the chemistry that these enzymes do are frequently exquisitely specific in that only one alcohol reacts and onlymore » one product is produced. One enzyme molecule can catalyze the reaction of numerous substrate molecules which in itself is an amplification of the recognition signal. Alcohol dehydrogenase (ADH) and alcohol oxidase (AO) are two possible enzymatic targets for EtOH sensor development.1 The ADH oxidizes the alcohol using a co-factor nicotinamide adenine dinucleotide. This co-factor needs to be within close proximity of the ADH. AO also oxidizes the ethanol using molecular oxygen giving rise to the production of the aldehyde and hydrogen peroxide.« less

The study of CaO and MgO heterogenic nano-catalyst coupling on transesterification reaction efficacy in the production of biodiesel from recycled cooking oil.

PubMed

Tahvildari, Kambiz; Anaraki, Yasaman Naghavi; Fazaeli, Reza; Mirpanji, Sogol; Delrish, Elham

2015-01-01

Fossil fuels' pollution and their non-renewability have motivated the search for alternative fuels. Some common example of seed oils are sunflower oil, date seed oil, soy bean oil. For instance, soy methyl and soy-based biodiesel are the main biodiesel. Biodiesel is a clean diesel fuel that can be produced through transesterification reaction. Recycled cooking oil, on the other hand, is one of the inexpensive, easily available sources for producing biodiesel. This article is aimed at production of biodiesel via trans-esterification method, Nano CaO synthesis using sol-gel method, and Nano MgO synthesis using sol-gel self-combustion. Two catalysts' combination affecting the reaction's efficacy was also discussed. Optimum conditions for the reaction in the presence of Nano CaO are 1.5 % weight fracture, 1:7 alcohol to oil proportion and 6 h in which biodiesel and glycerin (the byproduct) are produced. Moreover, the optimum conditions for this reaction in the presence of Nano CaO and Nano MgO mixture are 3 % weight fracture (0.7 g of Nano CaO and 0.5 g of Nano MgO), 1:7 alcohols to oil proportion and 6 h. Nano MgO is not capable of catalyzing the transesterification by itself, because it has a much weaker basic affinity but when used with Nano CaO due to its surface structure, the basic properties increase and it becomes a proper base for the catalyst so that CaO contact surface increases and transesterification reaction yield significantly increases as well. This study investigates the repeatability of transesterification reaction in the presence of these Nano catalysts as well.

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

PubMed

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

2006-06-29

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

Dermal Toxicity Evaluation of Neutralized Chemical Agent Identification Sets (CAIS) with an Overview of the Dermal Toxicity of Vesicant Agents and their Degradation Products.

DTIC Science & Technology

1996-10-01

Food and Water Consumption and Locomotor Movement in Rats, Lab Animals, 26:180-189 (1992). Mann, F.G. and Pope, W.J., "Production and Reactions of ý...and Use: t-butyl alcohol is used in the manufacture of flotation agents, flavors, perfumes, used extensively as a solvent, as a gasoline additive

Transesterification process to manufacture ethyl ester of rape oil

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

Korus, R.A.; Hoffman, D.S.; Bam, N.

1993-12-31

A process for the production of the ethyl ester of winter rape [EEWR] for use as a biodiesel fuel has been studied. The essential part of the process is the transesterification of rape oil with ethanol, in the presence of a catalyst, to yield the ethyl ester of rape oil as a product and glycerin as a by-product. Experiments have been performed to determine the optimum conditions for the preparation of EEWR. The process variables were: (1) temperature, (2) catalyst, (3) rate of agitation, (4) water content of the alcohol used, and (5) the amount of excess alcohol used. Themore » optimum conditions were: (1) room temperature, (2) 0.5% sodium methoxide or 1% potassium hydroxide catalyst by weight of rapeseed oil, (3) extremely vigorous agitation with some splashing during the initial phase of the reaction and agitation was not necessary after the reaction mixture became homogeneous, (4) absolute ethanol was necessary for high conversion, and (5) 50% excess ethanol with NaOCH{sub 3} or 100% excess with KOH gave a maximum conversion. Viscosity, cloud point and pour point of the EEWR were measured. A preliminary break-even cost for the commercial production of EEWR was found to be $0.55/liter [$2.08/US gallon].« less

A new approach to synthesis of benzyl cinnamate: Optimization by response surface methodology.

PubMed

Zhang, Dong-Hao; Zhang, Jiang-Yan; Che, Wen-Cai; Wang, Yun

2016-09-01

In this work, the new approach to synthesis of benzyl cinnamate by enzymatic esterification of cinnamic acid with benzyl alcohol is optimized by response surface methodology. The effects of various reaction conditions, including temperature, enzyme loading, substrate molar ratio of benzyl alcohol to cinnamic acid, and reaction time, are investigated. A 5-level-4-factor central composite design is employed to search for the optimal yield of benzyl cinnamate. A quadratic polynomial regression model is used to analyze the experimental data at a 95% confidence level (P<0.05). The coefficient of determination of this model is found to be 0.9851. Three sets of optimum reaction conditions are established, and the verified experimental trials are performed for validating the optimum points. Under the optimum conditions (40°C, 31mg/mL enzyme loading, 2.6:1 molar ratio, 27h), the yield reaches 97.7%, which provides an efficient processes for industrial production of benzyl cinnamate. Copyright © 2016 Elsevier Ltd. All rights reserved.

Multi-catalysis cascade reactions based on the methoxycarbonylketene platform: diversity-oriented synthesis of functionalized non-symmetrical malonates for agrochemicals and pharmaceuticals.

PubMed

Ramachary, Dhevalapally B; Venkaiah, Chintalapudi; Reddy, Y Vijayendar; Kishor, Mamillapalli

2009-05-21

In this paper we describe new multi-catalysis cascade (MCC) reactions for the one-pot synthesis of highly functionalized non-symmetrical malonates. These metal-free reactions are either five-step (olefination/hydrogenation/alkylation/ketenization/esterification) or six-step (olefination/hydrogenation/alkylation/ketenization/esterification/alkylation), and employ aldehydes/ketones, Meldrum's acid, 1,4-dihydropyridine/o-phenylenediamine, diazomethane, alcohols and active ethylene/acetylenes, and involve iminium-, self-, self-, self- and base-catalysis, respectively. Many of the products have direct application in agricultural and pharmaceutical chemistry.

Regioselective SN2' Mitsunobu reaction of Morita-Baylis-Hillman alcohols: A facile and stereoselective synthesis of α-alkylidene-β-hydrazino acid derivatives.

PubMed

Xu, Silong; Shang, Jian; Zhang, Junjie; Tang, Yuhai

2014-01-01

A highly regioselective SN2' Mitsunobu reaction between Morita-Baylis-Hillman (MBH) alcohols, azodicarboxylates, and triphenylphosphine is developed, which provides an easy access to α-alkylidene-β-hydrazino acid derivatives in high yields and good stereoselectivity. This reaction represents the first direct transformation of MBH alcohols into hydrazines.

Catalysts for the production of hydrocarbons from carbon monoxide and water

DOEpatents

Sapienza, R.S.; Slegeir, W.A.; Goldberg, R.I.

1985-11-06

A method of converting low H/sub 2//CO ratio syngas to carbonaceous products comprising reacting the syngas with water or steam at 200 to 350/sup 0/C in the presence of a metal catalyst supported on zinc oxide. Hydrocarbons are produced with a catalyst selected from cobalt, nickel or ruthenium and alcohols are produced with a catalyst selected from palladium, platinum, ruthenium or copper on the zinc oxide support. The ratio of the reactants are such that for alcohols and saturated hydrocarbons: (2n + 1) greater than or equal to x greater than or equal to O and for olefinic hydrocarbons: 2n greater than or equal to x greater than or equal to O where n is the number of carbon atoms in the product and x is the molar amount of water in the reaction mixture.

Prebiotic molecules formation through the gas-phase reaction between HNO and CH2CHOH2+

NASA Astrophysics Data System (ADS)

Redondo, Pilar; Martínez, Henar; Largo, Antonio; Barrientos, Carmen

2017-07-01

Context. Knowing how the molecules that are present in the ISM can evolve to more complex ones is an interesting topic in interstellar chemistry. The study of possible reactions between detected species can help to understand the evolution in complexity of the interstellar matter and also allows knowing the formation of new molecules which could be candidates to be detected. We focus our attention on two molecules detected in space, vinyl alcohol (CH2CHOH) and azanone (HNO). Aims: We aim to carry out a theoretical study of the ion-molecule reaction between protonated vinyl alcohol and azanone. The viability of formation of complex organic molecules (COMs) from these reactants is expected to provide some insight into the formation of prebiotic species through gas phase reactions. Methods: The reaction of protonated vinyl alcohol with azanone has been theoretically studied by using ab initio methods. Stationary points on the potential energy surface (PES) were characterized at the second-order Moller-Plesset level in conjunction with the aug-cc-pVTZ (correlation-consistent polarized valence triple-zeta) basis set. In addition, the electronic energies were refined by means of single-point calculations at the CCSD(T) level (coupled cluster single and double excitation model augmented with a non-iterative treatment of triple excitations) with the same basis set. Results: From a thermodynamic point of view, twelve products, composed of carbon, oxygen, nitrogen, and hydrogen which could be precursors in the formation of more complex biological molecules, can be obtained from this reaction. Among these, we focus especially on ionized glycine and two of its isomers. The analysis of the PES shows that only formation of cis- and trans-O-protonated imine acetaldehyde, CH2NHCOH+ and, CHNHCHOH+, are viable under interstellar conditions. Conclusions: The reaction of protonated vinyl alcohol with azanone can evolve in the interstellar medium to more complex organic molecules of prebiotic interest. Our results suggest that imine acetaldehyde could be a feasible candidate molecule to be searched for in space.

Method for the synthesis of chiral allylic alcohols utilizing selone based chiral derivatizing agents

DOEpatents

Silks, III, Louis A.

2002-01-01

Molecules containing a chiral 1,2-diol unit are synthesized from reactions between aldehydes and N-acyl selones. A chilled N-acyl selone is reacted with a Lewis acid such as TiCl.sub.4 and mixed with a tertiary amine such as diisopropylethylamine to generate an enolate solution. Upon further chilling of the enolate solution a desired aldehyde is added and after an acceptable reaction period a quencher is introduced and the product isolated.

Alcohol Oxidation at Platinum–Gas and Platinum–Liquid Interfaces: The Effect of Platinum Nanoparticle Size, Water Coadsorption, and Alcohol Concentration

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

Tatsumi, Hironori; Liu, Fudong; Han, Hui-Ling

Platinum nanoparticles size range from 1 to 8 nm deposited on mesoporous silica MCF-17 catalyzed alcohol oxidations were studied in the gas and liquid phases. Among methanol, ethanol, 2- propanol and 2-butanol reactions, the turnover frequency increased with Pt nanoparticle size for all the alcohols utilized. The activation energies for the oxidations were almost same among all alcohol species, but higher in the gas phase than those in the liquid phase. Water coadsorption poisoned the reaction in the gas phase, while it increased the reaction turnover rates in the liquid phase. Sum frequency generation (SFG) vibrational spectroscopy studies and DFTmore » calculations revealed that the alcohol molecules pack horizontally on the metal surface in low concentrations and stand up in high concentrations, which affect the dissociation of β-hydrogen of the alcohols as the critical step in alcohol oxidations.« less

Alcohol Oxidation at Platinum–Gas and Platinum–Liquid Interfaces: The Effect of Platinum Nanoparticle Size, Water Coadsorption, and Alcohol Concentration

DOE PAGES

Tatsumi, Hironori; Liu, Fudong; Han, Hui-Ling; ...

2017-03-21

Platinum nanoparticles size range from 1 to 8 nm deposited on mesoporous silica MCF-17 catalyzed alcohol oxidations were studied in the gas and liquid phases. Among methanol, ethanol, 2- propanol and 2-butanol reactions, the turnover frequency increased with Pt nanoparticle size for all the alcohols utilized. The activation energies for the oxidations were almost same among all alcohol species, but higher in the gas phase than those in the liquid phase. Water coadsorption poisoned the reaction in the gas phase, while it increased the reaction turnover rates in the liquid phase. Sum frequency generation (SFG) vibrational spectroscopy studies and DFTmore » calculations revealed that the alcohol molecules pack horizontally on the metal surface in low concentrations and stand up in high concentrations, which affect the dissociation of β-hydrogen of the alcohols as the critical step in alcohol oxidations.« less

Isoprenoid Alcohols are Susceptible to Oxidation with Singlet Oxygen and Hydroxyl Radicals.

PubMed

Komaszylo Née Siedlecka, Joanna; Kania, Magdalena; Masnyk, Marek; Cmoch, Piotr; Lozinska, Iwona; Czarnocki, Zbigniew; Skorupinska-Tudek, Karolina; Danikiewicz, Witold; Swiezewska, Ewa

2016-02-01

Isoprenoids, as common constituents of all living cells, are exposed to oxidative agents--reactive oxygen species, for example, singlet oxygen or hydroxyl radicals. Despite this fact, products of oxidation of polyisoprenoids have never been characterized. In this study, chemical oxidation of isoprenoid alcohols (Prenol-2 and -10) was performed using singlet oxygen (generated in the presence of hydrogen peroxide/molybdate or upon photochemical reaction in the presence of porphyrin), oxygen (formed upon hydrogen peroxide dismutation) or hydroxyl radical (generated by the hydrogen peroxide/sonication, UV/titanium dioxide or UV/hydrogen peroxide) systems. The structure of the obtained products, hydroxy-, peroxy- and heterocyclic derivatives, was studied with the aid of mass spectrometry (MS) and nuclear magnetic resonance (NMR) methods. Furthermore, mass spectrometry with electrospray ionization appeared to be a useful analytical tool to detect the products of oxidation of isoprenoids (ESI-MS analysis), as well as to establish their structure on the basis of the fragmentation spectra of selected ions (ESI-MS/MS analysis). Taken together, susceptibility of polyisoprenoid alcohols to various oxidizing agents was shown for the first time.

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

PubMed

Haddad, Terra D; Hirayama, Lacie C; Singaram, Bakthan

2010-02-05

We report a simple, efficient, and general method for the indium-mediated enantioselective allylation of aromatic and aliphatic aldehydes and ketones under Barbier-type conditions in a one-pot synthesis affording the corresponding chiral alcohol products in very good yield (up to 99%) and enantiomeric excess (up to 93%). Our method is able to tolerate various functional groups, such as esters, nitriles, and phenols. Additionally, more substituted allyl bromides, such as crotyl and cinnamyl bromide, can be used providing moderate enantioselectivity (72% and 56%, respectively) and excellent diastereoselectivity when employing cinnamyl bromide (>95/5 anti/syn). However, the distereoselectivity when using crotyl bromide was poor and other functionalized allyl bromides under our method afforded low enantioselectivities for the alcohol products. In these types of indium-mediated additions, solvent plays a major role in determining the nature of the organoindium intermediate and we observed the susceptibility of some allylindium intermediates to hydrolysis in protic solvents. Under our reaction conditions using a polar aprotic solvent, we suggest that an allylindium(III) species is the active allylating intermediate. In addition, we have observed the presence of a shiny, indium(0) nugget throughout the reaction, irrespective of the stoichiometry, indicating disproportionation of indium halide byproduct formed during the reaction.

Cyclopentadienone Oxidation Reaction Kinetics and Thermochemistry for the Alcohols, Hydroperoxides, and Vinylic, Alkoxy, and Alkylperoxy Radicals.

PubMed

Yommee, Suriyakit; Bozzelli, Joseph W

2016-01-28

Cyclopentadienone has one carbonyl and two olefin groups resulting in 4n + 2 π-electrons in a cyclic five-membered ring structure. Thermochemical and kinetic parameters for the initial reactions of cyclopentadienone radicals with O2 and the thermochemical properties for cyclopentadienone-hydroperoxides, alcohols, and alkenyl, alkoxy, and peroxy radicals were determined by use of computational chemistry. The CBS-QB3 composite and B3LYP density functional theory methods were used to determine the enthalpies of formation (ΔfH°298) using the isodesmic reaction schemes with several work reactions for each species. Entropy and heat capacity, S°(T) and Cp°(T) (50 K ≤ T ≤ 5000 K) are determined using geometric parameters, internal rotor potentials, and frequencies from B3LYP/6-31G(d,p) calculations. Standard enthalpies of formation are reported for parent molecules as cyclopentadienone, cyclopentadienone with alcohol, hydroperoxide substituents, and the cyclopentadienone-yl vinylic, alkoxy, and peroxy radicals corresponding to loss of a hydrogen atom from the carbon and oxygen sites. Entropy and heat capacity vs temperature also are reported for the parent molecules and for radicals. The thermochemical analysis shows The R(•) + O2 well depths are deep, on the order of 50 kcal mol(-1), and the R(•) + O2 reactions to RO + O (chain branching products) for cyclopentadienone-2-yl and cyclopentadienone-3-yl have unusually low reaction (ΔHrxn) enthalpies, some 20 or so kcal/mol below the entrance channels. Chemical activation kinetics using quantum RRK analysis for k(E) and master equation for falloff are used to show that significant chain branching as a function of temperature and pressure can occur when these vinylic radicals are formed.

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

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

Bataineh, Hajem; Pestovsky, Oleg; Bakac, Andreja

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

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

DOE PAGES

Bataineh, Hajem; Pestovsky, Oleg; Bakac, Andreja

2015-02-11

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

Biosynthesis of optically pure chiral alcohols by a substrate coupled and biphasic system with a short-chain dehydrogenase from Streptomyces griseus.

PubMed

Tan, Zhuotao; Ma, Hongmin; Li, Qing; Pu, Lingling; Cao, Yang; Qu, Xudong; Zhu, Chenjie; Ying, Hanjie

2016-11-01

The increasing demand for biocatalysts in synthesizing enantiomerically pure chiral alcohols results from the outstanding characteristics of enzymes in reaction, economic, ecological issues. Many carbonyl reductases for producing chiral alcohols have been reported but there is still a lack of good catalytic efficacies. Herein, five carbonyl reductases from different Streptomyces were discovered by the strategy of genome mining. These reductases were overexpressed, and we chose SgCR for further study as it owned better enzyme activity. This protein was purified to apparent homogeneity, and its amino acid sequence was analyzed in comparison with that of the reported SDRs. The biocatalytic properties of SgCR were investigated, and this enzyme was confirmed to have the ability to convert various prochiral ketones into highly optically active alcohols. SgCR exhibited the highest activity towards ethyl 4-chloro-3-oxobutanoate (COBE) and the corresponding product ethyl (S)-4-chloro-3-hydroxybutanoate ((S)-CHBE) was obtained with high yield and excellent e.e. value by optimizing the biphasic system. Eventually, using isopropanol as the co-substrate for NADH recycling in the substrate-coupled reaction, the yield and enantioselectivity of (S)-CHBE were obtained at the values of 90% and 99%, respectively. These results indicate that SgCR is a promising boicatalyst for the synthesis of chiral alcohols in industry. Copyright © 2016 Elsevier Inc. All rights reserved.

Environmental Processing of Lipids Driven by Aqueous Photochemistry of α-Keto Acids

PubMed Central

2018-01-01

Sunlight can initiate photochemical reactions of organic molecules though direct photolysis, photosensitization, and indirect processes, often leading to complex radical chemistry that can increase molecular complexity in the environment. α-Keto acids act as photoinitiators for organic species that are not themselves photoactive. Here, we demonstrate this capability through the reaction of two α-keto acids, pyruvic acid and 2-oxooctanoic acid, with a series of fatty acids and fatty alcohols. We show for five different cases that a cross-product between the photoinitiated α-keto acid and non-photoactive species is formed during photolysis in aqueous solution. Fatty acids and alcohols are relatively unreactive species, which suggests that α-keto acids are able to act as radical initiators for many atmospherically relevant molecules found in the sea surface microlayer and on atmospheric aerosol particles. PMID:29806009

A Grignard-like Organic Reaction in Water

NASA Astrophysics Data System (ADS)

Breton, Gary W.; Hughey, Christine A.

1998-01-01

The addition of a Grignard reagent to a carbonyl-containing compound to form an alcohol is an important reaction to demonstrate in organic chemistry laboratory courses. However, the reaction presents several practical problems for the lab instructor including the need for anhydrous solvents (e.g., ether), dry glassware, and the occasional problem of slow reaction initiation. We have scaled, and tested, a known Grignard-like reaction between allyl bromide and benzaldehyde mediated by zinc metal in aqueous media. The procedure retains the desirable features of the traditional Grignard reaction, while eliminating some of the commonly encountered difficulties. Thus, addition of allyl bromide (1.2 eq) to benzaldehyde and zinc in a two-phase mixture of THF and saturated aqueous NH4Cl afforded addition product 1-phenyl-3-buten-1-ol in 70-85% yields.

Production and characterization of hydrophobic zinc borate by using palm oil

NASA Astrophysics Data System (ADS)

Acarali, Nil Baran; Tugrul, Nurcan; Derun, Emek Moroydor; Piskin, Sabriye

2013-11-01

Zinc borate (ZB) was synthesized using zinc oxide, boric acid synthesized from colemanite, and reference ZB as seed. The effects of reaction parameters such as reaction time, reactant ratio, and seed ratio on its yield were examined. Then, the effects of palm oil with solvents (isopropyl alcohol (IPA), ethanol, and methanol) added to the reaction on its hydrophobicity were explored. Reactions were carried out under determined reaction conditions with magnetically and mechanically stirred systems. The produced ZB was characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), and measurements of contact angle identified hydrophobicity. The results showed that hydrophobic ZB was successfully produced under determined reaction conditions. The change of process parameters influenced its yield and the usage of palm oil provided hydrophobicity.

Enzymatic Resolution and Separation of Secondary Alcohols Based on Fatty Esters as Acylating Agents

ERIC Educational Resources Information Center

Monteiro, Carlos M.; Afonso, Carlos A. M.; Lourenco, Nuno M. T.

2010-01-01

The enzymatic resolution of "rac"-1-phenylethanol using ethyl myristate as acylating agent and solvent and "Candida antarctica" lipase B (CAL-B) as biocatalyst was demonstrated with catalyst and medium reuse. Both enantiomers of 1-phenylethanol were isolated by sequential enzymatic reactions and product distillations. From the first enzymatic…

Synthesis of a Fluorescent Acridone Using a Grignard Addition, Oxidation, and Nucleophilic Aromatic Substitution Reaction Sequence

ERIC Educational Resources Information Center

Goodrich, Samuel; Patel, Miloni; Woydziak, Zachary R.

2015-01-01

A three-pot synthesis oriented for an undergraduate organic chemistry laboratory was developed to construct a fluorescent acridone molecule. This laboratory experiment utilizes Grignard addition to an aldehyde, alcohol oxidation, and iterative nucleophilic aromatic substitution steps to produce the final product. Each of the intermediates and the…

Cross-linked polyvinyl alcohol and method of making same

NASA Technical Reports Server (NTRS)

Hsu, L. C.; Sheibley, D. W.; Philipp, W. H. (Inventor)

1981-01-01

A film-forming polyvinyl alcohol polymer is mixed with a polyaldehyde-polysaccharide cross-linking agent having at least two monosaccharide units and a plurality of aldehyde groups per molecule, perferably an average of at least one aldehyde group per monosaccharide units. The cross-linking agent, such as a polydialdehyde starch, is used in an amount of about 2.5 to 20% of the theoretical amount required to cross-link all of the available hydroxyl groups of the polyvinyl alcohol polymer. Reaction between the polymer and cross-linking agent is effected in aqueous acidic solution to produce the cross-linked polymer. The polymer product has low electrical resistivity and other properties rendering it suitable for making separators for alkaline batteries.

Renewable energy from biomass: a sustainable option? - Hydrogen production from alcohols

NASA Astrophysics Data System (ADS)

Balla, Zoltán; Kith, Károly; Tamás, András; Nagy, Orsolya

2015-04-01

Sustainable development requires us to find new energy sources instead of fossil fuels. One possibility is the hydrogen fuel cell, which uses significantly more efficient than the current combustion engines. The task of the hydrogen is clean, carbon-free renewable energy sources to choose in the future by growing degree. Hungary can play a role in the renewable energy sources of biomass as a renewable biomass annually mass of about 350 to 360 million tons. The biomass is only a very small proportion of fossil turn carbonaceous materials substitution, while we may utilize alternative energy sources as well. To the hydrogen production from biomass, the first step of the chemical transformations of chemical bonds are broken, which is always activation energy investment needs. The methanol and ethanol by fermentation from different agricultural products is relatively easy to produce, so these can be regarded as renewable energy carriers of. The ethanol can be used directly, and used in several places in the world are mixed with the petrol additive. This method is the disadvantage that the anhydrous alcohol is to be used in the combustion process in the engine more undesired by-products may be formed, and the fuel efficiency of the engine is significantly lower than the efficiency of the fuel cells. More useful to produce hydrogen from the alcohol and is used in a fuel cell electric power generation. Particularly attractive option for the so-called on-board reforming of alcohols, that happens immediately when the vehicle hydrogen production. It does not need a large tank of hydrogen, because the hydrogen produced would be directly to the fuel cell. The H2 tank limit use of its high cost, the significant loss evaporation, the rare-station network, production capacity and service background and lack of opportunity to refuel problems. These can be overcome, if the hydrogen in the vehicle is prepared. As volume even 700 bar only about half the H2 pressure gas can be stored in the case, than the same volume of ethanol-water mixture can be prepared. The renewal of alcohol, the alcohol-water mixture is then passed through the catalytic reformer into a preheater. The exhaust gas contains a relatively large number of carbon monoxide, which would spoil the fuel cell, so the carbon monoxide concentration to a high and a low temperature water-gas reaction is reduced. This increases the hydrogen production. The last step of the carbon monoxide content to eliminate preferential oxidation. The alcohol reforming catalyst for the precious metals spread most of what arose from high activity and stability. However, the precious metals are very expensive, so a non-precious metal catalysts is the design and development of objective activity and stability which reaches the precious metal catalysts of. Using the new reaction catalysts opportunities are created, which are smaller than the activation energy than the non-catalytic process. The basic objective of the technological developments more active at lower temperatures, the selective target product, long-life, low cost design catalysts.

Synthesis of Formate Esters and Formamides Using an Au/TiO2-Catalyzed Aerobic Oxidative Coupling of Paraformaldehyde

PubMed Central

Metaxas, Ioannis; Vasilikogiannaki, Eleni

2017-01-01

A simple method for the synthesis of formate esters and formamides is presented based on the Au/TiO2-catalyzed aerobic oxidative coupling between alcohols or amines and formaldehyde. The suitable form of formaldehyde is paraformaldehyde, as cyclic trimeric 1,3,5-trioxane is inactive. The reaction proceeds via the formation of an intermediate hemiacetal or hemiaminal, respectively, followed by the Au nanoparticle-catalyzed aerobic oxidation of the intermediate. Typically, the oxidative coupling between formaldehyde (2 equiv) and amines occurs quantitatively at room temperature within 4 h, and there is no need to add a base as in analogous coupling reactions. The oxidative coupling between formaldehyde (typically 3 equiv) and alcohols is unprecedented and occurs more slowly, yet in good to excellent yields and selectivity. Minor side-products (2–12%) from the acetalization of formaldehyde by the alcohol are also formed. The catalyst is recyclable and can be reused after a simple filtration in five consecutive runs with a small loss of activity. PMID:29231853

Cell-free metabolic engineering: production of chemicals by minimized reaction cascades.

PubMed

Guterl, Jan-Karl; Garbe, Daniel; Carsten, Jörg; Steffler, Fabian; Sommer, Bettina; Reiße, Steven; Philipp, Anja; Haack, Martina; Rühmann, Broder; Koltermann, Andre; Kettling, Ulrich; Brück, Thomas; Sieber, Volker

2012-11-01

The limited supply of fossil resources demands the development of renewable alternatives to petroleum-based products. Here, biobased higher alcohols such as isobutanol are versatile platform molecules for the synthesis of chemical commodities and fuels. Currently, their fermentation-based production is limited by the low tolerance of microbial production systems to the end products and also by the low substrate flux into cell metabolism. We developed an innovative cell-free approach, utilizing an artificial minimized glycolytic reaction cascade that only requires one single coenzyme. Using this toolbox the cell-free production of ethanol and isobutanol from glucose was achieved. We also confirmed that these streamlined cascades functioned under conditions at which microbial production would have ceased. Our system can be extended to an array of industrially-relevant molecules. Application of solvent-tolerant biocatalysts potentially allows for high product yields, which significantly simplifies downstream product recovery. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Liquid-Phase Electrical Discharges: Fundamental Mechanisms and Applications

NASA Astrophysics Data System (ADS)

Franclemont, Joshua

The increased demand in alternative energy in recent decades has generated significant interest in cleaner fuel sources including hydrogen and syngas (hydrogen and carbon monoxide). Hydrogen and syngas are both primarily produced through the steam reforming of hydrocarbons, specifically natural gas. Although other processes are known, the cheapest source of these fuels is currently through the heating of natural gas in the presence of steam and a catalyst. However, due to the emissions associated with the steam reforming of natural gas and the lack of low cost, efficient, and reliable onboard hydrogen storage technologies for fuel cell powered vehicles, attention has been focused on plasma-assisted reforming of hydrocarbons. Plasma processes can be implemented onboard and are able to directly reform liquid hydrocarbons and alcohols without external heating or catalysts. In addition to hydrogen and syngas, the plasma-assisted reforming of hydrocarbons and alcohols offers other desirable products such as C2 gases (ethane, ethylene, and acetylene), methanol and ethanol. The primary goal of this study is to investigate the fundamental chemical reactions occurring during plasma-assisted reforming of liquid hydrocarbons and alcohols using streamer-like pulsed electrical discharges. Due to the relatively unexplored field of chemical reactions in liquid plasmas, the focus of this study is on elucidating chemical pathways responsible for the formation of hydrogen, syngas, and other products during the direct reforming of liquid methanol, glycerol, and pentane as model species.

Asymmetric Baylis-Hillman reactions promoted by chiral imidazolines.

PubMed

Xu, Junye; Guan, Yanyi; Yang, Shihui; Ng, Yurui; Peh, Guangrong; Tan, Choon-Hong

2006-11-20

The coupling of electrophiles with activated alkenes by using tertiary amines or phosphines is generally known as the Baylis-Hillman reaction. It is a useful and atom-economical carbon-carbon bond-forming reaction that generates multifunctionalized products. This reaction is notoriously slow; yields are often low and substrate-dependent. The asymmetric reaction is still limited especially for unactivated olefins such as acrylates. Imidazolines have been developed as ligands in metal-catalyzed reactions and have also been used as privileged structures in diversity-oriented synthesis. A series of novel chiral imidazolines were prepared and used to develop asymmetric Baylis-Hillman reactions. These imidazolines promote the reactions of various aromatic aldehydes with unactivated acrylates. Enantiomeric excesses of up to 60% and high yields were obtained by using stoichiometric amounts of the promoter. Furthermore, the imidazolines are also suitable promoters for the reactions between aromatic aldehydes and alkyl vinyl ketones. Enantiomeric excesses of up to 78% and high yields were obtained with 50 mol % of an imidazoline with a chiral methylnaphthyl group. These chiral imidazolines are easily prepared from commercially available amino alcohols and can be easily recovered for reuse without loss of product enantioselectivity.

Impact of reaction products from building materials and furnishings on indoor air quality—A review of recent advances in indoor chemistry

NASA Astrophysics Data System (ADS)

Uhde, E.; Salthammer, T.

The variety of chemical substances present in modern building products, household products and furnishings provides potential for chemical reactions in the material (case 1), on the material surface (case 2) and in the gas phase (case 3). Such "indoor chemistry" is known as one of the main reasons for primary and secondary emissions. The conditions of production often cause unwanted side reactions and a number of new compounds can be found in finished products. Elevated temperatures are responsible for the degradation of cellulose, decomposition of non-heat-resistant additives and other thermally induced reactions like Diels-Alder synthesis. Heterogeneous chemistry takes place on the surface of materials. Well-known examples are the formation of aliphatic aldehydes from the oxidation of unsaturated fatty acids or the cleavage of photoinitiators under the influence of light. In case of composite flooring structures hydrolysis is one of the major pathways for the appearance of alcohols from esters. If different kinds of material are fixed together, emissions of new VOCs formed by inter-species reactions are possible. Other indoor air pollutants are formed by rearrangement of cleavage products or by metabolism. Compounds with -C dbnd C- bonds like terpenes, styrene, 4-phenylcyclohexene, etc. undergo gas phase reactions with O 3, NO x, OH and other reactive gases. It has been shown that such products derived from indoor-related reactions may have a negative impact on indoor air quality due to their low odor threshold or health-related properties. Therefore, the understanding of primary and secondary emissions and the chemical processes behind is essential for the evaluation of indoor air quality. This publication gives an overview on the current state of research and new findings regarding primary and secondary emissions from building products and furnishings.

Hydrogen bonding effects on the reorganization energy for photoinduced charge separation reaction between porphyrin and quinone studied by nanosecond laser flash photolysis.

PubMed

Yago, Tomoaki; Gohdo, Masao; Wakasa, Masanobu

2010-02-25

Alcohol concentration dependences of photoinduced charge separation (CS) reaction of zinc tetraphenyl-porphyrin (ZnTPP) and duroquinone (DQ) were investigated in benzonitrile by a nanosecond laser flash photolysis technique. The photoinduced CS reaction was accelerated by the addition of alcohols, whereas the addition of acetonitrile caused little effect on the CS reactions. The simple theory was developed to calculate an increase in reorganization energies induced by the hydrogen bonding interactions between DQ and alcohols using the chemical equilibrium constants for the hydrogen bonding complexes through the concerted pathway and the stepwise one. The experimental results were analyzed by using the Marcus equation where we took into account the hydrogen bonding effects on the reorganization energy and the reaction free energy for the CS reaction. The observed alcohol concentration dependence of the CS reaction rates was well explained by the formation of the hydrogen bonding complexes through the concerted pathway, demonstrating the increase in the reorganization energy by the hydrogen bonding interactions.

Acetate ester production by Chinese yellow rice wine yeast overexpressing the alcohol acetyltransferase-encoding gene ATF2.

PubMed

Zhang, J; Zhang, C; Qi, Y; Dai, L; Ma, H; Guo, X; Xiao, D

2014-11-27

Acetate ester, which are produced by fermenting yeast cells in an enzyme-catalyzed intracellular reaction, are responsible for the fruity character of fermented alcoholic beverages such as Chinese yellow rice wine. Alcohol acetyltransferase (AATase) is currently believed to be the key enzyme responsible for the production of acetate ester. In order to determine the precise role of the ATF2 gene in acetate ester production, an ATF2 gene encoding a type of AATase was overexpressed and the ability of the mutant to form acetate esters (including ethyl acetate, isoamyl acetate, and isobutyl acetate) was investigated. The results showed that after 5 days of fermentation, the concentrations of ethyl acetate, isoamyl acetate, and isobutyl acetate in yellow rice wines fermented with EY2 (pUC-PIA2K) increased to 137.79 mg/L (an approximate 4.9-fold increase relative to the parent cell RY1), 26.68 mg/L, and 7.60 mg/L, respectively. This study confirms that the ATF2 gene plays an important role in the production of acetate ester production during Chinese yellow rice wine fermentation, thereby offering prospects for the development of yellow rice wine yeast starter strains with optimized ester-producing capabilities.

Some features of the oxidative conversion of Mo(CO)/sub 6/ in a medium of hydroperoxide or tert-butyl hydroperoxide and an aromatic hydrocarbon

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

Fomin, V.M.; Lunin, A.V.; Aleksandrov, Yu.A.

1988-03-10

Occurrence of the reaction under study was followed from the decrease in hydroperoxide or of Mo(CO)/sub 6/. The Mo(CO)/sub 6/ content of the reaction was found by determining either the concentration of this compound directly or by determining the concentration of the gaseous products from its transformations (CO + CO/sub 2/). Hydroperoxides (I) and (II) were determined iodometrically. Metal-containing products of the oxidation of Mo(CO)/sub 6/, molybdenum oxides and peroxides, were analyzed by IR and ESR spectroscopy, elemental analysis, and iodometry. Analysis of transformation products of the hydroperoxides (phenol, acetone, dimethylphenylcarbinol, acetophenone, tert-butyl alcohol, water, and oxygen) was performed usingmore » gas chromatography. Results are presented.« less

The Reactions of Polycyclic Aromatic Hydrocarbons with OH

NASA Technical Reports Server (NTRS)

Ricca, Alessandra; Bauschlicher, Charles W., Jr.; Arnold, James O. (Technical Monitor)

2000-01-01

The OH radical adds to naphthalene and naphthalene cation without a barrier. For the neutrals, the most favorable path for this intermediate is the loss of the OH, and the next most favorable option is the loss of an H atom to form the alcohol. For the cation, the most favorable path appears to be a hydrogen migration followed by the loss of a hydrogen to form the alcohol. The OH at carbon atom 1 is energetically most favorable for both the initial complex and final product. This is true for both the neutrals and cations.

Interaction of aromatic alcohols, aldehydes and acids with α-hydroxyl-containing carbon-centered radicals: A steady state radiolysis study

NASA Astrophysics Data System (ADS)

Samovich, S. N.; Brinkevich, S. D.; Shadyro, O. I.

2013-01-01

Benzaldehyde and its derivatives efficaciously oxidize in aqueous solutions α-hydroxyl-containing carbon-centered radicals (α-HCR) of various structures, suppressing thereby the radical recombination and fragmentation reactions. The compounds containing cinnamic moieties are capable of adding α-hydroxyethyl radicals (α-HER) to the carbon-carbon double bonds conjugated with the aromatic system to form molecular products identifiable by mass spectrometry. On radiolysis of aqueous ethanol solutions, reduction of α-HER by aromatic alcohols and acids has been shown to proceed via formation of their adducts with hydrated electron species.

Analysis of dynamic hydrogen (H2) generation

NASA Astrophysics Data System (ADS)

Buford, Marcelle C.

2003-03-01

The focus of this research is on-demand hydrogen generation for applications such as electric vehicles and electric appliances. Hydrogen can be generated by steam reformation of alcohols, hydrocarbons and other hydrogen containing complexes. Steam reformation can be represented as a simple chemical reaction between an alcohol, commonly methanol, and water vapor to produce hydrogen and carbon dioxide. A fuel cell can then be employed to produce electrical power from hydrogen and air. Numerical and experimental techniques are employed to analyze the most appropriate reforming fuel to maximize H2 yield and minimize by-products of which carbon monoxide is the most harmful

Enantioselective epoxidation with chiral MN(III)(salen) catalysts: kinetic resolution of aryl-substituted allylic alcohols.

PubMed

Adam, W; Humpf, H U; Roschmann, K J; Saha-Möller, C R

2001-08-24

A set of aryl-substituted allylic alcohols rac-2 has been epoxidized by chiral Mn(salen*) complexes 1 as the catalyst and iodosyl benzene (PhIO) as the oxygen source. Whereas one enantiomer of the allylic alcohol 2 is preferentially epoxidized to give the threo- or cis-epoxy alcohol 3 (up to 80% ee) as the main product (dr up to >95:5), the other enantiomer of 2 is enriched (up to 53% ee). In the case of 1,1-dimethyl-1,2-dihydronaphthalen-2-ol (2c), the CH oxidation to the enone 4c proceeds enantioselectively and competes with the epoxidation. The absolute configurations of the allylic alcohols 2 and their epoxides 3 have been determined by chemical correlation or CD spectroscopy. The observed diastereo- and enantioselectivities in the epoxidation reactions are rationalized in terms of a beneficial interplay between the hydroxy-directing effect and the attack along the Katsuki trajectory.

Microkinetic Modeling of Benzyl Alcohol Oxidation on Carbon-Supported Palladium Nanoparticles

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

Savara, Aditya; Rossetti, Ilenia; Chan-Thaw, Carine E.

Six products are formed from benzyl alcohol oxidation over Pd nanoparticles using O2 as the oxidant: benzaldehyde, toluene, benzyl ether, benzene, benzoic acid, and benzyl benzoate. Three experimental parameters were varied here: alcohol concentration, oxygen concentration, and temperature. Microkinetic modeling using a mechanism published recently with surface intermediates was able to produce all 18 trends observed experimentally with mostly quantitative agreement. Approximate analytical equations derived from the microkinetic model for isothermal conditions reproduced the isothermal trends and provided insight. The most important activation energies are Ea2=57.9 kJ mol₋1, Ea5=129 kJ mol₋1, and Ea6=175 kJ mol₋1, which correspond to alcohol dissociation,more » alkyl hydrogenation, and the reaction of alkyl species with alkoxy species. Upper limits for other activation energies were identified. The concepts of a sticking coefficient and steric factor in solution were applied.« less

Microkinetic Modeling of Benzyl Alcohol Oxidation on Carbon-Supported Palladium Nanoparticles

DOE PAGES

Savara, Aditya; Rossetti, Ilenia; Chan-Thaw, Carine E.; ...

2016-07-14

Six products are formed from benzyl alcohol oxidation over Pd nanoparticles using O2 as the oxidant: benzaldehyde, toluene, benzyl ether, benzene, benzoic acid, and benzyl benzoate. Three experimental parameters were varied here: alcohol concentration, oxygen concentration, and temperature. Microkinetic modeling using a mechanism published recently with surface intermediates was able to produce all 18 trends observed experimentally with mostly quantitative agreement. Approximate analytical equations derived from the microkinetic model for isothermal conditions reproduced the isothermal trends and provided insight. The most important activation energies are Ea2=57.9 kJ mol₋1, Ea5=129 kJ mol₋1, and Ea6=175 kJ mol₋1, which correspond to alcohol dissociation,more » alkyl hydrogenation, and the reaction of alkyl species with alkoxy species. Upper limits for other activation energies were identified. The concepts of a sticking coefficient and steric factor in solution were applied.« less

Gas-phase ozonolysis of ethene in the presence of carbonyl-oxide scavengers

NASA Astrophysics Data System (ADS)

Wolff, Silke; Boddenberg, Axel; Thamm, Jürgen; Turner, Walter V.; Gäb, Siegmar

Potential carbonyl-oxide scavengers are included in gas-phase ozonolysis experiments in an attempt to determine the extent to which the Criegee mechanism is involved. The scavengers selected are those whose reaction mechanism in the liquid phase is understood; water, hydrogen peroxide, alcohols and carboxylic acids have thus far been examined. The products of the ozonolysis of ethene in the gas phase depend on whether carbonyl-oxide scavengers are present. In the absence of scavengers, formaldehyde and formic acid are the major products, and only minor amounts of H 2O 2 and hydroxymethyl hydroperoxide are found. In the presence of a scavenger, certain products observed in addition to these can be regarded as arising from addition of the scavenger to the carbonyl oxide. Thus, H 2O 2 leads to the formation of hydroperoxymethyl hydroperoxide, while alcohols and formic acid give alkoxymethyl hydroperoxides and hydroperoxymethyl formate, respectively.

Enzymatic synthesis of chiral amino‐alcohols by coupling transketolase and transaminase‐catalyzed reactions in a cascading continuous‐flow microreactor system

PubMed Central

Gruber, Pia; Carvalho, Filipe; Marques, Marco P. C.; O'Sullivan, Brian; Subrizi, Fabiana; Dobrijevic, Dragana; Ward, John; Hailes, Helen C.; Fernandes, Pedro; Wohlgemuth, Roland; Baganz, Frank

2017-01-01

Abstract Rapid biocatalytic process development and intensification continues to be challenging with currently available methods. Chiral amino‐alcohols are of particular interest as they represent key industrial synthons for the production of complex molecules and optically pure pharmaceuticals. (2S,3R)‐2‐amino‐1,3,4‐butanetriol (ABT), a building block for the synthesis of protease inhibitors and detoxifying agents, can be synthesized from simple, non‐chiral starting materials, by coupling a transketolase‐ and a transaminase‐catalyzed reaction. However, until today, full conversion has not been shown and, typically, long reaction times are reported, making process modifications and improvement challenging. In this contribution, we present a novel microreactor‐based approach based on free enzymes, and we report for the first time full conversion of ABT in a coupled enzyme cascade for both batch and continuous‐flow systems. Using the compartmentalization of the reactions afforded by the microreactor cascade, we overcame inhibitory effects, increased the activity per unit volume, and optimized individual reaction conditions. The transketolase‐catalyzed reaction was completed in under 10 min with a volumetric activity of 3.25 U ml−1. Following optimization of the transaminase‐catalyzed reaction, a volumetric activity of 10.8 U ml−1 was attained which led to full conversion of the coupled reaction in 2 hr. The presented approach illustrates how continuous‐flow microreactors can be applied for the design and optimization of biocatalytic processes. PMID:28986983

Comprehensive near infrared study of Jatropha oil esterification with ethanol for biodiesel production

NASA Astrophysics Data System (ADS)

Oliveira, Alianda Dantas de; Sá, Ananda Franco de; Pimentel, Maria Fernanda; Pacheco, José Geraldo A.; Pereira, Claudete Fernandes; Larrechi, Maria Soledad

2017-01-01

This work presents a comprehensive near infrared study for in-line monitoring of the esterification reaction of high acid oils, such as Jatropha curcas oil, using ethanol. Parallel reactions involved in the process were carried out to select a spectral region that characterizes the evolution of the esterification reaction. Using absorbance intensities at 5176 cm- 1, the conversion and kinetic behaviors of the esterification reaction were estimated. This method was applied to evaluate the influence of temperature and catalyst concentration on the estimates of initial reaction rate and ester conversion as responses to a 22 factorial experimental design. Employment of an alcohol/oil ratio of 16:1, catalyst concentration of 1.5% w/w, and temperatures at 65 °C or 75 °C, made it possible to reduce the initial acidity from 18% to 1.3% w/w, which is suitable for transesterification of high free fatty acid oils for biodiesel production. Using the proposed analytical method in the esterification reaction of raw materials with high free fatty acid content for biodiesel makes the monitoring process inexpensive, fast, simple, and practical.

Tunable catalytic properties of bi-functional mixed oxides in ethanol conversion to high value compounds

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

Ramasamy, Karthikeyan K.; Gray, Michel J.; Job, Heather M.

2016-04-10

tA highly versatile ethanol conversion process to selectively generate high value compounds is pre-sented here. By changing the reaction temperature, ethanol can be selectively converted to >C2alcohols/oxygenates or phenolic compounds over hydrotalcite derived bi-functional MgO–Al2O3cata-lyst via complex cascade mechanism. Reaction temperature plays a role in whether aldol condensationor the acetone formation is the path taken in changing the product composition. This article containsthe catalytic activity comparison between the mono-functional and physical mixture counterpart to thehydrotalcite derived mixed oxides and the detailed discussion on the reaction mechanisms.

Tunable catalytic properties of bi-functional mixed oxides in ethanol conversion to high value compounds

DOE PAGES

Ramasamy, Karthikeyan K.; Gray, Michel; Job, Heather; ...

2016-02-03

Here, a highly versatile ethanol conversion process to selectively generate high value compounds is presented here. By changing the reaction temperature, ethanol can be selectively converted to >C 2 alcohols/oxygenates or phenolic compounds over hydrotalcite derived bi-functional MgO–Al 2O 3 catalyst via complex cascade mechanism. Reaction temperature plays a role in whether aldol condensation or the acetone formation is the path taken in changing the product composition. This article contains the catalytic activity comparison between the mono-functional and physical mixture counterpart to the hydrotalcite derived mixed oxides and the detailed discussion on the reaction mechanisms.

Yeast Metabolites of Glycated Amino Acids in Beer.

PubMed

Hellwig, Michael; Beer, Falco; Witte, Sophia; Henle, Thomas

2018-06-01

Glycation reactions (Maillard reactions) during the malting and brewing processes are important for the development of the characteristic color and flavor of beer. Recently, free and protein-bound Maillard reaction products (MRPs) such as pyrraline, formyline, and maltosine were found in beer. Furthermore, these amino acid derivatives are metabolized by Saccharomyces cerevisiae via the Ehrlich pathway. In this study, a method was developed for quantitation of individual Ehrlich intermediates derived from pyrraline, formyline, and maltosine. Following synthesis of the corresponding reference material, the MRP-derived new Ehrlich alcohols pyrralinol (up to 207 μg/L), formylinol (up to 50 μg/L), and maltosinol (up to 6.9 μg/L) were quantitated for the first time in commercial beer samples by reverse phase high performance liquid chromatography tandem mass spectrometry in the multiple reaction monitoring mode. This is equivalent to ca. 20-40% of the concentrations of the parent glycated amino acids. The metabolites were almost absent from alcohol-free beers and malt-based beverages. Two previously unknown valine-derived pyrrole derivatives were characterized and qualitatively identified in beer. The metabolites investigated represent new process-induced alkaloids that may influence brewing yeast performance due to structural similarities to quorum sensing and metal-binding molecules.

In situ fabricated platinum—poly(vinyl alcohol) nanocomposite thin film: a highly reusable ‘dip catalyst’ for hydrogenation

NASA Astrophysics Data System (ADS)

Divya Madhuri, U.; Kesava Rao, V.; Hariprasad, E.; Radhakrishnan, T. P.

2016-04-01

A simple protocol for the in situ generation of platinum nanoparticles in a poly(vinyl alcohol) (PVA) thin film is developed. Chloroplatinic acid as well as potassium platinum(II) chloride are used as precursors and the film is fabricated by spin coating followed by mild thermal annealing. The chemical process occurring inside the film, wherein the polymer itself acts as the reducing agent, is explored through different spectroscopy and microscopy techniques. The Pt-PVA film, <100 nm thick and containing ˜1 nm size Pt nanoparticles, is shown to be a highly efficient catalyst for the reduction of methylene blue using sodium borohydride. The ease of retrieval and reuse of the thin film is highlighted by the term ‘dip catalyst’. The reaction yield, kinetics and rate are reproducible through several reuses of the same catalyst film. Turnover number (TON = number of mols of product/number of mols of catalyst) and turnover frequency (TOF = TON/reaction time) are significantly higher than those reported earlier for this reaction using metal nanocatalysts. Utility of Pt-PVA film as an efficient catalyst for other hydrogenation reactions is demonstrated.

Study of the Low Temperature Oxidation of Propane

PubMed Central

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

2013-01-01

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

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

PubMed

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

2004-11-03

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

Optimized diazo scaffold for protein esterification.

PubMed

Mix, Kalie A; Raines, Ronald T

2015-05-15

The O-alkylation of carboxylic acids with diazo compounds provides a means to esterify carboxylic acids in aqueous solution. A Hammett analysis of the reactivity of diazo compounds derived from phenylglycinamide revealed that the (p-methylphenyl)glycinamide scaffold has an especially high reaction rate and ester/alcohol product ratio and esterifies protein carboxyl groups more efficiently than any known reagent.

Using polyfurfuryl alcohol to improve the hydrothermal stability of mesoporous oxides for reactions in the aqueous phase

USDA-ARS?s Scientific Manuscript database

Hydrodeoxygenation (HDO) of bio-oils derived from the pyrolysis of woody biomass is required to improve the stability and heating value of the liquid hydrocarbon products. Since pyrolysis produces bio-oils having up to 30 vol% water, HDO catalysts must not only be active and selective, but also sta...

Pyrolysis-GCMS Analysis of Solid Organic Products from Catalytic Fischer-Tropsch Synthesis Experiments

NASA Technical Reports Server (NTRS)

Locke, Darren R.; Yazzie, Cyriah A.; Burton, Aaron S.; Niles, Paul B.; Johnson, Natasha M.

2015-01-01

Abiotic synthesis of complex organic compounds in the early solar nebula that formed our solar system is hypothesized to occur via a Fischer-Tropsch type (FTT) synthesis involving the reaction of hydrogen and carbon monoxide gases over metal and metal oxide catalysts. In general, at low temperatures (less than 200 C), FTT synthesis is expected to form abundant alkane compounds while at higher temperatures (greater than 200 C) it is expected to product lesser amounts of n-alkanes and greater amounts of alkene, alcohol, and polycyclic aromatic hydrocarbons (PAHs). Experiments utilizing a closed-gas circulation system to study the effects of FTT reaction temperature, catalysts, and number of experimental cycles on the resulting solid insoluble organic products are being performed in the laboratory at NASA Goddard Space Flight Center. These experiments aim to determine whether or not FTT reactions on grain surfaces in the protosolar nebula could be the source of the insoluble organic matter observed in meteorites. The resulting solid organic products are being analyzed at NASA Johnson Space Center by pyrolysis gas chromatography mass spectrometry (PY-GCMS). PY-GCMS yields the types and distribution of organic compounds released from the insoluble organic matter generated from the FTT reactions. Previously, exploratory work utilizing PY-GCMS to characterize the deposited organic materials from these reactions has been reported. Presented here are new organic analyses using magnetite catalyst to produce solid insoluble organic FTT products with varying reaction temperatures and number of experimental cycles.

Focused and shifting attention in children with heavy prenatal alcohol exposure.

PubMed

Mattson, Sarah N; Calarco, Katherine E; Lang, Aimée R

2006-05-01

Attention deficits are a hallmark of the teratogenic effects of alcohol. However, characterization of these deficits remains inconclusive. Children with heavy prenatal alcohol exposure and nonexposed controls were evaluated using a paradigm consisting of three conditions: visual focus, auditory focus, and auditory-visual shift of attention. For the focus conditions, participants responded manually to visual or auditory targets. For the shift condition, participants alternated responses between visual targets and auditory targets. For the visual focus condition, alcohol-exposed children had lower accuracy and slower reaction time for all intertarget intervals (ITIs), while on the auditory focus condition, alcohol-exposed children were less accurate but displayed slower reaction time only on the longest ITI. Finally, for the shift condition, the alcohol-exposed group was accurate but had slowed reaction times. These results indicate that children with heavy prenatal alcohol exposure have pervasive deficits in visual focused attention and deficits in maintaining auditory attention over time. However, no deficits were noted in the ability to disengage and reengage attention when required to shift attention between visual and auditory stimuli, although reaction times to shift were slower. Copyright (c) 2006 APA, all rights reserved.

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

PubMed

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

2016-07-03

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

Production of higher quality bio-oils by in-line esterification of pyrolysis vapor

DOEpatents

Hilten, Roger Norris; Das, Keshav; Kastner, James R; Bibens, Brian P

2014-12-02

The disclosure encompasses in-line reactive condensation processes via vapor phase esterification of bio-oil to decease reactive species concentration and water content in the oily phase of a two-phase oil, thereby increasing storage stability and heating value. Esterification of the bio-oil vapor occurs via the vapor phase contact and subsequent reaction of organic acids with ethanol during condensation results in the production of water and esters. The pyrolysis oil product can have an increased ester content and an increased stability when compared to a condensed pyrolysis oil product not treated with an atomized alcohol.

Substrate specificity and subcellular localization of the aldehyde-alcohol redox-coupling reaction in carp cones.

PubMed

Sato, Shinya; Fukagawa, Takashi; Tachibanaki, Shuji; Yamano, Yumiko; Wada, Akimori; Kawamura, Satoru

2013-12-20

Our previous study suggested the presence of a novel cone-specific redox reaction that generates 11-cis-retinal from 11-cis-retinol in the carp retina. This reaction is unique in that 1) both 11-cis-retinol and all-trans-retinal were required to produce 11-cis-retinal; 2) together with 11-cis-retinal, all-trans-retinol was produced at a 1:1 ratio; and 3) the addition of enzyme cofactors such as NADP(H) was not necessary. This reaction is probably part of the reactions in a cone-specific retinoid cycle required for cone visual pigment regeneration with the use of 11-cis-retinol supplied from Müller cells. In this study, using purified carp cone membrane preparations, we first confirmed that the reaction is a redox-coupling reaction between retinals and retinols. We further examined the substrate specificity, reaction mechanism, and subcellular localization of this reaction. Oxidation was specific for 11-cis-retinol and 9-cis-retinol. In contrast, reduction showed low specificity: many aldehydes, including all-trans-, 9-cis-, 11-cis-, and 13-cis-retinals and even benzaldehyde, supported the reaction. On the basis of kinetic studies of this reaction (aldehyde-alcohol redox-coupling reaction), we found that formation of a ternary complex of a retinol, an aldehyde, and a postulated enzyme seemed to be necessary, which suggested the presence of both the retinol- and aldehyde-binding sites in this enzyme. A subcellular fractionation study showed that the activity is present almost exclusively in the cone inner segment. These results suggest the presence of an effective production mechanism of 11-cis-retinal in the cone inner segment to regenerate visual pigment.

Kinetics of the Reaction Between Alcohols and Isocyanates Catalyzed by Ferric Acetylacetonate

NASA Technical Reports Server (NTRS)

Schieler, Leroy

1961-01-01

The rate and temperature dependence of reaction for the ferric acetylacetonate catalyzed reaction between a-naphthyl, ortho-tolyl, and para-tolyl isocyanates and n-butyl alcohol are investigated. The effect of substituents on the reactivity of isocyanate and hydroxyl group are reported and for substituted isocyanates are correlated by means of the Hammett equation. Several metal chelates were studied and their catalytic activity was compared to that of ferric acetylacetonate. All rate data are interpreted in terms of a mechanism involving simultaneous second-order uncatalyzed and catalyzed reactions between alcohol and isocyanate.

Polydopamine-Coated TiO2 Nanotubes for Selective Photocatalytic Oxidation of Benzyl Alcohol to Benzaldehyde Under Visible Light.

PubMed

Tripathy, Jyotsna; Loget, Gabriel; Altomare, Marco; Schmuki, Patrik

2016-05-01

TiO2 nanotube arrays grown by anodization were coated with thin layers of polydopamine as visible light sensitizer. The PDA-coated TiO2 scaffolds were used as photocatalyst for selective oxidation of benzyl alcohol under monochromatic irradiation at 473 nm. Benzaldehyde was selectively formed and no by-products could be detected. A maximized reaction yield was obtained in O2-saturated acetonitrile. A mechanism is proposed that implies firstly the charge carrier generation in polydopamine as a consequence of visible light absorption. Secondly, photo-promoted electrons are injected in TiO2 conduction band, and subsequently transferred to dissolved O2 to form O*2- radicals. These radicals react with benzyl alcohol and lead to its selective dehydrogenation oxidation towards benzaldehyde.

Engineering high-level production of fatty alcohols by Saccharomyces cerevisiae from lignocellulosic feedstocks.

PubMed

d'Espaux, Leo; Ghosh, Amit; Runguphan, Weerawat; Wehrs, Maren; Xu, Feng; Konzock, Oliver; Dev, Ishaan; Nhan, Melissa; Gin, Jennifer; Reider Apel, Amanda; Petzold, Christopher J; Singh, Seema; Simmons, Blake A; Mukhopadhyay, Aindrila; García Martín, Héctor; Keasling, Jay D

2017-07-01

Fatty alcohols in the C12-C18 range are used in personal care products, lubricants, and potentially biofuels. These compounds can be produced from the fatty acid pathway by a fatty acid reductase (FAR), yet yields from the preferred industrial host Saccharomyces cerevisiae remain under 2% of the theoretical maximum from glucose. Here we improved titer and yield of fatty alcohols using an approach involving quantitative analysis of protein levels and metabolic flux, engineering enzyme level and localization, pull-push-block engineering of carbon flux, and cofactor balancing. We compared four heterologous FARs, finding highest activity and endoplasmic reticulum localization from a Mus musculus FAR. After screening an additional twenty-one single-gene edits, we identified increasing FAR expression; deleting competing reactions encoded by DGA1, HFD1, and ADH6; overexpressing a mutant acetyl-CoA carboxylase; limiting NADPH and carbon usage by the glutamate dehydrogenase encoded by GDH1; and overexpressing the Δ9-desaturase encoded by OLE1 as successful strategies to improve titer. Our final strain produced 1.2g/L fatty alcohols in shake flasks, and 6.0g/L in fed-batch fermentation, corresponding to ~ 20% of the maximum theoretical yield from glucose, the highest titers and yields reported to date in S. cerevisiae. We further demonstrate high-level production from lignocellulosic feedstocks derived from ionic-liquid treated switchgrass and sorghum, reaching 0.7g/L in shake flasks. Altogether, our work represents progress towards efficient and renewable microbial production of fatty acid-derived products. Published by Elsevier Inc.

Alcohol biosensing by polyamidoamine (PAMAM)/cysteamine/alcohol oxidase-modified gold electrode.

PubMed

Akin, Mehriban; Yuksel, Merve; Geyik, Caner; Odaci, Dilek; Bluma, Arne; Höpfner, Tim; Beutel, Sascha; Scheper, Thomas; Timur, Suna

2010-01-01

A highly stable and sensitive amperometric alcohol biosensor was developed by immobilizing alcohol oxidase (AOX) through Polyamidoamine (PAMAM) dendrimers on a cysteamine-modified gold electrode surface. Ethanol determination is based on the consumption of dissolved oxygen content due to the enzymatic reaction. The decrease in oxygen level was monitored at -0.7 V vs. Ag/AgCl and correlated with ethanol concentration. Optimization of variables affecting the system was performed. The optimized ethanol biosensor showed a wide linearity from 0.025 to 1.0 mM with 100 s response time and detection limit of (LOD) 0.016 mM. In the characterization studies, besides linearity some parameters such as operational and storage stability, reproducibility, repeatability, and substrate specificity were studied in detail. Stability studies showed a good preservation of the bioanalytical properties of the sensor, 67% of its initial sensitivity was kept after 1 month storage at 4 degrees C. The analytical characteristics of the system were also evaluated for alcohol determination in flow injection analysis (FIA) mode. Finally, proposed biosensor was applied for ethanol analysis in various alcoholic beverage as well as offline monitoring of alcohol production through the yeast cultivation. Copyright 2010 American Institute of Chemical Engineers

Conversion of Methanol, Ethanol and Propanol over Zeolites

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

Ramasamy, Karthikeyan K.; Wang, Yong

2013-06-04

Renewable fuel from lignocellulosic biomass has recently attracted more attention due to its environmental and the potential economic benefits over the crude oil [1]. In particular the production of fuel range hydrocarbon (HC) from alcohol generated lots of interest since the alcohol can be produced from biomass via thermochemical [2] (mixed alcohol from gasification derived synthesis gas) as well as the biochemical routes [3] (alcohol fermentation). Along with the development of ZSM5 synthesis and the discovery of methanol-to-gasoline (MTG) process by Mobil in 1970’s triggered lots of interest in research and development arena to understand the reaction mechanisms of alcoholsmore » over zeolites in particular ZSM5 [4]. More detailed research on methanol conversion was extensively reported [5] and in recent times the research work can be found on ethanol [6] and other alcohols as well but comprehensive comparison of catalyst activity and the deactivation mechanism of the conversion of various alcohols over zeolites has not been reported. The experiments were conducted on smaller alcohols such as methanol, ethanol and 1-propanol over HZSM5. The experimental results on the catalyst activity and the catalyst deactivation mechanism will be discussed.« less

Catalytic Dehydrogenative Coupling of Hydrosilanes with Alcohols for the Production of Hydrogen On-demand: Application of a Silane/Alcohol Pair as a Liquid Organic Hydrogen Carrier.

PubMed

Ventura-Espinosa, David; Carretero-Cerdán, Alba; Baya, Miguel; García, Hermenegildo; Mata, Jose A

2017-08-10

The compound [Ru(p-cym)(Cl) 2 (NHC)] is an effective catalyst for the room-temperature coupling of silanes and alcohols with the concomitant formation of molecular hydrogen. High catalyst activity is observed for a variety of substrates affording quantitative yields in minutes at room temperature and with a catalyst loading as low as 0.1 mol %. The coupling reaction is thermodynamically and, in the presence of a Ru complex, kinetically favourable and allows rapid molecular hydrogen generation on-demand at room temperature, under air, and without any additive. The pair silane/alcohol is a potential liquid organic hydrogen carrier (LOHC) for energy storage over long periods in a safe and secure way. Silanes and alcohols are non-toxic compounds and do not require special handling precautions such as high pressure or an inert atmosphere. These properties enhance the practical applications of the pair silane/alcohol as a good LOHC in the automotive industry. The variety and availability of silanes and alcohols permits a pair combination that fulfils the requirements for developing an efficient LOHC. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Alkali promoted molybdenum (IV) sulfide based catalysts, development and characterization for alcohol synthesis from carbon monoxide and hydrogen

NASA Astrophysics Data System (ADS)

Molina, Belinda Delilah

For more than a century transition metal sulfides (TMS) have been the anchor of hydro-processing fuels and upgrading bitumen and coal in refineries worldwide. As oil supplies dwindle and environmental laws become more stringent, there is a greater need for cleaner alternative fuels and/or synthetic fuels. The depletion of oil reserves and a rapidly increasing energy demand worldwide, together with the interest to reduce dependence on foreign oil makes alcohol production for fuels and chemicals via the Fischer Tropsch synthesis (FTS) very attractive. The original Fischer-Tropsch (FT) reaction is the heart of all gas-to-liquid technologies; it creates higher alcohols and hydrocarbons from CO/H2 using a metal catalyst. This research focuses on the development of alkali promoted MoS2-based catalysts to investigate an optimal synthesis for their assistance in the production of long chain alcohols (via FTS) for their use as synthetic transportation liquid fuels. Properties of catalytic material are strongly affected by every step of the preparation together with the quality of the raw materials. The choice of a laboratory method for preparing a given catalyst depends on the physical and chemical characteristics desired in the final composition. Characterization methods of K0.3/Cs0.3-MoS2 and K0.3 /Cs0.3-Co0.5MoS2 catalysts have been carried out through Scanning Electron Microscopy (SEM), BET porosity and surface analysis, Transmission Electron Microscopy (TEM) and X-Ray Diffraction (XRD). Various characterization methods have been deployed to correlate FTS products versus crystal and morphological properties of these heterogeneous catalysts. A lab scale gas to liquid system has been developed to evaluate its efficiency in testing FT catalysts for their production of alcohols.

Effect of Bronsted Acids and Bases, and Lewis Acid (Sn(2+)) on the Regiochemistry of the Reaction of Amines with Trifluoromethyl-β-diketones: Reaction of 3-Aminopyrrole to Selectively Produce Regioisomeric 1H-Pyrrolo[3,2-b]pyridines.

PubMed

De Rosa, Michael; Arnold, David; Hartline, Douglas; Truong, Linda; Verner, Roman; Wang, Tianwei; Westin, Christian

2015-12-18

Reaction of 3-aminopyrrole (as its salt) with trifluoromethyl-β-diketones gave γ-1H-pyrrolo[3,2-b]pyridines via reaction at the less reactive carbonyl group. The trifluoromethyl group increased the electrophilicity of the adjacent carbonyl group and decreased the basicity of the hydroxyl group of the CF3 amino alcohol formed. This amino alcohol was formed faster, but its subsequent dehydration to the β-enaminone was slow resulting in the preferential formation of the γ-regioisomer. Reaction of 4,4,4-trifluoro-1-phenyl-1,3-butadione with 3-aminopyrrole was carried out using a series of 6 amine buffers. Yields of the α-1H-pyrrolo[3,2-b]pyridine increased as the pKa of the amine buffer decreased. Surprisingly the yield went down at higher pKas. There was a change in mechanism as the reaction mixture became more basic. With strong amines trifluoromethyl-β-diketones were present mainly or completely as the enolate. Under reductive conditions (3-nitropyrrole/Sn/AcOH/trifluoromethyl-β-diketone) the α-1H-pyrrolo[3,2-b]pyridine was the major product as a result of Lewis acid catalysis by Sn(2+). Similar α-regiochemistry was observed when the reaction of the 3-aminopyrrole salt with trifluoromethyl-β-diketones was carried out in the presence of base and tin(II) acetate.

An assessment of potential degradation products in the gas-phase reactions of alternative fluorocarbons in the troposphere

NASA Technical Reports Server (NTRS)

Niki, Hiromi

1990-01-01

Tropospheric chemical transformations of alternative hydrofluorocarbons (HCF's) and hydrochlorofluorocarbons (HCFC's) are governed by hydroxyl radical initiated oxidation processes, which are likely to be analogous to those known for alkanes and chloroalkanes. A schematic diagram is used to illustrate plausible reaction mechanisms for their atmospheric degradation, where R, R', and R'' denote the F- and/or Cl-substituted alkyl groups derived from HCF's and HCFC's subsequent th the initial H atom abstraction by HO radicals. At present, virtually no kinetic data exist for the majority of these reactions, particularly for those involving RO. Potential degradation intermediates and final products include a large variety of fluorine- and/or chlorine-containing carbonyls, acids, peroxy acids, alcohols, hydrogen peroxides, nitrates and peroxy nitrates, as summarized in the attached table. Probably atmospheric lifetimes of these compounds were also estimated. For some carbonyl and nitrate products shown in this table, there seem to be no significant gas-phase removal mechanisms. Further chemical kinetics and photochemical data are needed to quantitatively assess the atmospheric fate of HCF's and HCFC's, and of the degradation products postulated in this report.

Catalytic ethanolysis of Kraft lignin into high-value small-molecular chemicals over a nanostructured α-molybdenum carbide catalyst.

PubMed

Ma, Rui; Hao, Wenyue; Ma, Xiaolei; Tian, Ye; Li, Yongdan

2014-07-07

We report the complete ethanolysis of Kraft lignin over an α-MoC1-x /AC catalyst in pure ethanol at 280 °C to give high-value chemicals of low molecular weight with a maximum overall yield of the 25 most abundant liquid products (LP25) of 1.64 g per gram of lignin. The LP25 products consisted of C6 -C10 esters, alcohols, arenes, phenols, and benzyl alcohols with an overall heating value of 36.5 MJ kg(-1) . C6 alcohols and C8 esters predominated and accounted for 82 wt % of the LP25 products. No oligomers or char were formed in the process. With our catalyst, ethanol is the only effective solvent for the reaction. Supercritical ethanol on its own degrades Kraft lignin into a mixture of small molecules and molecular fragments of intermediate size with molecular weights in the range 700-1400, differing in steps of 58 units, which is the weight of the branched-chain linkage C3 H6 O in lignin. Hydrogen was found to have a negative effect on the formation of the low-molecular-weight products. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Formation of formaldehyde and peroxides by air oxidation of high purity polyoxyethylene surfactants.

PubMed

Bergh, M; Magnusson, K; Nilsson, J L; Karlberg, A T

1998-07-01

Ethoxylated alcohols are non-ionic surfactants. The majority are used in household cleaners, laundry products, toiletries and in industrial and institutional cleaners. In previous studies, an ethoxylated non-ionic surfactant of technical quality showed allergenic activity in guinea pig experiments. Chemical analysis revealed a content of formaldehyde, a well-known contact allergen, and peroxides in the surfactant. Most cases of occupational contact dermatitis are considered to be of irritant origin, caused by contact with water and surfactants, but if allergenic autoxidation products can be formed, allergic contact dermatitis cannot be excluded. The sensitizing potential of a chemically defined high purity ethoxylated alcohol was investigated and oxidation under various storage and handling conditions was studied for this and a homologous product. The pure surfactant showed no significant allergenic activity on predictive testing in guinea pigs. When ethoxylated alcohols were stored in the refrigerator, their deterioration was limited. At room temperature, their content of peroxides and formaldehyde increased with time. Levels of formaldehyde above those capable of causing positive patch test reactions were found. Since such surfactants have wide applications, resulting exposure to formaldehyde could be more frequent than is generally realized, contributing to persistence of dermatitis in individuals allergic to formaldehyde.

Green synthesis of isopropyl myristate in novel single phase medium Part II: Packed bed reactor (PBR) studies.

PubMed

Vadgama, Rajeshkumar N; Odaneth, Annamma A; Lali, Arvind M

2015-12-01

Isopropyl myristate is a useful functional molecule responding to the requirements of numerous fields of application in cosmetic, pharmaceutical and food industry. In the present work, lipase-catalyzed production of isopropyl myristate by esterification of myristic acid with isopropyl alcohol (molar ratio of 1:15) in the homogenous reaction medium was performed on a bench-scale packed bed reactors, in order to obtain suitable reaction performance data for upscaling. An immobilized lipase B from Candida antartica was used as the biocatalyst based on our previous study. The process intensification resulted in a clean and green synthesis process comprising a series of packed bed reactors of immobilized enzyme and water dehydrant. In addition, use of the single phase reaction system facilitates efficient recovery of the product with no effluent generated and recyclability of unreacted substrates. The single phase reaction system coupled with a continuous operating bioreactor ensures a stable operational life for the enzyme.

Support Effects in Catalysis Studied by in-situ Sum Frequency Generation Vibrational Spectroscopy and in-situ X-Ray Spectroscopies

NASA Astrophysics Data System (ADS)

Kennedy, Griffin John

Kinetic measurements are paired with in-situ spectroscopic characterization tools to investigate colloidally based, supported Pt catalytic model systems in order to elucidate the mechanisms by which metal and support work in tandem to dictate activity and selectivity. The results demonstrate oxide support materials, while inactive in absence of Pt nanoparticles, possess unique active sites for the selective conversion of gas phase molecules when paired with an active metal catalyst. In order to establish a paradigm for metal-support interactions using colloidally synthesized Pt nanoparticles the ability of the organic capping agent to inhibit reactivity and interaction with the support must first be assessed. Pt nanoparticles capped by poly(vinylpyrrolidone) (PVP), and those from which the PVP is removed by UV light exposure, are investigated for two reactions, the hydrogenation of ethylene and the oxidation of methanol. It is shown that prior to PVP removal the particles are moderately active for both reactions. Following removal, the activity for the two reactions diverges, the ethylene hydrogenation rate increases 10-fold, while the methanol oxidation rate decreases 3-fold. To better understand this effect the capping agent prior to, and the residual carbon remaining after UV treatment are probed by sum frequency generation vibrational spectroscopy. Prior to removal no major differences are observed when the particles are exposed to alternating H2 and O2 environments. When the PVP is removed, carbonaceous fragments remain on the surface that dynamically restructure in H2 and O2. These fragments create a tightly bound shell in an oxygen environment and a porous coating of hydrogenated carbon in the hydrogen environment. Reaction rate measurements of thermally cleaned PVP and oleic acid capped particles show this effect to be independent of cleaning method or capping agent. In all this demonstrates the ability of the capping agent to mediate nanoparticle catalysis. With this established the hydrogenation of furfural by Pt supported on SiO2 and TiO2 was investigated by an approach combining reaction studies with SFG in order to gain molecular level insight into the nature of the metal-support interaction. This is the first instance of SFG being used to probe the factors governing selectivity in a supported catalyst system. This work revealed that TiO2 possessed sites that, while inactive without Pt, became highly active for the selective conversion of furfural to furfuryl alcohol. By SFG a TiO2 bound intermediate species was identified that could explain the highly selective nature of the reaction by Pt/TiO2. In combination with density functional theory calculations it was determined that furfural bound favorably to oxygen vacancy sites on the TiO2 surface through the aldehyde oxygen, which in turn activated the aldehyde group for hydrogenation by a charge transfer mechanism. This intermediate could then react with spillover hydrogen from the Pt surface to form furfuryl alcohol. In an effort to generalize this mechanism to additional molecules and reducible oxides the work was expanded to the hydrogenation of crotonaldehyde with cobalt oxide as an additional support. Reaction studies and SFG study of the Pt/TiO2, Pt/Co3O4, and Pt/SiO 2 catalysts, revealed a reaction pathway for Pt/TiO2 and Pt/Co3O4 which selectively produced alcohol products, crotyl alcohol and butanol, while no alcohol production was observed for the Pt/SiO2 catalyst. A thorough study of the possible secondary reaction pathways revealed that butanol was formed in a concerted manner, rather than through sequential hydrogenation of the C=C and C=O groups. Sum frequency generation studies revealed that Pt supported on SiO2 yielded identical reaction intermediates as Pt single crystals, further cementing the passive role of SiO2. Spectra obtained from the cobalt and titanium oxide supported catalysts revealed adsorption sites exist on the oxide surfaces through which the molecule binds via the aldehyde group. These sites are believed to be the active sites for alcohol production. In the case of Co3O 4 ambient pressure x-ray photoelectron spectroscopy and x-ray absorption spectroscopy reveal a reduction of the oxide surface under reaction conditions indicating the adsorption sites on the oxide exist on a reduced surface, additional evidence for the site being an O-vacancy. Lastly a before undiscovered example of encapsulation of a metal particle by an oxide support is observed for the Pt/Co3O4 system by ambient pressure x-ray photoelectron spectroscopy. Under mild conditions an encapsulated state is reached in which the oxide covers the Pt surface, yet does not inhibit reactivity. In fact the total activity of the catalyst increases dramatically and a change in product selectivity was observed. (Abstract shortened by ProQuest.).

Insight into reaction pathways in CO hydrogenation reactions over K/MoS 2 supported catalysts via alcohol/olefin co-feed experiments

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

Taborga Claure, Micaela; Morrill, Michael R.; Goh, Jin Wai

2016-01-01

Reaction pathways for higher alcohol synthesis from syngas are studied over K/MoS 2domains supported on mesoporous carbon (C) and mixed MgAl oxide (MMO)viaaddition of methanol, ethanol, and ethylene co-feeds.

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

PubMed

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

2016-11-16

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

Purification, Characterization, and Potential Bacterial Wax Production Role of an NADPH-Dependent Fatty Aldehyde Reductase from Marinobacter aquaeolei VT8▿ †

PubMed Central

Wahlen, Bradley D.; Oswald, Whitney S.; Seefeldt, Lance C.; Barney, Brett M.

2009-01-01

Wax esters, ester-linked fatty acids and long-chain alcohols, are important energy storage compounds in select bacteria. The synthesis of wax esters from fatty acids is proposed to require the action of a four-enzyme pathway. An essential step in the pathway is the reduction of a fatty aldehyde to the corresponding fatty alcohol, although the enzyme responsible for catalyzing this reaction has yet to be identified in bacteria. We report here the purification and characterization of an enzyme from the wax ester-accumulating bacterium Marinobacter aquaeolei VT8, which is a proposed fatty aldehyde reductase in this pathway. The enzyme, a 57-kDa monomer, was expressed in Escherichia coli as a fusion protein with the maltose binding protein on the N terminus and was purified to near homogeneity by using amylose affinity chromatography. The purified enzyme was found to reduce a number of long-chain aldehydes to the corresponding alcohols coupled to the oxidation of NADPH. The highest specific activity was observed for the reduction of decanal (85 nmol decanal reduced/min/mg). Short-chain and aromatic aldehydes were not substrates. The enzyme showed no detectable catalysis of the reverse reaction, the oxidation of decanol by NADP+. The mechanism of the enzyme was probed with several site-specific chemical probes. The possible uses of this enzyme in the production of wax esters are discussed. PMID:19270127

Synthesis of substituted pyrazines

DOEpatents

Pagoria, Philip F.; Zhang, Mao Xi

2016-10-04

A method for synthesizing a pyrazine-containing material according to one embodiment includes contacting an iminodiacetonitrile derivative with a base and a reagent selected from a group consisting of hydroxylamine, a hydroxylamine salt, an aliphatic primary amine, a secondary amine, an aryl-substituted alkylamine a heteroaryl-substituted alkyl amine, an alcohol, an alkanolamine and an aryl alcoholamine. Additional methods and several reaction products are presented. ##STR00001##

Optimized Diazo Scaffold for Protein Esterification

PubMed Central

Mix, Kalie A.

2015-01-01

The O-alkylation of carboxylic acids with diazo compounds provides a means to esterify carboxylic acids in aqueous solution. A Hammett analysis of the reactivity of diazo compounds derived from phenylglycinamide revealed that the p-methylphenylglycinamide scaffold has an especially high reaction rate and ester:alcohol product ratio, and esterifies protein carboxyl groups more efficiently than does any known reagent. PMID:25938936

Alcohol Intolerance

MedlinePlus

... ingredients commonly found in alcoholic beverages, especially in beer or wine, can cause intolerance reactions. These include: Sulfites or other preservatives Chemicals, grains or other ingredients Histamine, a byproduct of fermentation or brewing In some cases, reactions can be ...

Biodiesel production from vegetable oil and waste animal fats in a pilot plant.

PubMed

Alptekin, Ertan; Canakci, Mustafa; Sanli, Huseyin

2014-11-01

In this study, corn oil as vegetable oil, chicken fat and fleshing oil as animal fats were used to produce methyl ester in a biodiesel pilot plant. The FFA level of the corn oil was below 1% while those of animal fats were too high to produce biodiesel via base catalyst. Therefore, it was needed to perform pretreatment reaction for the animal fats. For this aim, sulfuric acid was used as catalyst and methanol was used as alcohol in the pretreatment reactions. After reducing the FFA level of the animal fats to less than 1%, the transesterification reaction was completed with alkaline catalyst. Due to low FFA content of corn oil, it was directly subjected to transesterification. Potassium hydroxide was used as catalyst and methanol was used as alcohol for transesterification reactions. The fuel properties of methyl esters produced in the biodiesel pilot plant were characterized and compared to EN 14214 and ASTM D6751 biodiesel standards. According to the results, ester yield values of animal fat methyl esters were slightly lower than that of the corn oil methyl ester (COME). The production cost of COME was higher than those of animal fat methyl esters due to being high cost biodiesel feedstock. The fuel properties of produced methyl esters were close to each other. Especially, the sulfur content and cold flow properties of the COME were lower than those of animal fat methyl esters. The measured fuel properties of all produced methyl esters met ASTM D6751 (S500) biodiesel fuel standards. Copyright © 2014 Elsevier Ltd. All rights reserved.

A review on production of biodiesel using catalyzed transesterification

NASA Astrophysics Data System (ADS)

Dash, Santosh Kumar; Lingfa, Pradip

2017-07-01

Biodiesel is arguably an important fuel for compression ignition engine as far as sustainability and environmental issues are concerned. It can be produced from both edible and non-edible vegetable oils and animal fats. Owing to higher viscosity, the utilization of crude vegetable oil is not advisable as it results engine failure. For reducing the viscosity and improving the other fuel characteristics comparable to that of diesel fuel, different approaches have been developed. However, transesterification process is very reliable, less costly and easy method compared to other methods. Due to more free fatty acids content in most of the non-edible vegetable oils, a pretreatment is employed to convert the acids to ester, then transesterified with suitable alcohol. Primarily yield of biodiesel depends upon the molar ratio of oil/alcohol, reaction temperature, reaction time, amount of catalyst, type of catalyst, stirring speed. Both homogeneous and heterogeneous catalysts are used for synthesis purposes. Heterogeneous catalysts are less costly, environmental benign and can be derived from natural resources. Enzymatic catalysts are more environmental benign than heterogeneous catalysts but are costly, which hinders its widespread research and utilization. This article reviews the results of prominent works and researches in the field of production of biodiesel via catalyzed transesterification process.

Highly efficient direct aerobic oxidative esterification of cinnamyl alcohol with alkyl alcohols catalysed by gold nanoparticles incarcerated in a nanoporous polymer matrix: a tool for investigating the role of the polymer host.

PubMed

Buonerba, Antonio; Noschese, Annarita; Grassi, Alfonso

2014-04-25

The selective aerobic oxidation of cinnamyl alcohol to cinnamaldehyde, as well as direct oxidative esterification of this alcohol with primary and secondary aliphatic alcohols, were achieved with high chemoselectivity by using gold nanoparticles supported in a nanoporous semicrystalline multi-block copolymer matrix, which consisted of syndiotactic polystyrene-co-cis-1,4-polybutadiene. The cascade reaction that leads to the alkyl cinnamates occurs through two oxidation steps: the selective oxidation of cinnamyl alcohol to cinnamaldehyde, followed by oxidation of the hemiacetal that results from the base-catalysed reaction of cinnamaldehyde with an aliphatic alcohol. The rate constants for the two steps were evaluated in the temperature range 10-45 °C. The cinnamyl alcohol oxidation is faster than the oxidative esterification of cinnamaldehyde with methanol, ethanol, 2-propanol, 1-butanol, 1-hexanol or 1-octanol. The rate constants of the latter reaction are pseudo-zero order with respect to the aliphatic alcohol and decrease as the bulkiness of the alcohol is increased. The activation energy (Ea) for the two oxidation steps was calculated for esterification of cinnamyl alcohol with 1-butanol (Ea = 57.8±11.5 and 62.7±16.7 kJ mol(-1) for the first and second step, respectively). The oxidative esterification of cinnamyl alcohol with 2-phenylethanol follows pseudo-first-order kinetics with respect to 2-phenylethanol and is faster than observed for other alcohols because of fast diffusion of the aromatic alcohol in the crystalline phase of the support. The kinetic investigation allowed us to assess the role of the polymer support in the determination of both high activity and selectivity in the title reaction. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Diazo Reagents with Small Steric Footprints for Simultaneous Arming/SAR Studies of Alcohol-Containing Natural Products via O–H Insertion

PubMed Central

Chamni, Supakarn; He, Qing-Li; Dang, Yongjun; Bhat, Shridhar; Liu, Jun O.; Romo, Daniel

2011-01-01

Natural products are essential tools for basic cellular studies leading to the identification of medically relevant protein targets and the discovery of potential therapeutic leads. The development of methods that enable mild and selective derivatization of natural products continues to be of significant interest for mining their information-rich content. Herein, we describe novel diazo reagents for simultaneous arming and structure-activity relationship (SAR) studies of alcohol-containing natural products with a small steric footprint, namely an α-trifluoroethyl (HTFB) substituted reagent. The Rh(II)-catalyzed O–H insertion reaction of several natural products, including the potent translation inhibitor lactimidomycin, was investigated and useful reactivity and both chemo- and site (chemosite) selectivities were observed. Differential binding to the known protein targets of both FK506 and fumagillol was demonstrated, validating the advantage of the smaller steric footprint of trifluoroethyl derivatives. A p-azidophenyl diazo reagent is also described that will prove useful for photoaffinity labeling of low affinity small molecule protein receptors. PMID:21894934

Enzymatic synthesis of chiral amino-alcohols by coupling transketolase and transaminase-catalyzed reactions in a cascading continuous-flow microreactor system.

PubMed

Gruber, Pia; Carvalho, Filipe; Marques, Marco P C; O'Sullivan, Brian; Subrizi, Fabiana; Dobrijevic, Dragana; Ward, John; Hailes, Helen C; Fernandes, Pedro; Wohlgemuth, Roland; Baganz, Frank; Szita, Nicolas

2018-03-01

Rapid biocatalytic process development and intensification continues to be challenging with currently available methods. Chiral amino-alcohols are of particular interest as they represent key industrial synthons for the production of complex molecules and optically pure pharmaceuticals. (2S,3R)-2-amino-1,3,4-butanetriol (ABT), a building block for the synthesis of protease inhibitors and detoxifying agents, can be synthesized from simple, non-chiral starting materials, by coupling a transketolase- and a transaminase-catalyzed reaction. However, until today, full conversion has not been shown and, typically, long reaction times are reported, making process modifications and improvement challenging. In this contribution, we present a novel microreactor-based approach based on free enzymes, and we report for the first time full conversion of ABT in a coupled enzyme cascade for both batch and continuous-flow systems. Using the compartmentalization of the reactions afforded by the microreactor cascade, we overcame inhibitory effects, increased the activity per unit volume, and optimized individual reaction conditions. The transketolase-catalyzed reaction was completed in under 10 min with a volumetric activity of 3.25 U ml -1 . Following optimization of the transaminase-catalyzed reaction, a volumetric activity of 10.8 U ml -1 was attained which led to full conversion of the coupled reaction in 2 hr. The presented approach illustrates how continuous-flow microreactors can be applied for the design and optimization of biocatalytic processes. © 2017 The Authors. Biotechnology and Bioengineering Published by Wiley Periodicals, Inc.

Stereoselectivity in ene reactions with 1O2: matrix effects in polymer supports, photo-oxygenation of organic salts and asymmetric synthesis.

PubMed

Griesbeck, Axel G; Bartoschek, Anna; Neudörfl, Jörg; Miara, Claus

2006-01-01

The ene reaction of chiral allylic alcohols is applied as a tool for the investigation of intrapolymer effects by means of the stereoselectivity of the singlet-oxygen addition. The diastereo selectivity strongly depends on the structure of the polymer, the substrate loading degree and also on the degree of conversion demonstrating additional supramolecular effects evolving during the reaction. The efficiency and the stability of polymer-bound sensitizers were evaluated by the ene reaction of singlet oxygen with citronellol. The ene reaction with chiral ammonium salts of tiglic acid was conducted under solution phase conditions or in polystyrene beads under chiral contact ion-pair conditions. The products thus obtained precipitate during the photoreaction as ammonium salts. Moderate asymmetric induction was observed for this procedure for the first time.

Methods of refining natural oils, and methods of producing fuel compositions

DOEpatents

Firth, Bruce E.; Kirk, Sharon E.

2015-10-27

A method of refining a natural oil includes: (a) providing a feedstock that includes a natural oil; (b) reacting the feedstock in the presence of a metathesis catalyst to form a metathesized product that includes olefins and esters; (c) passivating residual metathesis catalyst with an agent that comprises nitric acid; (d) separating the olefins in the metathesized product from the esters in the metathesized product; and (e) transesterifying the esters in the presence of an alcohol to form a transesterified product and/or hydrogenating the olefins to form a fully or partially saturated hydrogenated product. Methods for suppressing isomerization of olefin metathesis products produced in a metathesis reaction, and methods of producing fuel compositions are described.

Lewis Acid Catalyzed Asymmetric Three-Component Coupling Reaction: Facile Synthesis of α-Fluoromethylated Tertiary Alcohols.

PubMed

Aikawa, Kohsuke; Kondo, Daisuke; Honda, Kazuya; Mikami, Koichi

2015-12-01

A chiral dicationic palladium complex is found to be an efficient Lewis acid catalyst for the synthesis of α-fluoromethyl-substituted tertiary alcohols using a three-component coupling reaction. The reaction transforms three simple and readily available components (terminal alkyne, arene, and fluoromethylpyruvate) to valuable chiral organofluorine compounds. This strategy is completely atom-economical and results in perfect regioselectivities and high enantioselectivities of the corresponding tertiary allylic alcohols in good to excellent yields. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

High-Resolution Mass Spectrometric Analysis of Secondary Organic Aerosol Produced by Ozonation of Limonene

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

Walser, Maggie L.; Dessiaterik, Yury; Laskin, Julia

2008-02-08

Secondary organic aerosol (SOA) particles formed from the ozone-initiated oxidation of limonene are characterized by high-resolution electrospray ionization mass spectrometry in both the positive and negative ion modes. The mass spectra reveal a large number of both monomeric (m/z < 300) and oligomeric (m/z > 300) products of oxidation. A combination of high resolving power (m/Δm ~60,000) and Kendrick mass defect analysis makes it possible to unambiguously determine the composition for hundreds of individual compounds in SOA samples. Van Krevelen analysis shows that the SOA compounds are heavily oxidized, with average O:C ratios of 0.43 and 0.50 determined from themore » positive and negative ion mode spectra, respectively. An extended reaction mechanism for the formation of the first generation SOA molecular components is proposed. The mechanism includes known isomerization and addition reactions of the carbonyl oxide intermediates generated during the ozonation of limonene, and numerous isomerization pathways for alkoxy radicals resulting from the decomposition of unstable carbonyl oxides. The isomerization reactions yield numerous products with a progressively increasing number of alcohol and carbonyl groups, whereas C-C bond scission reactions in alkoxy radicals shorten the carbon chain. Together these reactions yield a large number of isomeric products with broadly distributed masses. A qualitative agreement is found between the number and degree of oxidation of the predicted and measured reaction products in the monomer range.« less

First-principles quantum-mechanical investigations: The role of water in catalytic conversion of furfural on Pd(111)

NASA Astrophysics Data System (ADS)

Xue, Wenhua; Borja, Miguel Gonzalez; Resasco, Daniel E.; Wang, Sanwu

2015-03-01

In the study of catalytic reactions of biomass, furfural conversion over metal catalysts with the presence of water has attracted wide attention. Recent experiments showed that the proportion of alcohol product from catalytic reactions of furfural conversion with palladium in the presence of water is significantly increased, when compared with other solvent including dioxane, decalin, and ethanol. We investigated the microscopic mechanism of the reactions based on first-principles quantum-mechanical calculations. We particularly identified the important role of water and the liquid/solid interface in furfural conversion. Our results provide atomic-scale details for the catalytic reactions. Supported by DOE (DE-SC0004600). This research used the supercomputer resources at NERSC, of XSEDE, at TACC, and at the Tandy Supercomputing Center.

Oxidation catalysis of Nb(salan) complexes: asymmetric epoxidation of allylic alcohols using aqueous hydrogen peroxide as an oxidant.

PubMed

Egami, Hiromichi; Oguma, Takuya; Katsuki, Tsutomu

2010-04-28

Several optically active Nb(salan) complexes were synthesized, and their oxidation catalysis was examined. A dimeric mu-oxo Nb(salan) complex that was prepared from Nb(OiPr)(5) and a salan ligand was found to catalyze the asymmetric epoxidation of allylic alcohols using a urea-hydrogen peroxide adduct as an oxidant with good enantioselectivity. However, subsequent studies of the time course of this epoxidation and of the relationship between the ee of the ligand and the ee of the product indicated that the mu-oxo dimer dissociates into a monomeric species prior to epoxidation. Moreover, monomeric Nb(salan) complexes prepared in situ from Nb(OiPr)(5) and salan ligands followed by water treatment were found to catalyze the epoxidation of allylic alcohols better using aqueous hydrogen peroxide in CHCl(3)/brine or toluene/brine solution with high enantioselectivity ranging from 83 to 95% ee, except for the reaction of cinnamyl alcohol that showed a moderate ee of 74%. This is the first example of the highly enantioselective epoxidation of allylic alcohols using aqueous hydrogen peroxide as an oxidant.

Recognition and liking of tobacco and alcohol advertisements among adolescents: relationships with susceptibility to substance use.

PubMed

Unger, J B; Johnson, C A; Rohrbach, L A

1995-09-01

Exposure to tobacco and alcohol advertising has been associated with adolescent substance use. However, it is not clear whether favorable reactions to advertising are an antecedent to or a consequence of substance use. This study investigated relationships between adolescents' levels of susceptibility to substance use and their recognition and liking of tobacco and alcohol advertising. Eighth-grade students viewed pictures of tobacco and alcohol advertisements with brand names and identifying information obscured, attempted to identify the brand name and type of product being advertised, and rated their liking of the advertisements. Subjects were divided into three substance use status groups: nonsusceptible nonusers (have never used and do not intend to do so), susceptible nonusers (have not used but have not made a firm commitment not to experiment in the future), and users (have tried the substance). Susceptible nonusers liked the tobacco advertisements at a level that was significantly greater than that of the nonsusceptible nonsmokers and comparable to that of the users. Liking of the alcohol advertisements generally increased with alcohol use status. These results suggest that tobacco advertisements ostensibly targeted to adult smokers may have the effect of recruiting new adolescent smokers.

Biocatalytic anti-Prelog reduction of prochiral ketones with whole cells of Acetobacter pasteurianus GIM1.158.

PubMed

Du, Peng-Xuan; Wei, Ping; Lou, Wen-Yong; Zong, Min-Hua

2014-06-10

Enantiomerically pure alcohols are important building blocks for production of chiral pharmaceuticals, flavors, agrochemicals and functional materials and appropriate whole-cell biocatalysts offer a highly enantioselective, minimally polluting route to these valuable compounds. At present, most of these biocatalysts follow Prelog's rule, and thus the (S)-alcohols are usually obtained when the smaller substituent of the ketone has the lower CIP priority. Only a few anti-Prelog (R)-specific whole cell biocatalysts have been reported. In this paper, the biocatalytic anti-Prelog reduction of 2-octanone to (R)-2-octanol was successfully conducted with high enantioselectivity using whole cells of Acetobacter pasteurianus GIM1.158. Compared with other microorganisms investigated, Acetobacter pasteurianus GIM1.158 was shown to be more effective for the reduction reaction, affording much higher yield, product enantiomeric excess (e.e.) and initial reaction rate. The optimal temperature, buffer pH, co-substrate and its concentration, substrate concentration, cell concentration and shaking rate were 35°C, 5.0, 500 mmol/L isopropanol, 40 mmol/L, 25 mg/mL and 120 r/min, respectively. Under the optimized conditions, the maximum yield and the product e.e. were 89.5% and >99.9%, respectively, in 70 minutes. Compared with the best available data in aqueous system (yield of 55%), the yield of (R)-2-octanol was greatly increased. Additionally, the efficient whole-cell biocatalytic process was feasible on a 200-mL preparative scale and the chemical yield increased to 95.0% with the product e.e. being >99.9%. Moreover, Acetobacter pasteurianus GIM1.158 cells were proved to be capable of catalyzing the anti-Prelog bioreduction of other prochiral carbonyl compounds with high efficiency. Via an effective increase in the maximum yield and the product e.e. with Acetobacter pasteurianus GIM1.158 cells, these results open the way to use of whole cells of this microorganism for challenging enantioselective reduction reactions on laboratory and commercial scales.

Recovery of organic acids

DOEpatents

Verser, Dan W.; Eggeman, Timothy J.

2009-10-13

A method is disclosed for the recovery of an organic acid from a dilute salt solution in which the cation of the salt forms an insoluble carbonate salt. A tertiary amine and CO.sub.2 are introduced to the solution to form the insoluble carbonate salt and a complex between the acid and an amine. A water immiscible solvent, such as an alcohol, is added to extract the acid/amine complex from the dilute salt solution to a reaction phase. The reaction phase is continuously dried and a product between the acid and the solvent, such as an ester, is formed.

Recovery of organic acids

DOEpatents

Verser, Dan W [Menlo Park, CA; Eggeman, Timothy J [Lakewood, CO

2011-11-01

A method is disclosed for the recovery of an organic acid from a dilute salt solution in which the cation of the salt forms an insoluble carbonate salt. A tertiary amine and CO.sub.2 are introduced to the solution to form the insoluble carbonate salt and a complex between the acid and an amine. A water immiscible solvent, such as an alcohol, is added to extract the acid/amine complex from the dilute salt solution to a reaction phase. The reaction phase is continuously dried and a product between the acid and the solvent, such as an ester, is formed.

Carbon and Hydrogen Isotope Measurements of Alcohols and Organic Acids by Online Pyroprobe-GC-IRMS

NASA Technical Reports Server (NTRS)

Socki, Richard A.; Fu, Qi; Niles, Paul B.; Gibson, Everett K., Jr.

2012-01-01

The detection of methane in the atmosphere of Mars, combined with evidence showing widespread water-rock interaction during martian history, suggests that the production of methane on Mars may be the result of mineral surface-catalyzed CO2 and or CO reduction during Fisher-Tropsch Type (FTT) reactions. A better understanding of these reaction pathways and corresponding C and H isotope fractionations is critical to deciphering the synthesis of organic compounds produced under abiotic hydrothermal conditions. Described here is a technique for the extraction and analysis of both C and H isotopes from alcohols (C1-C4) and organic acids (C1-C6). This work is meant to provide a "proof of concept" for making meaningful isotope measurements on complex mixtures of solid-phase hydrocarbons and other intermediary products produced during high-temperature and high-pressure synthesis on mineral-catalyzed surfaces. These analyses are conducted entirely "on-line" utilizing a CDS model 5000 Pyroprobe connected to a Thermo Trace GC Ultra that is interfaced with a Thermo MAT 253 isotope ratio mass spectrometer operating in continuous flow mode. Also, this technique is designed to carry a split of the GC-separated product to a DSQ II quadrupole mass spectrometer as a means of making semi-quantitative compositional measurements. Therefore, both chemical and isotopic measurements can be carried out on the same sample.

Effect on the use of ultrasonic cavitation for biodiesel production from crued Jatropha curcas L. seed oil with a high content of free fatty acid

NASA Astrophysics Data System (ADS)

Worapun, Ittipon; Pianthong, Kulachate; Thaiyasuit, Prachasanti; Thinvongpituk, Chawalit

2010-03-01

A typical way to produce biodiesel is the transesterification of plant oils. This is commonly carried out by treating the pre-extracted oil with an appropriate alcohol in the presence of an acidic or alkaline catalyst over one or two hours in a batch reactor.Because oils and methanol are not completely miscible. It has been widely demonstrated that low-frequency ultrasonic irradiation is an effective tool for emulsifying immiscible liquids. The objective of this research is to investigate the optimum conditions for biodiesel production from crude Jatropha curcas oil with short chain alcohols by ultrasonic cavitation (at 40 kHz frequency and 400 Watt) assisted, using two step catalyst method. Usually, the crude Jatropha curcas oil has very high free fatty acid which obstructs the transesterification reaction. As a result it provides low yield of biodiesel production. In the first step, the reaction was carried out in the presence of sulfuric acid as an acid catalyst. The product was then further transesterified with potassium hydroxide in the second step. The effects of different operating parameters such as molar ratio of reactants, catalyst quantity, and operating temperature, have been studied with the aim of process optimization. It has been observed that the mass transfer and kinetic rate enhancements were due to the increase in interfacial area and activity of the microscopic and macroscopic bubbles formed. For example, the product yield levels of more than 90% have been observed with the use of ultrasonic cavitation in about 60 minutes under room temperature operating conditions.

Enzymatic Production of Biodiesel: Strategies to Overcome Methanol Inactivation.

PubMed

Lotti, Marina; Pleiss, Jürgen; Valero, Francisco; Ferrer, Pau

2018-05-01

Lipase-catalyzed transesterification of triglycerides and alcohols to obtain biodiesel is an environmentally friendly and sustainable route for fuels production since, besides proceeding in mild reaction conditions, it allows for the use of low-cost feedstocks that contain water and free fatty acids, for example non-edible oils and waste oils. This review article reports recent advances in the field and focus in particular on a major issue in the enzymatic process, the inactivation of most lipases caused by methanol, the preferred acyl acceptor used for alcoholysis. The recent results about immobilization of enzymes on nano-materials and the use of whole-cell biocatalysts, as well as the use of cell-surface display technologies and metabolic engineering strategies for microbial production of biodiesel are described. It is discussed also insight into the effects of methanol on lipases obtained by modeling approaches and report on studies aimed at mining novel alcohol stable enzymes or at improving robustness in existing ones by protein engineering. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

[Enzymatic conversion of tetradecanol in heterogenous phase by yeast-alcohol dehydrogenase].

PubMed

Rothe, U; Schöpp, W; Aurich, H

1976-01-01

Alcohol dehydrogenase from yeast converts long-chain primary alcohols not only in the dissolved state, but also at the surface of undissolved particles. Tetradecanol beads with a defined surface can be produced and employed as model substrate. The reaction rate was determined by the proton release accomplished in the reaction. The initial reaction rate depends on the enzyme concentration. The relation is nonlinear (vi = k-[e]0,4); the numerical value of the exponent (n = 0.4) argues in favour of a reaction occurring at the interface. The Lineweaver-Burk plots become linear if the substrate concentrations are based on the molar surface concentrations of the particles. The pH optimum for the reaction at the surface is displaced by 0.25 pH units towards the alkaline region (compared with ethanol as substrate). The activation energy of the reaction with tetradecanol beads as substrate is 30% lower than that for the ethanol oxydation.

Face-Name Association Learning and Brain Structural Substrates in Alcoholism

PubMed Central

Pitel, Anne-Lise; Chanraud, Sandra; Rohlfing, Torsten; Pfefferbaum, Adolf; Sullivan, Edith V.

2011-01-01

Background Associative learning is required for face-name association and is impaired in alcoholism, but the cognitive processes and brain structural components underlying this deficit remain unclear. It is also unknown whether prompting alcoholics to implement a deep level of processing during face-name encoding would enhance performance. Methods Abstinent alcoholics and controls performed a levels-of-processing face-name learning task. Participants indicated whether the face was that of an honest person (deep encoding) or that of a man (shallow encoding). Retrieval was examined using an associative (face-name) recognition task and a single-item (face or name only) recognition task. Participants also underwent a 3T structural MRI. Results Compared with controls, alcoholics had poorer associative and single-item recognition, each impaired to the same extent. Level of processing at encoding had little effect on recognition performance but affected reaction time. Correlations with brain volumes were generally modest and based primarily on reaction time in alcoholics, where the deeper the processing at encoding, the more restricted the correlations with brain volumes. In alcoholics, longer control task reaction times correlated modestly with volumes across several anterior to posterior brain regions; shallow encoding correlated with calcarine and striatal volumes; deep encoding correlated with precuneus and parietal volumes; associative recognition RT correlated with cerebellar volumes. In controls, poorer associative recognition with deep encoding correlated significantly with smaller volumes of frontal and striatal structures. Conclusions Despite prompting, alcoholics did not take advantage of encoding memoranda at a deep level to enhance face-name recognition accuracy. Nonetheless, conditions of deeper encoding resulted in faster reaction times and more specific relations with regional brain volumes than did shallow encoding. The normal relation between associative recognition and corticostriatal volumes was not present in alcoholics. Rather, their speeded reaction time occurred at the expense of accuracy and was related most robustly to cerebellar volumes. PMID:22509954

Screening For Alcohol-Producing Microbes

NASA Technical Reports Server (NTRS)

Schubert, Wayne W.

1988-01-01

Dye reaction rapidly identifies alcohol-producing microbial colonies. Method visually detects alcohol-producing micro-organisms, and distinguishes them from other microbial colonies that do not produce alcohol. Method useful for screening mixed microbial populations in environmental samples.

[Diet and migraine].

PubMed

Leira, R; Rodríguez, R

1996-05-01

Some foods in our diet can spark off migraine attacks in susceptible individuals. Some foods can bring an attack on through an allergic reaction. A certain number such as citrus fruits, tea, coffee, pork, chocolate, milk, nuts, vegetables and cola drinks have been cited as possible allergens associated with migraine. This mechanism has however been criticized: an improvement in symptoms by eliminating some food(s) from our diet does not necessarily mean an immunologically based allergic reaction. The high IgE incidence rate is not greater in such patients than in the population at large. Other allergic reactions unrelated to diet may also be associated with migraine attacks. On the other hand substances in food may be the cause of modifications in vascular tone and bring migraine on in those so prone. Among such substances are tyramine, phenylalanine, phenolic flavonoids, alcohol, food additives (sodium nitrate, monosodium glutamate, aspartame) and caffeine. Another recognized trigger for migraine is hypoglycemia. Such foods as chocolate, cheese, citrus fruits, bananas, nuts, 'cured' meats, dairy products, cereals, beans, hot dogs, pizza, food additives (sodium nitrate, monosodium glutamate in Chinese restaurant food, aspartame as a sweetener), coffee, tea, cola drinks, alcoholic drinks such as red wine, beer or whisky distilled in copper stills, all may bring on a migraine attack. For every patient we have to assess which foodstuffs are involved in the attack (not necessarily produced by consuming the product concerned) in order to try to avoid their consumptions as a means of prophylaxis for migraine.

Furfural to Furfuryl Alcohol: Computational Study of the Hydrogen Transfer on Lewis Acidic BEA Zeolites and Effects of Cation Exchange and Tetravalent Metal Substitution.

PubMed

Prasertsab, Anittha; Maihom, Thana; Probst, Michael; Wattanakit, Chularat; Limtrakul, Jumras

2018-06-04

The hydrogen transfer of furfural to furfuryl alcohol with i-propanol as the hydrogen source over cation-exchanged Lewis acidic BEA zeolite has been investigated by means of density functional calculations. The reaction proceeds in three steps. First the O-H bond of i-propanol is broken to form a propoxide intermediate. After that, the furylmethoxy intermediate is formed via hydrogen transfer process, and finally furylmethoxy abstracts the proton to form the furfuryl alcohol product. The second step is rate-determining by requiring the highest activation energy (23.8 kcal/mol) if the reaction takes place on Li-Sn-BEA zeolite. We find that the catalytic activity of various cation-exchanged Sn-BEA zeolites is in the order Li-Sn-BEA > Na-Sn-BEA > K-Sn-BEA. The lower activation energy for Li-Sn-BEA compared to Na-Sn-BEA and K-Sn-BEA can be explained by the larger charge transfer from the carbonyl bond to the catalyst, leading to its activation and to the attraction of the hydrogen being transferred. The larger charge transfer in turn is due to the smaller gap between the energies of furfural HOMO and the zeolite LUMO in Li-Sn-BEA, compared to both Na-Sn-BEA and K-Sn-BEA. In a similar way, we also compare the catalytic activity of tetravalent metal centers (Sn, Zr, and Hf) substituted into BEA and find in the order Zr ≥ Hf > Sn, based on activation energies. Finally we investigate statistically which property of the reactants is a suitable descriptor for an approximative prediction of the reaction rate in order to be able to quickly screen promising catalytic materials for this reaction.

Density functional theory study of the mechanism and origins of stereoselectivity in the asymmetric Simmons-Smith cyclopropanation with Charette chiral dioxaborolane ligand.

PubMed

Wang, Tao; Liang, Yong; Yu, Zhi-Xiang

2011-06-22

Asymmetric Simmons-Smith reaction using Charette chiral dioxaborolane ligand is a widely applied method for the construction of enantiomerically enriched cyclopropanes. The detailed mechanism and the origins of stereoselectivity of this important reaction were investigated using density functional theory (DFT) calculations. Our computational studies suggest that, in the traditional Simmons-Smith reaction conditions, the monomeric iodomethylzinc allyloxide generated in situ from the allylic alcohol and the zinc reagent has a strong tendency to form a dimer or a tetramer. The tetramer can easily undergo an intramolecular cyclopropanation to give the racemic cyclopropane product. However, when a stoichiometric amount of Charette chiral dioxaborolane ligand is employed, monomeric iodomethylzinc allyloxide is converted into an energetically more stable four-coordinated chiral zinc/ligand complex. The chiral complex has the zinc bonded to the CH(2)I group and coordinated by three oxygen atoms (one from the allylic alcohol and the other two oxygen atoms from the carbonyl oxygen and the ether oxygen in the dioxaborolane ligand), and it can undergo the cyclopropanation reaction easily. Three key factors influencing the enantioselectivity have been identified through examining the cyclopropanation transition states: (1) the torsional strain along the forming C-C bond, (2) the 1,3-allylic strain caused by the chain conformation, and (3) the ring strain generated in the transition states. In addition, the origin of the high anti diastereoselectivity for the substituent on the zinc reagent and the hydroxymethyl group of the allylic alcohol has been rationalized through analyzing the steric repulsion and the ring strain in the cyclopropanation transition states.

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

Underwood, R.P.

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

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

Underwood, R.P.

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

The Piancatelli reaction and its variants: recent applications to high added-value chemicals and biomass valorization.

PubMed

Verrier, Charlie; Moebs-Sanchez, Sylvie; Queneau, Yves; Popowycz, Florence

2018-01-31

The Piancatelli reaction, also called the Piancatelli rearrangement, consists in the direct conversion of furfuryl alcohols to cyclopentenone derivatives through a furan ring opening-electrocyclization process. Discovered in the late 70's, this reaction has been scarcely used for more than 40 years but recently has been the focus of particular interest from the scientific community and an increasing number of publications on the topic have emerged in the last few years. The first part of this review provides an overview of the recent achievements in classical Piancatelli reactions, discussing reaction conditions and catalytic systems, whereas the second part focuses on the variants recently developed, including the use of new nucleophiles in the process. Finally, the third part of this review deals with the recent application of this transformation to the production of commodity chemicals from renewable carbon feedstocks based on sugar-derived furanic platforms.

Simultaneous phase and morphology controllable synthesis of copper selenide films by microwave-assisted nonaqueous approach

NASA Astrophysics Data System (ADS)

Li, Jing; Fa, Wenjun; Li, Yasi; Zhao, Hongxiao; Gao, Yuanhao; Zheng, Zhi

2013-02-01

Copper selenide films with different phase and morphology were synthesized on copper substrate through controlling reaction solvent by microwave-assisted nonaqueous approach. The films were characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM). The result showed that the pure films could be obtained using cyclohexyl alcohol or benzyl alcohol as solvent. The cubic Cu2-xSe dendrites were synthesized in cyclohexyl alcohol reaction system and hexagonal CuSe flaky crystals were obtained with benzyl alcohol as solvent.

Application of lower aliphatic alcohols as reducing agents for increasing efficiency of the LCLD process

NASA Astrophysics Data System (ADS)

Semenok, Dmitrii

2014-05-01

A method is described that is promising for application metal conductors on ceramic substrates during printed-circuit boards (PCBs) production without masking plate. The main idea of laser-induced metal deposition from solution (LCLD) consists of implementation of chemical micro reactor by using a focused laser beam. In this reactor the red/ox reaction would be initiated due to heating of a reaction medium. We used a 532 nm DPSS laser (power: 2100 mW) and water solutions of organic alcohols with low molecular weight, ethanol and isopropanol as reductants. The results of deposition were studied using the SEM, EDX methods and impedance spectroscopy. The equivalent resistance-capacitance circuit of copper tracks was constructed. The experiments showed that increasing the rate of deposition of nanostructured copper tracks up to 50 μm/s with electrical resistivity 5 Ohm/cm is possible by replacing the well-known reductants such as formaldehyde and D-sorbitol with iso-propanol.

Fast cleavage of phycocyanobilin from phycocyanin for use in food colouring.

PubMed

Roda-Serrat, Maria Cinta; Christensen, Knud Villy; El-Houri, Rime Bahij; Fretté, Xavier; Christensen, Lars Porskjær

2018-02-01

Phycocyanins from cyanobacteria are possible sources for new natural blue colourants. Their chromophore, phycocyanobilin (PCB), was cleaved from the apoprotein by solvolysis in alcohols and alcoholic aqueous solutions. In all cases two PCB isomers were obtained, while different solvent adducts were formed upon the use of different reagents. The reaction is believed to take place via two competing pathways, a concerted E2 elimination and a S N 2 nucleophilic substitution. Three cleavage methods were compared in terms of yield and purity: conventional reflux, sealed vessel heated in an oil bath, and microwave assisted reaction. The sealed vessel method is a new approach for fast cleavage of PCB from phycocyanin and gave at 120°C the same yield within 30min compared to 16h by the conventional reflux method (P<0.05). In addition the sealed vessel method resulted in improved purity compared to the other methods. Microwave irradiation increased product degradation. Copyright © 2017 Elsevier Ltd. All rights reserved.

Nickel-Catalyzed Coupling of Alkenes, Aldehydes, and Silyl Triflates

PubMed Central

Ng, Sze-sze; Ho, Chun-Yu; Jamison, Timothy F.

2011-01-01

A full account of two recently developed nickel-catalyzed coupling reactions of alkenes, aldehydes and silyl triflates is presented. These reactions provide either allylic alcohol or homoallylic alcohol derivatives selectively, depending on the ligand employed. These processes are believed to be mechanistically distinct from Lewis acid-catalyzed carbonyl-ene reactions, and several lines of evidence supporting this hypothesis are discussed. PMID:16939275

7 CFR Appendix C to Subpart E of... - Guidelines for Loan Guarantees for Alcohol Fuel Production Facilities

Code of Federal Regulations, 2010 CFR

2010-01-01

... facilities necessary for the production and storage of alcohol and the processing of the by-products of alcohol production. The intent is to limit the alcohol and by-products processing facilities to those... alcohol or by-products in another manufacturing process, are not considered part of the alcohol production...

Electrochemical reduction of carbon dioxide. Final report

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

LaConti, A.B.; Molter, T.M.; Zagaja, J.A.

1986-05-01

Many researchers have studied the electrochemical reduction of carbon dioxide and related organic species to form concentrated liquid/gaseous products in laboratory-scale hardware. Hamilton Standard has developed a high pressure SPE electrolysis cell capable of reducing carbon dioxide streams to form pure, concentrated alcohols, carboxylic acids, and other hydrocarbons. The process is unique in that the byproducts of reaction include oxygen and, under some test conditions water. In addition, a relatively simple test system was designed and constructed permitting both batch and semibatch type electrochemical reduction studies. In this study, cathode materials were developed which 1) had a characteristic high hydrogenmore » overvoltage, and 2) possessed the intrinsic affinity for electrochemical reduction of the carbon dioxide species. In addition, suitable anode electrocatalyst materials were identified. Studies involving the electrochemical reduction of carbon dioxide required the ability to identify and quantify reaction products obtained during cell evaluation. Gas chromatographic techniques were developed along with the establishment of ion chromatographic methods permitting the analysis of organic reaction products. Hamilton Standard has evaluated electrochemical carbon dioxide reduction cells under a variety of test conditions.« less

Evaluation of Biodiesel Production, Engine Performance, and Emissions

NASA Astrophysics Data System (ADS)

Gürü, Metin; Keskïn, Ali

2016-08-01

Nowadays, to decrease environmental pollution and dependence on fossil-based fuels, research on alternative renewable energy sources has been increasing. One such renewable energy source is biodiesel, which is used as an alternative fuel for diesel engines. Biodiesel is renewable, nontoxic, biodegradable, and environmentally friendly. Biodiesel is domestically produced from vegetable oil (edible or nonedible), animal fat, and used cooking oils. In the biodiesel production process, oil or fat undergoes transesterification reaction through use of simple alcohols such as methanol, ethanol, propanol, butanol, etc. Use of methanol is most feasible because of its low cost, and physical and chemical advantages. Acid catalysis, alkali catalysis, and enzyme catalysis are usually used to improve the reaction rate and yield. Glycerol is a byproduct of the reaction and can be used as an industrial raw material. In this study, biodiesel production methods (direct use, pyrolysis, microemulsion, transesterification, supercritical processes, ultrasound- assisted, and microwave-assisted) and types of catalyst (homogeneous, heterogeneous, and enzyme) have been evaluated and compared. In addition, the effects of biodiesel and its blends on diesel engine performance and exhaust emissions are described and reviewed.

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

Martinez-Guerra, Edith; Gude, Veera Gnaneswar, E-mail: gude@cee.msstate.edu

Highlights: • Pulse sonication effect on transesterification of waste vegetable oil was studied. • Effects of ethanol, methanol, and alcohol mixtures on FAMEs yield were evaluated. • Effect of ultrasonic intensity, power density, and its output rates were evaluated. • Alcohol mixtures resulted in higher biodiesel yields due to better solubility. - Abstract: This study reports on the effects of direct pulse sonication and the type of alcohol (methanol and ethanol) on the transesterification reaction of waste vegetable oil without any external heating or mechanical mixing. Biodiesel yields and optimum process conditions for the transesterification reaction involving ethanol, methanol, andmore » ethanol–methanol mixtures were evaluated. The effects of ultrasonic power densities (by varying sample volumes), power output rates (in W), and ultrasonic intensities (by varying the reactor size) were studied for transesterification reaction with ethanol, methanol and ethanol–methanol (50%-50%) mixtures. The optimum process conditions for ethanol or methanol based transesterification reaction of waste vegetable oil were determined as: 9:1 alcohol to oil ratio, 1% wt. catalyst amount, 1–2 min reaction time at a power output rate between 75 and 150 W. It was shown that the transesterification reactions using ethanol–methanol mixtures resulted in biodiesel yields as high as >99% at lower power density and ultrasound intensity when compared to ethanol or methanol based transesterification reactions.« less

Promotion or suppression of glucose isomerization in subcritical aqueous straight- and branched-chain alcohols.

PubMed

Gao, Da-Ming; Kobayashi, Takashi; Adachi, Shuji

2015-01-01

The influence of water-miscible alcohols (methanol, 1-propanol, 2-propanol, and t-butyl alcohol) on the isomerization of glucose to fructose and mannose was investigated under subcritical aqueous conditions (180-200 °C). Primary and secondary alcohols promoted the conversion and isomerization of glucose to afford fructose and mannose with high and low selectivity, respectively. On the other hand, the decomposition (side-reaction) of glucose was suppressed in the presence of the primary and secondary alcohols compared with that in subcritical water. The yield of fructose increased with increasing concentration of the primary and secondary alcohols, and the species of the primary and secondary alcohols tested had little effect on the isomerization behavior of glucose. In contrast, the isomerization of glucose was suppressed in subcritical aqueous t-butyl alcohol. Both the conversion of glucose and the yield of fructose decreased with increasing concentration of t-butyl alcohol. In addition, mannose was not detected in reactions using subcritical aqueous t-butyl alcohol.

Hexafluoroisopropyl alcohol mediated synthesis of 2,3-dihydro-4H-pyrido[1,2-a]pyrimidin-4-ones.

PubMed

Alam, Mohammad A; Alsharif, Zakeyah; Alkhattabi, Hessa; Jones, Derika; Delancey, Evan; Gottsponer, Adam; Yang, Tianhong

2016-11-02

An efficient synthesis of novel 2,3-dihydro-4H-pyrido[1,2-a]pyrimidin-4-ones has been reported. Inexpensive and readily available substrates, environmentally benign reaction condition, and product formation up to quantitative yield are the key features of this methodology. Products are formed by the aza-Michael addition followed by intramolecular acyl substitution in a domino process. The polar nature and strong hydrogen bond donor capability of 1,1,1,3,3,3-hexafluoropropan-2-ol is pivotal in this cascade protocol.

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

DOE PAGES

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

2016-04-01

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

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

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

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

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

The Production of Biodiesel from Cottonseed Oil Using Rhizopus oryzae Whole Cell Biocatalysts

NASA Astrophysics Data System (ADS)

Athalye, Sneha Kishor

Biodiesel is an environmentally friendly alternative to fossil fuels which have become increasingly expensive in recent times. An alternate approach to alkaline biodiesel production is needed as catalyst miscibility with the glycerol by-product, generation of large amounts of waste water, and saponification of the feedstock are major disadvantages associated with the process. Lipases are water soluble enzymes which act as catalysts in many lipid based reactions. Reuse of lipases can significantly reduce cost of enzymatic biodiesel production; however retention of lipolytic activity still remains a challenge. Use of microbial cells immobilized on various surfaces like sponge, foam and plastics as biocatalysts instead of extracted enzyme could help overcome this problem. A novel, rigid biomass support with high surface area made from recyclable polyethylene (Bioblok(TM)) was used in this study. Several fungal and bacterial species have been reported to possess appreciable levels of lipase activity. The biomass production and immobilization as well as lipase activity of three different species; Candida rugosa (ATCC #38772), Aspergillus oryzae (ATCC #58299), and Rhizopus oryzae (ATTC #34612) were tested. C. rugosa did not attach well to the support particles while A.oryzae had lower biomass accumulation of 6.1 g (dry cell wt)/L compared to 11.8 g (dry cell wt)/L for R.oryzae. Hence Rhizopus oryzae, fungal specie with cell surface bound lipase was selected for the current study. The study investigated the influence of media composition and growth time of the R.oryzae whole cell biocatalysts, immobilized on the BSPs, for FAME production from cottonseed oil. R.oryzae BSPs grown in basal media supplemented with 1% (w/v) of glucose or oil or both for 48 h, 72 h or 90 h were used in a 36 h transesterification reaction with cottonseed oil and methanol. BSPs grown in both glucose and oil supplemented medium for 72 h had the highest conversion of 22.4% (wt/wt) and a biomass accumulation of 15.6 g (dry cell wt)/L. A reduction in dynamic viscosity of the reaction mixture from 47.3 centipoise to 30.6 centipoise was observed. The impact of moisture addition to the reaction mixture and use of ethanol as acylating agent on R.oryzae BSP fatty acid alkyl ester production was also tested. The presence of 10 wt % moisture in the reaction system had a significant effect (p ≤ 0.05) on the transesterification reaction with ethanol unlike methanol. Fatty acid ethyl ester concentration tripled from 39.3 to 129.1 g/L when moisture was added during transesterification .When oil to acyl acceptor ratio was increased from 1:3 and 1:6 to determine effect of excess alcohol on conversion, an ester conversion of 128.1 g/L for methanol and 129.1 g/L for ethanol were observed. Use of excess amount of acylating agent had a significant adverse effect (p ≤ 0.05) on the overall FAAE production due to deactivation of lipases on contact with large amounts of insoluble alcohol in the oil phase of the reaction. The effect of short chain alcohols on the enzymatic transesterification of cottonseed oil using freeze dried Rhizopus oryzae biomass was examined with and without water addition using methanol, ethanol, 1-Propanol and 1-Butanol at various molar ratios. 1- Butanol in the absence of water resulted in a significantly higher (p . 0.1) conversion of cottonseed oil to 12.5 % fatty acid butyl esters (FABEs). Addition of 10 % water to the reaction mixture significantly reduced (p ≤ 0.1) conversion. No significant difference (p > 0.1) between the conversions was observed for time points after 24 h for a 72 h reaction. 1- Butanol in ratios higher than 3:1 to cottonseed oil had a significant impact (p ≤ 0.1) on conversion. Increasing the amount of biomass used during the reaction lead to significantly higher conversion (p ≤ 0.1). The highest conversion of 27.9 % was observed for the transesterification reaction between cottonseed oil and 1-Butanol, in a 1:6 molar ratio, in the absence of water, when 100 mg of freeze dried R.oryzae biomass was used. The present study concluded that R.oryzae biomass attached better to the Bioblok. material and had highest lipase activity when grown in presence of oil and glucose for 72h. Addition of water to the reaction system gave higher fatty acid alkyl ester conversion when whole immobilized R.oryzae BSPs were used but absence of water promoted conversion with freeze dried biomass.

Non-thermal plasma destruction of allyl alcohol in waste gas: kinetics and modelling

NASA Astrophysics Data System (ADS)

DeVisscher, A.; Dewulf, J.; Van Durme, J.; Leys, C.; Morent, R.; Van Langenhove, H.

2008-02-01

Non-thermal plasma treatment is a promising technique for the destruction of volatile organic compounds in waste gas. A relatively unexplored technique is the atmospheric negative dc multi-pin-to-plate glow discharge. This paper reports experimental results of allyl alcohol degradation and ozone production in this type of plasma. A new model was developed to describe these processes quantitatively. The model contains a detailed chemical degradation scheme, and describes the physics of the plasma by assuming that the fraction of electrons that takes part in chemical reactions is an exponential function of the reduced field. The model captured the experimental kinetic data to less than 2 ppm standard deviation.

One-Pot Synthesis of N-Substituted β-Amino Alcohols from Aldehydes and Isocyanides.

PubMed

Cioc, Răzvan C; van der Niet, Daan J H; Janssen, Elwin; Ruijter, Eelco; Orru, Romano V A

2015-05-18

A practical two-stage one-pot synthesis of N-substituted β-amino alcohols using aldehydes and isocyanides as starting materials has been developed. This method features mild reaction conditions, broad scope, and general tolerance of functional groups. Based on a less common central carbon-carbon bond disconnection, this protocol complements traditional approaches that involve amines and various carbon electrophiles (epoxides, α-halo ketones, β-halohydrins). Medicinally relevant products can be prepared in a concise and efficient way from simple building blocks, as demonstrated in the synthesis of the antiasthma drug salbutamol. Upgrading the synthesis to an enantioselective variant is also feasible. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Studies on a Total Synthesis of the Microbial Immunosuppresive Agent FR901483

PubMed Central

Kropf, Jeffrey E.; Meigh, Ivona C.; Bebbington, Magnus W.P.; Weinreb, Steven M.

2008-01-01

A strategy is outlined for construction of the fungal immunosuppressant FR901483 (1). It was possible to convert 1,4-cyclohexanedione monoethylene ketal in five simple steps to iodoacetamide ketone 10, which was cyclized in good yield to the key bridged keto lactam 11 containing the A/B 2-azabicyclo[3.3.1]nonane ring system of the natural product. This intermediate could be transformed to N-Boc lactam 16, whose derived enolate underwent stereoselective hydroxylation with the Davis oxaziridine to produce alcohol 17 having the desired C-2 configuration. Compound 17 was then converted in three steps to alkoxy carbamate 20. The N-acyliminium ion derived from intermediate 20 could be alkylated in good overall yield with p-methoxybenzylmagnesium chloride to afford a 5:4 mixure of the desired PMB product 21 and the epimer 23. In an attempt to improve the stereoselectivity in this alkylation, the inverted C-4 protected alcohol N-Boc lactam 33 was prepared and its enolate was hydroxylated. Inexplicably, the product of this reaction was the undesired equatorial alcohol 34. Some model systems were investigated towards annulation of the C-ring of the natural product. It was found that homoallylic amine 40 could be cyclized with PhSCl in the presence of silica gel to generate the desired 5-endo tetracyclic product 42 in moderate yield. This cyclization protocol was also successfully applied to the actual FR901483 system 22, leading to the requisite tricycle 43. PMID:16496992

Cross-linked chitosan aerogel modified with Au: Synthesis, characterization and catalytic application.

PubMed

Keshipour, Sajjad; Mirmasoudi, Seyyedeh Sahra

2018-09-15

Dimercaprol as the chelating agent of Au(III) was loaded on chitosan aerogel. Dimercaprol supported on chitosan aerogel efficiently was complexed with Au(III). The new organometallic compound showed good catalytic activity in the oxidation reaction of some aliphatic alcohols, benzyl alcohol, and ethylbenzene. High conversions and excellent selectivities were obtained in the solvent-free oxidation reactions under mild reaction conditions. Also, turnover numbers were calculated for the oxidation reactions with 203, 134, 308, 282, 392, and 153 for 1-pentanol, 1-octanol, 2-propanol, 2-butanol, benzyl alcohol, and ethylbenzene, respectively. The organometallic compound is applicable as a heterogeneous Au(III) catalyst with high chemical stabilityand recyclability up to 6 times. Copyright © 2018 Elsevier Ltd. All rights reserved.

Optimization of transesterification of rubber seed oil using heterogeneous catalyst calcium oxide

NASA Astrophysics Data System (ADS)

Inggrid, Maria; Kristanto, Aldi; Santoso, Herry

2015-12-01

Biodiesel is an alternative fuel manufactured with the help of alkali hydroxide catalyst through transesterification reaction of vegetable oil. This study aims to examine methods and the most suitable conditions for transesterification reaction producing biodiesel from crude rubber seed oil by varying process parameters such as the molar ratio of alcohol, CaO amount as the alkaline catalyst, and reaction time. The rubber seed oil has a high level of free fatty acid content, which means the use of homogenous alkaline catalyst gives some technological problems such as soap formation which leaded in difficulty in the separation and purification of the product. Calcium oxide (CaO) is one of the most favorable heterogeneous base catalysts because it's reusable, noncorrosive, and low cost. Pre-treatment was performed by acid esterification with H2SO4 as the catalyst to decrease the content of free fatty acid in the rubber seed oil, in this pretreatment process the 12% FFA of crude oil could be reduced to below 3% FFA. The product after esterification process was then transesterified by alkaline transesterification by varying process parameters to convert triglyceride into biodiesel. The study found that maximum curvature for biodiesel yield occurred at 9:1 molar ratio of alcohol, 5%w catalyst loading, and 3 hours reaction time. Design expert software is used to determine the optimum point from experimental data. The result showed that the optimum yield of methyl ester from transesterification was 73.5 % by mass with 0.69 degree of desirability. The yielded methyl ester was tested for its density, viscosity, acid number, and solubility to meet SNI requirement standards.

Engineering of carboligase activity reaction in Candida glabrata for acetoin production.

PubMed

Li, Shubo; Xu, Nan; Liu, Liming; Chen, Jian

2014-03-01

Utilization of Candida glabrata overproducing pyruvate is a promising strategy for high-level acetoin production. Based on the known regulatory and metabolic information, acetaldehyde and thiamine were fed to identify the key nodes of carboligase activity reaction (CAR) pathway and provide a direction for engineering C. glabrata. Accordingly, alcohol dehydrogenase, acetaldehyde dehydrogenase, pyruvate decarboxylase, and butanediol dehydrogenase were selected to be manipulated for strengthening the CAR pathway. Following the rational metabolic engineering, the engineered strain exhibited increased acetoin biosynthesis (2.24 g/L). In addition, through in silico simulation and redox balance analysis, NADH was identified as the key factor restricting higher acetoin production. Correspondingly, after introduction of NADH oxidase, the final acetoin production was further increased to 7.33 g/L. By combining the rational metabolic engineering and cofactor engineering, the acetoin-producing C. glabrata was improved stepwise, opening a novel pathway for rational development of microorganisms for bioproduction. Copyright © 2013. Published by Elsevier Inc.

Reduction of unsaturated compounds under interstellar conditions: chemoselective reduction of C≡C and C=C bonds over C=O functional group

NASA Astrophysics Data System (ADS)

Jonusas, Mindaugas; Guillemin, Jean-Claude; Krim, Lahouari

2017-07-01

The knowledge of the H-addition reactions on unsaturated organic molecules bearing a triple or a double carbon-carbon bond such as propargyl or allyl alcohols and a CO functional group such as propynal, propenal or propanal may play an important role in the understanding of the chemical complexity of the interstellar medium. Why different aldehydes like methanal, ethanal, propynal and propanal are present in dense molecular clouds while the only alcohol detected in those cold regions is methanol? In addition, ethanol has only been detected in hot molecular cores. Are those saturated and unsaturated aldehyde and alcohol species chemically linked in molecular clouds through solid phase H-addition surface reactions or are they formed through different chemical routes? To answer such questions, we have investigated a hydrogenation study of saturated and unsaturated aldehydes and alcohols at 10 K. We prove through this experimental study that while pure unsaturated alcohol ices bombarded by H atoms lead to the formation of the corresponding fully or partially saturated alcohols, surface H-addition reactions on unsaturated aldehyde ices exclusively lead to the formation of fully saturated aldehyde. Such results show that in addition to a chemoselective reduction of C≡C and C=C bonds over the C=O group, there is no link between aldehydes and their corresponding alcohols in reactions involving H atoms in dense molecular clouds. Consequently, this could be one of the reasons why some aldehydes such as propanal are abundant in dense molecular clouds in contrast to the non-detection of alcohol species larger than methanol.

From a Decomposition Product to an Efficient and Versatile Catalyst: The [Ru(η5-indenyl)(PPh3)2Cl] Story

PubMed Central

2014-01-01

Conspectus One of the most important challenges in catalyst design is the synthesis of stable promoters without compromising their activity. For this reason, it is important to understand the factors leading to decomposition of such catalysts, especially if side-products negatively affect the activity and selectivity of the starting complex. In this context, the understanding of termination and decomposition processes in olefin metathesis is receiving significant attention from the scientific community. For example, the decomposition of ruthenium olefin metathesis precatalysts in alcohol solutions can occur during either the catalyst synthesis or the metathesis process, and such decomposition has been found to be common for Grubbs-type precatalysts. These decomposition products are usually hydridocarbonyl complexes, which are well-known to be active in several transformations such as hydrogenation, terminal alkene isomerization, and C–H activation chemistry. The reactivity of these side products can be unwanted, and it is therefore important to understand how to avoid them and maybe also important to keep an open mind and think of ways to use these in other catalytic reactions. A showcase of these decomposition studies is reported in this Account. These reports analyze the stability of ruthenium phenylindenylidene complexes, highly active olefin metathesis precatalysts, in basic alcohol solutions. Several different decomposition processes can occur under these conditions depending on the starting complex and the alcohol used. These indenylidene-bearing metathesis complexes display a completely different behavior compared with that of other metathesis precatalysts and show an alternative competitive alcoholysis pathway, where rather than forming the expected hydrido carbonyl complexes, the indenylidene fragment is transformed into a η1-indenyl, which then rearranges to its η5-indenyl form. In particular, [RuCl(η5-(3-phenylindenylidene)(PPh3)2] has been found to be extremely active in numerous transformations (at least 20) as well as compatible with a broad range of reaction conditions, rendering it a versatile catalytic tool. It should be stated that the η5-phenyl indenyl ligand shows enhanced catalytic activity over related half-sandwich ruthenium complexes. The analogous half-sandwich (cyclopentadienyl and indenyl) ruthenium complexes show lower activity in transfer hydrogenation and allylic alcohol isomerization reactions. In addition, this catalyst allows access to new phenylindenyl ruthenium complexes, which can be achieved in a very straightforward manner and have been successfully used in catalysis. This Account provides an overview of how mechanistic insights into decomposition and stability of a well-known family of ruthenium metathesis precatalysts has resulted in a series of novel and versatile ruthenium complexes with unexpected reactivity. PMID:25264626

A direct conversion of benzylic and allylic alcohols to phosphonates

PubMed Central

Barney, Rocky J.; Richardson, Rebekah M.; Wiemer, David F.

2011-01-01

Benzyl phosphonate esters often serve as reagents in Horner-Wadsworth-Emmons reactions. In most cases, they can be prepared from benzylic alcohols via formation of the corresponding halide followed by an Arbuzov reaction. To identify a more direct synthesis of phosphonate esters, we have developed a one-flask procedure for conversion of benzylic and allylic alcohols to the corresponding phosphonates through treatment with triethyl phosphite and ZnI2. PMID:21405073

Alcohol and Kids: Facing Our Problem.

ERIC Educational Resources Information Center

Long, Nicholas; And Others

1993-01-01

Introduces special journal issue on alcohol use among children and adolescents. Describes scope of the problem, claiming that alcohol is the most consumed drug among children and youth. Discusses possible progression in alcohol use, parents' reactions to their children using alcohol or other drugs, and effects of the media and advertising on…

Carbon-coated magnetic palladium: applications in partial oxidation of alcohols and coupling reactions.

EPA Science Inventory

Magnetic carbon supported Pd catalyst has been synthesized via in situ generation of nanoferrites and incorporation of carbon from renewable cellulose via calcination; catalyst can be used for oxidation of alcohols, amination reaction and arylation of aryl halides (cross coupli...

Facts on the Effects of Alcohol. Clearinghouse Fact Sheet.

ERIC Educational Resources Information Center

Milgram, Gail Gleason

Ethyl alcohol (ethanol) is one of the few alcohols that humans can drink. This alcohol is a byproduct of yeast's reaction with the sugars in fruit or vegetable juice and the process stops naturally with about an 11 to 14 percent alcoholic concentration, although distillation can greatly increase the alcoholic content. Once ingested, most alcohol…

Spectral and catalytic properties of aryl-alcohol oxidase, a fungal flavoenzyme acting on polyunsaturated alcohols

PubMed Central

2005-01-01

Spectral and catalytic properties of the flavoenzyme AAO (aryl-alcohol oxidase) from Pleurotus eryngii were investigated using recombinant enzyme. Unlike most flavoprotein oxidases, AAO does not thermodynamically stabilize a flavin semiquinone radical and forms no sulphite adduct. AAO catalyses the oxidative dehydrogenation of a wide range of unsaturated primary alcohols with hydrogen peroxide production. This differentiates the enzyme from VAO (vanillyl-alcohol oxidase), which is specific for phenolic compounds. Moreover, AAO is optimally active in the pH range of 5–6, whereas VAO has an optimum at pH 10. Kinetic studies showed that AAO is most active with p-anisyl alcohol and 2,4-hexadien-1-ol. AAO converts m- and p-chlorinated benzyl alcohols at a similar rate as it does benzyl alcohol, but introduction of a p-methoxy substituent in benzyl alcohol increases the reaction rate approx. 5-fold. AAO also exhibits low activity on aromatic aldehydes. 19F NMR analysis showed that fluorinated benzaldehydes are converted into the corresponding benzoic acids. Inhibition studies revealed that the AAO active site can bind a wide range of aromatic ligands, chavicol (4-allylphenol) and p-anisic (4-methoxybenzoic) acid being the best competitive inhibitors. Uncompetitive inhibition was observed with 4-methoxybenzylamine. The properties described above render AAO a unique oxidase. The possible mechanism of AAO binding and oxidation of substrates is discussed in the light of the results of the inhibition and kinetic studies. PMID:15813702

Chemical transformations of glucose to value added products using Cu-based catalytic systems.

PubMed

Yepez, Alfonso; Pineda, Antonio; Garcia, Angel; Romero, Antonio A; Luque, Rafael

2013-08-07

Cu nanoparticles have been supported by two types of aluminosilicate materials with and without Zn in their composition in view of their application in the microwave-assisted conversion of glucose to valuable products via tandem formic acid-promoted dehydration (to 5-hydroxymethylfurfural--HMF) and further selective hydrogenation to 5-methylfurfuryl alcohol (MFA). Results show that interesting selectivities (up to 60% to MFA or HMF) could be achieved after short times of reaction (typically 2-30 min) using Cu-containing nanomaterials. Zn was found to play an interesting role in the selectivity to reduced products, even if present in very small quantities (0.2 wt%).

Comparative techno-economic analysis and process design for indirect liquefaction pathways to distillate-range fuels via biomass-derived oxygenated intermediates upgrading: Liquid Transportation Fuel Production via Biomass-derived Oxygenated Intermediates Upgrading

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

Tan, Eric C. D.; Snowden-Swan, Lesley J.; Talmadge, Michael

This paper presents a comparative techno-economic analysis (TEA) of five conversion pathways from biomass to gasoline-, jet-, and diesel-range hydrocarbons via indirect liquefaction with specific focus on pathways utilizing oxygenated intermediates. The four emerging pathways of interest are compared with one conventional pathway (Fischer-Tropsch) for the production of the hydrocarbon blendstocks. The processing steps of the four emerging pathways include: biomass to syngas via indirect gasification, gas cleanup, conversion of syngas to alcohols/oxygenates followed by conversion of alcohols/oxygenates to hydrocarbon blendstocks via dehydration, oligomerization, and hydrogenation. Conversion of biomass-derived syngas to oxygenated intermediates occurs via three different pathways, producing: 1)more » mixed alcohols over a MoS2 catalyst, 2) mixed oxygenates (a mixture of C2+ oxygenated compounds, predominantly ethanol, acetic acid, acetaldehyde, ethyl acetate) using an Rh-based catalyst, and 3) ethanol from syngas fermentation. This is followed by the conversion of oxygenates/alcohols to fuel-range olefins in two approaches: 1) mixed alcohols/ethanol to 1-butanol rich mixture via Guerbet reaction, followed by alcohol dehydration, oligomerization, and hydrogenation, and 2) mixed oxygenates/ethanol to isobutene rich mixture and followed by oligomerization and hydrogenation. The design features a processing capacity of 2,000 tonnes/day (2,205 short tons) of dry biomass. The minimum fuel selling prices (MFSPs) for the four developing pathways range from $3.40 to $5.04 per gasoline-gallon equivalent (GGE), in 2011 US dollars. Sensitivity studies show that MFSPs can be improved with co-product credits and are comparable to the commercial Fischer-Tropsch benchmark ($3.58/GGE). Overall, this comparative TEA study documents potential economics for the developmental biofuel pathways via mixed oxygenates.« less

Convenient stereocontrolled amidoglycosylation of alcohols with acetylated glycals and trichloroethoxysulfonamide.

PubMed

Murakami, Teiichi; Sato, Yukari; Yoshioka, Kyoko; Tanaka, Mutsuo

2016-11-03

A regio- and stereo-controlled, rhodium(II)-catalyzed amidoglycosylation of alcohols has been developed using O-acetylated glycals, trichloroethoxysulfonamide, and iodosobenzene. This one-pot amidoglycosylation was applied to a variety of primary and secondary alcohols to afford the β-O-glycosides with acceptable yields up to 84%. The reaction would proceed via stereoselective intermolecular aziridination of the glycal from the α-face followed by S N 2 reaction with alcohol at C-1 from the β-face to give 1,2:2,3-di-trans-substituted isomer only. Copyright © 2016 Elsevier Ltd. All rights reserved.

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

Cheng, Chiu Tung; Chan, Man Nin; Wilson, Kevin R.

Oxygenated organic molecules are abundant in atmospheric aerosols and are transformed by oxidation reactions near the aerosol surface by gas-phase oxidants such as hydroxyl (OH) radicals. To gain better insights into how the structure of an organic molecule, particularly in the presence of hydroxyl groups, controls the heterogeneous reaction mechanisms of oxygenated organic compounds, this study investigates the OH-radical initiated oxidation of aqueous tartaric acid (C 4 H 6 O 6 ) droplets using an aerosol flow tube reactor. The molecular composition of the aerosols before and after reaction is characterized by a soft atmospheric pressure ionization source (Direct Analysismore » in Real Time) coupled with a high-resolution mass spectrometer. The aerosol mass spectra reveal that four major reaction products are formed: a single C 4 functionalization product (C 4 H 4 O 6 ) and three C 3 fragmentation products (C 3 H 4 O 4 , C 3 H 2 O 4 , and C 3 H 2 O 5 ). The C 4 functionalization product does not appear to originate from peroxy radical self-reactions but instead forms via an α-hydroxylperoxy radical produced by a hydrogen atom abstraction by OH at the tertiary carbon site. The proximity of a hydroxyl group to peroxy group enhances the unimolecular HO 2 elimination from the α-hydroxylperoxy intermediate. This alcohol-to-ketone conversion yields 2-hydroxy-3-oxosuccinic acid (C 4 H 4 O 6 ), the major reaction product. While in general, C-C bond scission reactions are expected to dominate the chemistry of organic compounds with high average carbon oxidation states (OS C ), our results show that molecular structure can play a larger role in the heterogeneous transformation of tartaric acid (OS C = 1.5). These results are also compared with two structurally related dicarboxylic acids (succinic acid and 2,3-dimethylsuccinic acid) to elucidate how the identity and location of functional groups (methyl and hydroxyl groups) alter heterogeneous reaction mechanisms.« less

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

PubMed

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

2014-05-20

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

Sustainable synthesis of aldehydes, ketones or acids from neat alcohols using nitrogen dioxide gas, and related reactions.

PubMed

Naimi-Jamal, M Reza; Hamzeali, Hamideh; Mokhtari, Javad; Boy, Jürgen; Kaupp, Gerd

2009-01-01

Benzylic alcohols are quantitatively oxidized by gaseous nitrogen dioxide to give pure aromatic aldehydes. The reaction gas mixtures are transformed to nitric acid, which renders the processes free of waste. The exothermic gas-liquid or gas-solid reactions profit from the solubility of nitrogen dioxide in the neat benzylic alcohols. The acid formed impedes further oxidation of the benzaldehydes. The neat isolated benzaldehydes and nitrogen dioxide quantitatively give the benzoic acids. Solid long-chain primary alcohols are directly and quantitatively oxidized with nitrogen dioxide gas to give the fatty acids in the solid state. The oxidations with ubiquitous nitrogen dioxide are extended to solid heterocyclic thioamides, which gives disulfides, and to diphenylamine, which gives tetraphenylhydrazine. These sustainable (green) specific oxidation procedures produce no dangerous residues from the oxidizing agent or from auxiliaries.

Studies of Heterogenous Palladium and Related Catalysts for Aerobic Oxidation of Primary Alcohols

NASA Astrophysics Data System (ADS)

Ahmed, Maaz S.

Development of aerobic oxidation methods is of critical importance for the advancement of green chemistry, where the only byproduct produced is water. Recent work by our lab has produced an efficient Pd based heterogenous catalyst capable of preforming the aerobic oxidation of a wide spectrum of alcohols to either carboxylic acid or methyl ester. The well-defined catalyst PdBi 0.35Te0.23/C (PBT/C) catalyst has been shown to can perform the aerobic oxidation of alcohols to carboxylic acids in basic conditions. Additionally, we explored this catalyst for a wide range of alcohols and probed the nature of the selectivity of PBT/C for methyl esterification over other side products. Finally, means by which the catalyst operates with respect to oxidation states of the three components, Pd, Bi, and Te, was probed. Carboxylic acids are an important functional group due to their prevalence in various pharmaceutically active agents, agrochemicals, and commodity scale chemicals. The well-defined catalyst PBT/C catalyst was discovered to be effective for the oxidation of a wide spectrum of alcohols to carboxylic acid. The demonstrated substrate scope and functional group tolerance are the widest reported for an aerobic heterogeneous catalyst. Additionally, the catalyst has been implemented in a packed bed reactor with quantitative yield of benzoic acid maintained throughout a two-day run. Biomass derived 5-(hydroxymethyl)furfural (HMF) is also oxidized to 2,5-furandicarboxylic acid (FDCA) in high yield. Exploration of PBT/C for the oxidative methyl esterification was found to exhibit exquisite selectivity for the initial oxidation of primary alcohol instead of methanol, which is the bulk solvent. We explored this selectivity and conclude that it results from various substrate-surface interactions, which are not attainable by methanol. The primary alcohol can outcompete the methanol for binding on the catalyst surface through various interactions between the side chain of the alcohol solvent and the surface of the catalyst: (listed in order of strength) lone pair-surface (heterocyclic primary alcohols) > pi-surface (aryl primary alcohols) > van der Waals-surface (alkyl primary alcohols). These interactions were previously underappreciated in condensed phase heterogeneously catalyzed aerobic oxidations. Bi and Te serve as synergistic promoters that enhance both the rate and yield of the reactions relative to reactions employing Pd alone or Pd in combination with Bi or with Te as the sole promoter. We report X-ray absorption spectroscopic studies of the heterogenous catalyst. These methods show that the promoters undergo oxidation in preference to Pd, maintaining the Pd surface in the active metallic state and preventing inhibition by surface Pd-oxide formation. The data also suggest formation of a Pd-Te alloy phase that modifies the electronic properties of the Pd catalyst. Collectively, these results provide valuable insights into the synergistic benefits of multiple promoters in heterogeneous catalytic oxidation reactions.

Enzymatic transformation of hydrocarbons by methanotrophic organisms

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

Patel, R.N.; Hou, C.T.

Soluble methane monooxygenase from a facultative methane-utilizing organism, Methylobacterium sp. CRL-26 or R6, catalyzed the NAD(P)H-dependent epoxidation/hydroxylation of a variety of hydrocarbons, including terminal alkenes, internal alkenes, substituted alkenes, branch-chain alkenes, alkanes (C1-C8), substituted alkanes, branch-chain alkanes, carbon monoxide, ether, cyclic and aromatic compounds. The NAD -linked dehydrogenases such as formate dehydrogenase or secondary alcohol dehydrogenase in the presence of formate or secondary alcohol, respectively, regenerated NAD/NADH required for the methane monooxygenase in a coupled enzymes reactions. Oxidation of secondary alcohols to the corresponding methylketones in methanotrophs is catalyzed by an NAD -dependent, zinc-containing, secondary alcohol hydrogenase. Primary alcohols weremore » oxidized to the corresponding aldehydes by a phenazine methosulfate-dependent, pyrollo quinoline quinone (methoxatin or PQQ) containing, methanol dehydrogenase. Oxidation of aldehydes (C1 to C10) to the corresponding carboxylic acids is catalyzed by a heme-containing aldehyde dehydrogenase. Methanotrophs have been considered potentially useful for single cell protein (SCP), amino acids, and biopolymer production at the expense of growth on cheap and readily available C1 compounds. 80 references, 1 figure, 6 tables.« less

Practical Synthesis of Amides via Copper/ABNO-Catalyzed Aerobic Oxidative Coupling of Alcohols and Amines.

PubMed

Zultanski, Susan L; Zhao, Jingyi; Stahl, Shannon S

2016-05-25

A modular Cu/ABNO catalyst system has been identified that enables efficient aerobic oxidative coupling of alcohols and amines to amides. All four permutations of benzylic/aliphatic alcohols and primary/secondary amines are viable in this reaction, enabling broad access to secondary and tertiary amides. The reactions exhibit excellent functional group compatibility and are complete within 30 min-3 h at rt. All components of the catalyst system are commercially available.

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

PubMed

Usui, Ippei; Schmidt, Stefan; Breit, Bernhard

2009-03-19

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

Electrochemical method for producing a biodiesel mixture comprising fatty acid alkyl esters and glycerol

DOEpatents

Lin, YuPo J; St. Martin, Edward J

2013-08-13

The present invention relates to an integrated method and system for the simultaneous production of biodiesel from free fatty acids (via esterification) and from triglycerides (via transesterification) within the same reaction chamber. More specifically, one preferred embodiment of the invention relates to a method and system for the production of biodiesel using an electrodeionization stack, wherein an ion exchange resin matrix acts as a heterogeneous catalyst for simultaneous esterification and transesterification reactions between a feedstock and a lower alcohol to produce biodiesel, wherein the feedstock contains significant levels of free fatty acid. In addition, because of the use of a heterogeneous catalyst, the glycerol and biodiesel have much lower salt concentrations than raw biodiesel produced by conventional transesterification processes. The present invention makes it much easier to purify glycerol and biodiesel.

An introduction of CO₂ conversion by dry reforming with methane and new route of low-temperature methanol synthesis.

PubMed

Shi, Lei; Yang, Guohui; Tao, Kai; Yoneyama, Yoshiharu; Tan, Yisheng; Tsubaki, Noritatsu

2013-08-20

Carbon dioxide is one of the highest contributors to the greenhouse effect, as well as a cheap and nontoxic building block for single carbon source chemistry. As such, CO₂ conversion is one of most important research areas in energy and environment sciences, as well as in catalysis technology. For chemical conversion of CO₂, natural gas (mainly CH₄) is a promising counterpart molecule to the CO₂-related reaction, due to its high availability and low price. More importantly, being able to convert CH₄ to useful fuels and molecules is advantageous, because it is also a kind of "greenhouse effect" gas, and can be an energy alternative to petroleum oil. In this Account, we discuss our development of efficient catalysts with precisely designed nanostructure for CO₂ reforming of CH₄ to produce syngas (mixture of CO and H₂), which can then be converted to many chemicals and energy products. This new production flow can establish a GTL (gas-to-liquid) industry, being currently pushed by the shale gas revolution. From the viewpoint of GTL industry, developing a catalyst for CO₂ reforming of CH₄ is a challenge, because they need a very high production rate to make the huge GTL methane reformer as small as possible. In addition, since both CO₂ and CH₄ give off carbon deposits that deactivate non-precious metallic catalysts very quickly, the total design of catalyst support and supported metallic nanoparticles is necessary. We present a simple but useful method to prepare bimodal catalyst support, where small pores are formed inside large ones during the self-organization of nanoparticles from solution. Large pores enhance the mass transfer rate, while small pores provide large surface areas to disperse active metallic nanoparticles. More importantly, building materials for small pores can also be used as promoters or cocatalysts to further enhance the total activity and stability. Produced syngas from methane reforming is generally catalytically converted in situ via one of two main routes. The first is to use Fischer-Tropsch synthesis (FTS), a process that catalytically converts syngas to hydrocarbons of varying molecular weights. The second is methanol synthesis. The latter has better atomic economy, since the oxygen atom in CO is included in the product and CO₂ can be blended into syngas as a reactant. However, production of methanol is very inefficient in this reaction: only 10-15% one-pass conversion typically at 5.0-10.0 MPa and 523-573 K, due to the severe thermodynamic limitations of this exothermal reaction (CO + 2H₂ = CH₃OH). In this Account, we propose and develop a new route of low-temperature methanol synthesis from CO₂-containing syngas only by adding alcohols, including methanol itself. These alcohols act as homogeneous cocatalysts and the solvent, realizing 70-100% one-pass conversion at only 5.0 MPa and 443 K. The key step is the reaction of the adsorbed formate species with alcohols to yield ester species at low temperatures, followed by the hydrogenation of ester by hydrogen atoms on metallic Cu. This changes the normal reaction path of conventional, high-temperature methanol synthesis from formate via methoxy to methanol.

Comparative techno-economic analysis and process design for indirect liquefaction pathways to distillate-range fuels via biomass-derived oxygenated intermediates upgrading

DOE PAGES

Tan, Eric C. D.; Snowden-Swan, Lesley J.; Talmadge, Michael; ...

2016-09-27

This paper presents a comparative techno-economic analysis (TEA) of five conversion pathways from biomass to gasoline-, jet-, and diesel-range hydrocarbons via indirect liquefaction with a specific focus on pathways utilizing oxygenated intermediates. The four emerging pathways of interest are compared with one conventional pathway (Fischer-Tropsch) for the production of the hydrocarbon blendstocks. The processing steps of the four emerging pathways include biomass-to-syngas via indirect gasification, syngas clean-up, conversion of syngas to alcohols/oxygenates followed by conversion of alcohols/oxygenates to hydrocarbon blendstocks via dehydration, oligomerization, and hydrogenation. Conversion of biomass-derived syngas to oxygenated intermediates occurs via three different pathways, producing: (i) mixedmore » alcohols over a MoS 2 catalyst, (ii) mixed oxygenates (a mixture of C 2+ oxygenated compounds, predominantly ethanol, acetic acid, acetaldehyde, ethyl acetate) using an Rh-based catalyst, and (iii) ethanol from syngas fermentation. This is followed by the conversion of oxygenates/alcohols to fuel-range olefins in two approaches: (i) mixed alcohols/ethanol to 1-butanol rich mixture via Guerbet reaction, followed by alcohol dehydration, oligomerization, and hydrogenation, and (ii) mixed oxygenates/ethanol to isobutene rich mixture and followed by oligomerization and hydrogenation. The design features a processing capacity of 2000 tonnes/day (2205 short tons) of dry biomass. The minimum fuel selling prices (MFSPs) for the four developing pathways range from 3.40 dollars to 5.04 dollars per gasoline-gallon equivalent (GGE), in 2011 US dollars. Sensitivity studies show that MFSPs can be improved with co-product credits and are comparable to the commercial Fischer-Tropsch benchmark ($3.58/GGE). Altogether, this comparative TEA study documents potential economics for the developmental biofuel pathways via mixed oxygenates.« less

Comparative techno-economic analysis and process design for indirect liquefaction pathways to distillate-range fuels via biomass-derived oxygenated intermediates upgrading

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

Tan, Eric C. D.; Snowden-Swan, Lesley J.; Talmadge, Michael

This paper presents a comparative techno-economic analysis (TEA) of five conversion pathways from biomass to gasoline-, jet-, and diesel-range hydrocarbons via indirect liquefaction with a specific focus on pathways utilizing oxygenated intermediates. The four emerging pathways of interest are compared with one conventional pathway (Fischer-Tropsch) for the production of the hydrocarbon blendstocks. The processing steps of the four emerging pathways include biomass-to-syngas via indirect gasification, syngas clean-up, conversion of syngas to alcohols/oxygenates followed by conversion of alcohols/oxygenates to hydrocarbon blendstocks via dehydration, oligomerization, and hydrogenation. Conversion of biomass-derived syngas to oxygenated intermediates occurs via three different pathways, producing: (i) mixedmore » alcohols over a MoS 2 catalyst, (ii) mixed oxygenates (a mixture of C 2+ oxygenated compounds, predominantly ethanol, acetic acid, acetaldehyde, ethyl acetate) using an Rh-based catalyst, and (iii) ethanol from syngas fermentation. This is followed by the conversion of oxygenates/alcohols to fuel-range olefins in two approaches: (i) mixed alcohols/ethanol to 1-butanol rich mixture via Guerbet reaction, followed by alcohol dehydration, oligomerization, and hydrogenation, and (ii) mixed oxygenates/ethanol to isobutene rich mixture and followed by oligomerization and hydrogenation. The design features a processing capacity of 2000 tonnes/day (2205 short tons) of dry biomass. The minimum fuel selling prices (MFSPs) for the four developing pathways range from 3.40 dollars to 5.04 dollars per gasoline-gallon equivalent (GGE), in 2011 US dollars. Sensitivity studies show that MFSPs can be improved with co-product credits and are comparable to the commercial Fischer-Tropsch benchmark ($3.58/GGE). Altogether, this comparative TEA study documents potential economics for the developmental biofuel pathways via mixed oxygenates.« less

Transesterification of oil mixtures catalyzed by microencapsulated cutinase in reversed micelles.

PubMed

Badenes, Sara M; Lemos, Francisco; Cabral, Joaquim M S

2010-03-01

Recombinant cutinase from Fusarium solani pisi was used to catalyze the transesterification reaction between a mixture of triglycerides (oils) and methanol in reversed micelles of bis(2-ethylhexyl) sodium sulfosuccinate (AOT) in isooctane for the purposes of producing biodiesel. The use of a bi-phase lipase-catalyzed system brings advantages in terms of catalyst re-use and the control of water activity in the medium and around the enzyme micro-environment. Small-scale batch studies were performed to study the influence of the initial enzyme and alcohol concentrations, and the substrates molar ratio. Conversions in excess of 75 were obtained with reaction times under 24 h, which makes this enzymatic process highly competitive when compared to similar lipase catalyzed reactions for biodiesel production using methanol.

Transetherification method

DOEpatents

Hearn, D.

1985-04-09

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

Transetherification method

DOEpatents

Hearn, Dennis

1985-01-01

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

Relative binding affinities of monolignols to horseradish peroxidase

DOE PAGES

Sangha, Amandeep K.; Petridis, Loukas; Cheng, Xiaolin; ...

2016-07-22

Monolignol binding to the peroxidase active site is the first step in lignin polymerization in plant cell walls. Using molecular dynamics, docking, and free energy perturbation calculations, we investigate the binding of monolignols to horseradish peroxidase C. Our results suggest that p-coumaryl alcohol has the strongest binding affinity followed by sinapyl and coniferyl alcohol. Stacking interactions between the monolignol aromatic rings and nearby phenylalanine residues play an important role in determining the calculated relative binding affinities. p-Coumaryl and coniferyl alcohols bind in a pose productive for reaction in which a direct H-bond is formed between the phenolic –OH group andmore » a water molecule (W2) that may facilitate proton transfer during oxidation. In contrast, in the case of sinapyl alcohol there is no such direct interaction, the phenolic –OH group instead interacting with Pro139. Furthermore, since proton and electron transfer is the rate-limiting step in monolignol oxidation by peroxidase, the binding pose (and thus the formation of near attack conformation) appears to play a more important role than the overall binding affinity in determining the oxidation rate.« less

Why are sec-alkylperoxyl bimolecular self-reactions orders of magnitude faster than the analogous reactions of tert-alkylperoxyls? The unanticipated role of CH hydrogen bond donation.

PubMed

Lee, Richmond; Gryn'ova, Ganna; Ingold, K U; Coote, Michelle L

2016-08-24

High-level ab initio calculations are used to identify the mechanism of secondary (and primary) alkylperoxyl radical termination and explain why their reactions are much faster than their tertiary counterparts. Contrary to existing literature, the decomposition of both tertiary and non-tertiary tetroxides follows the same asymmetric two-step bond cleavage pathway to form a caged intermediate of overall singlet multiplicity comprising triplet oxygen and two alkoxyl radicals. The alpha hydrogen atoms of non-tertiary species facilitate this process by forming unexpected CHO hydrogen bonds to the evolving O2. For non-tertiary peroxyls, subsequent alpha hydrogen atom transfer then yields the experimentally observed non-radical products, ketone, alcohol and O2, whereas for tertiary species, this reaction is precluded and cage escape of the (unpaired) alkoxyl radicals is a likely outcome with important consequences for autoxidation.

Pathways for Ethanol Dehydrogenation and Dehydration Catalyzed by Ceria (111) and (100) Surfaces

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

Beste, Ariana; Steven Overbury

2015-01-08

We have performed computations to better understand how surface structure affects selectivity in dehydrogenation and dehydration reactions of alcohols. Ethanol reactions on the (111) and (100) ceria surfaces were studied starting from the dominant surface species, ethoxy. We used DFT (PBE+U) to explore reaction pathways leading to ethylene and acetaldehyde and calculated estimates of rate constants employing transition state theory. To assess pathway contributions, we carried out kinetic analysis. Our results show that intermediate and transition state structures are stabilized on the (100) surface compared to the (111) surface. Formation of acetaldehyde over ethylene is kinetically and thermodynamically preferred onmore » both surfaces. Our results are consistent with temperature programmed surface reaction and steady-state experiments, where acetaldehyde was found as the main product and evidence was presented that ethylene formation at higher temperature originates from changes in adsorbate and surface structure.« less

Synthetic Studies on Tricyclic Diterpenoids: Direct Allylic Amination Reaction of Isopimaric Acid Derivatives†

PubMed Central

Timoshenko, Mariya A.; Kharitonov, Yurii V.; Shakirov, Makhmut M.; Bagryanskaya, Irina Yu.

2015-01-01

Abstract A selective synthesis of 7‐ or 14‐nitrogen containing tricyclic diterpenoids was completed according to a strategy in which the key step was the catalyzed direct allylic amination of methyl 14α‐hydroxy‐15,16‐dihydroisopimarate with a wide variety of nitrogenated nucleophiles. It was revealed that the selectivity of the reaction depends on the nature of nucleophile. The catalyzed reaction of the mentioned diterpenoid allylic alcohol with 3‐nitroaniline, 3‐(trifluoromethyl)aniline, and 4‐(trifluoromethyl)aniline yield the subsequent 7α‐, 7β‐ and 14αnitrogen‐containing diterpenoids. The reaction with 2‐nitroaniline, 4‐nitro‐2‐chloroaniline, 4‐methoxy‐2‐nitroaniline, phenylsulfamide, or tert‐butyl carbamate proceeds with the formation of 7α‐nitrogen‐substituted diterpenoids as the main products. PMID:27308214

A Boron Protecting Group Strategy for 1,2-Azaborines.

PubMed

Baggett, Andrew W; Liu, Shih-Yuan

2017-10-25

Upon reaction with either molecular oxygen or di-tert-butylperoxide in the presence of a simple copper(I) salt and an alcohol, a range of 1,2-azaborines readily exchange B-alkyl or B-aryl moieties for B-alkoxide fragments. This transformation allows alkyl and aryl groups to serve for the first time as removable protecting groups for the boron position of 1,2-azaborines during reactions that are not compatible with the easily modifiable B-alkoxide moiety. This reaction can be applied to synthesize a previously inaccessible BN isostere of ethylbenzene, a compound of interest in biomedical research. A sequence of epoxide ring opening using N-deprotonated 1,2-azaborines followed by an intramolecular version of the boron deprotection reaction can be applied to access the first examples of BN isosteres of dihydrobenzofurans and benzofurans, classes of compounds that are important to medicinal chemistry and natural product synthesis.

27 CFR 19.366 - Alcohol.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 27 Alcohol, Tobacco Products and Firearms 1 2011-04-01 2011-04-01 false Alcohol. 19.366 Section 19.366 Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO TAX AND TRADE BUREAU, DEPARTMENT OF THE..., and Removal of Products § 19.366 Alcohol. (a) Containers. A proprietor may put alcohol for industrial...

Major contribution of the Ehrlich pathway for 2-phenylethanol/rose flavor production in Ashbya gossypii.

PubMed

Ravasio, Davide; Wendland, Jürgen; Walther, Andrea

2014-09-01

Aroma alcohols of fermented food and beverages are derived from fungal amino acids catabolism via the Ehrlich pathway. This linear pathway consists of three enzymatic reactions to form fusel alcohols. Regulation of some of the enzymes occurs on the transcriptional level via Aro80. The riboflavin overproducer Ashbya gossypii produces strong fruity flavours in contrast to its much less aromatic relative Eremothecium cymbalariae. Genome comparisons indicated that A. gossypii harbors genes for aromatic amino acid catabolism (ARO8a, ARO8b, ARO10, and ARO80) while E. cymbalariae only encodes ARO8a and thus lacks major components of aromatic amino acid catabolism. Volatile compound (VOC) analysis showed that both Eremothecium species produce large amounts of isoamyl alcohol while A. gossypii also produces high levels of 2-phenylethanol. Deletion of the A. gossypii ARO-genes did not confer any growth deficiencies. However, A. gossypii ARO-mutants (except Agaro8a) were strongly impaired in aroma production, particularly in the production of the rose flavour 2-phenylethanol. Conversely, overexpression of ARO80 via the AgTEF1 promoter resulted in 50% increase in VOC production. Together these data indicate that A. gossypii is a very potent flavour producer and that amongst the non-Saccharomyces biodiversity strains can be identified that could provide positive sensory properties to fermented beverages. © 2014 Federation of European Microbiological Societies. Published by John Wiley & Sons Ltd. All rights reserved.

Organocatalyzed Domino [3+2] Cycloaddition/Payne-Type Rearrangement using Carbon Dioxide and Epoxy Alcohols.

PubMed

Kleij, Arjan Willem; Sopeña, Sergio; Cozzolino, Mariachiara; Escudero-Adán, Eduardo C; Martínez Belmonte, Marta; Maquilón, Cristina

2018-05-09

An unprecedented organocatalytic approach towards highly substituted cyclic carbonates from tri- and tetra-substituted oxiranes and carbon dioxide has been developed. The protocol involves the use of a simple and cheap superbase under mild, additive- and metal-free conditions towards the initial formation of a less substituted carbonate product that equilibrates to a tri- or even tetra-substituted cyclic carbonate under thermodynamic control. The latter are conveniently trapped in situ providing overall a new domino process for synthetically elusive heterocyclic scaffolds. Control experiments provide a rationale for the observed cascade reactions, which demonstrate high similarity with the well-known Payne rearrangement of epoxy alcohols. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrogen-bond formation between isoindolo[2,1-a]indol-6-one and aliphatic alcohols in n-hexane.

PubMed

Demeter, Attila; Bérces, Tibor

2005-03-17

The spectroscopic, kinetic, and equilibrium properties of isoindolo[2,1-a]indol-6-one (I) were studied in n-hexane in the presence and absence of alcohols (X). Hydrogen-bonded-complex formation was found to occur between the alcohol and the ground state as well as the excited state of the I molecule. The spectra of I and its singly complexed derivative (IX) are similar; however, that of IX is red shifted. The extent of red shift increases with the hydrogen-bonding ability of the alcohol. Equilibrium constant measurements were made to determine the hydrogen-bond basicity (beta(2)(H)) for I and the singlet excited (1)I. The beta(2)(H) value for (1)I is found to be about twice that of the ground-state I. Time-resolved fluorescence decay measurements indicate that the reaction of singlet excited I with fluorinated alcohols is diffusion controlled, while the rate of complexation with nonfluorinated (weaker hydrogen bonding) aliphatic alcohols depends on the Gibbs energy change in the complexation reaction. The quantitative correlation between the rate coefficient of complexation of (1)I with alcohols and the Gibbs energy change in the complexation process allowed us to estimate the rate coefficient for the complexation of the ground-state I with alcohols. The formation of the singlet excited hydrogen-bonded complex is irreversible; (1)IX disappears in a first order and an alcohol induced second order reaction. The first order decay is predominantly due to internal conversion to the ground state, the rate of which depends on the ionization energy of the complexing alcohol.

JPRS Report, Science & Technology, USSR: Chemistry.

DTIC Science & Technology

1988-12-23

Escape Accidents at Nuclear Power Plant With Water Moderated Reactors [S. A. Kabakehi, M. A. Budayev, et al.; KHIMIYA VYSOKIKH ENERGIY, Vol 22 No 4...water on the reactor surface also lowered loss of radicals. In general, the extent and temperature function Study of Radicals Desorbing From Surface... reactor sur- Alcohols With Oxygen face, by adsorption of the reagents and reaction products 184100 13f Moscow KHIMICHESKA YA FIZIKA on this surface and the

Methods of refining natural oils and methods of producing fuel compositions

DOEpatents

Firth, Bruce E; Kirk, Sharon E; Gavaskar, Vasudeo S

2015-11-04

A method of refining a natural oil includes: (a) providing a feedstock that includes a natural oil; (b) reacting the feedstock in the presence of a metathesis catalyst to form a metathesized product that includes olefins and esters; (c) passivating residual metathesis catalyst with an agent selected from the group consisting of phosphorous acid, phosphinic acid, and a combination thereof; (d) separating the olefins in the metathesized product from the esters in the metathesized product; and (e) transesterifying the esters in the presence of an alcohol to form a transesterified product and/or hydrogenating the olefins to form a fully or partially saturated hydrogenated product. Methods for suppressing isomerization of olefin metathesis products produced in a metathesis reaction, and methods of producing fuel compositions are described.

Asymmetric Synthesis of Secondary and Tertiary Propargylic Alcohols by Umpolung of Acetylenic Sulfones and ortho-Sulfinyl Carbanions.

PubMed

Rodríguez, Ricardo I; Ramírez, Elsie; Yuste, Francisco; Sánchez-Obregón, Rubén; Alemán, José

2018-02-16

The generation of diastereomerically enriched secondary benzyl propargyl alcohols by the asymmetric addition of ortho-sulfinylbenzyl carbanions to sulfonylacetylene derivatives via formation of a Csp-Csp 3 bond is described. This reaction proceeds through an unusual α-attack (anti-Michael addition) of the ortho-sulfinylbenzyl carbanions, followed by elimination of the arylsulfonyl moiety. The scope of this alkynylation reaction is also discussed. Moreover, the development of a new approach for the synthesis of optically active tertiary benzylpropargyl alcohols is described, discussing the possible stereocourse of the reaction so as the influence of the ether 18-crown-6 and steric importance of acetylenic substituent.

Ambient cure polyimide foams prepared from aromatic polyisocyanates, aromatic polycarboxylic compounds, furfuryl alcohol, and a strong inorganic acid

NASA Technical Reports Server (NTRS)

Sawko, Paul M. (Inventor); Riccitiello, Salvatore R. (Inventor); Hamermesh, Charles L. (Inventor)

1980-01-01

Flame and temperature resistant polyimide foams are prepared by the reaction of an aromatic dianhydride, e.g., pyromellitic dianhydride, with an aromatic polyisocyanate, e.g., polymethylene polyphenylisocyanate (PAPI) in the presence of an inorganic acid and a lower molecular weight alcohol, e.g., dilute sulfuric acid or phosphoric acid and furfuryl alcohol. The exothermic reaction between the acid and the alcohol provides the heat necessary for the other reactants to polymerize without the application of any external heat. Such mixtures, therefore, are ideally suited for in situ foam formation, especially where the application of heat is not practical or possible.

Homogeneous Palladium-Catalyzed Transfer Hydrogenolysis of Benzylic Alcohols Using Formic Acid as Reductant.

PubMed

Ciszek, Benjamin; Fleischer, Ivana

2018-04-12

Herein we report the first homogeneous palladium-based transfer hydrogenolysis of benzylic alcohols using an in situ formed palladium-phosphine complex and formic acid as reducing agent. The reaction requires a catalyst loading as low as only 1 mol% of palladium and just a slight excess of reductant to obtain the deoxygenated alkylarenes in good to excellent yields. Besides demonstrating the broad applicability for primary, secondary and tertiary benzylic alcohols, a reaction intermediate could be identified. Additionally, it could be shown that partial oxidation of the applied phosphine ligand was beneficial for the course of the reaction, presumably by stabilizing the active catalyst. Reaction profiles and catalyst poisoning experiments were used to characterize the catalyst, the results indicate a homogeneous metal complex as active species. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

AgI /TMG-Promoted Cascade Reaction of Propargyl Alcohols, Carbon Dioxide, and 2-Aminoethanols to 2-Oxazolidinones.

PubMed

Li, Xue-Dong; Song, Qing-Wen; Lang, Xian-Dong; Chang, Yao; He, Liang-Nian

2017-11-17

Chemical valorization of CO 2 to access various value-added compounds has been a long-term and challenging objective from the viewpoint of sustainable chemistry. Herein, a one-pot three-component reaction of terminal propargyl alcohols, CO 2 , and 2-aminoethanols was developed for the synthesis of 2-oxazolidinones and an equal amount of α-hydroxyl ketones promoted by Ag 2 O/TMG (1,1,3,3-tetramethylguanidine) with a TON (turnover number) of up to 1260. By addition of terminal propargyl alcohol, the thermodynamic disadvantage of the conventional 2-aminoethanol/CO 2 coupling was ameliorated. Mechanistic investigations including control experiments, DFT calculation, kinetic and NMR studies suggest that the reaction proceeds through a cascade pathway and TMG could activate propargyl alcohol and 2-aminoethanol through the formation of hydrogen bonds and also activate CO 2 . © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

The Palladium-Catalyzed Aerobic Kinetic Resolution of Secondary Alcohols: Reaction Development, Scope, and Applications

PubMed Central

Ebner, David C.; Bagdanoff, Jeffrey T.; Ferreira, Eric M.; McFadden, Ryan M.; Caspi, Daniel D.; Trend, Raissa M.

2010-01-01

The first palladium-catalyzed enantioselective oxidation of secondary alcohols has been developed, utilizing the readily available diamine (−)-sparteine as chiral ligand and molecular oxygen as the stoichiometric oxidant. Mechanistic insights regarding the role of base and hydrogen bond donors have resulted in several improvements to the original system. Namely, addition of cesium carbonate and tert-butyl alcohol greatly enhances reaction rates, promoting rapid resolutions. The use of chloroform as solvent allows the use of ambient air as the terminal oxidant at 23 °C, resulting in enhanced catalyst selectivity. These improved reaction conditions have permitted the successful kinetic resolution of benzylic, allylic, and cyclopropyl secondary alcohols to high enantiomeric excess with good to excellent selectivity factors. This catalyst system has also been applied to the desymmetrization of meso-diols, providing high yields of enantioenriched hydroxyketones. PMID:19904777

Hexafluoroisopropyl alcohol mediated synthesis of 2,3-dihydro-4H-pyrido[1,2-a]pyrimidin-4-ones

PubMed Central

Alam, Mohammad A.; Alsharif, Zakeyah; Alkhattabi, Hessa; Jones, Derika; Delancey, Evan; Gottsponer, Adam; Yang, Tianhong

2016-01-01

An efficient synthesis of novel 2,3-dihydro-4H-pyrido[1,2-a]pyrimidin-4-ones has been reported. Inexpensive and readily available substrates, environmentally benign reaction condition, and product formation up to quantitative yield are the key features of this methodology. Products are formed by the aza-Michael addition followed by intramolecular acyl substitution in a domino process. The polar nature and strong hydrogen bond donor capability of 1,1,1,3,3,3-hexafluoropropan-2-ol is pivotal in this cascade protocol. PMID:27805054

Laboratory testing of alcohol safety interlock systems employing divided attention tests

DOT National Transportation Integrated Search

1975-12-01

Author's abstract: Prototype Alcohol Safety Interlock Systems employing measurements of tracking ability, reaction time, and response accuracy to discern alcohol impairment were submitted to laboratory testing. These systems were modified versions of...

Rhodium-catalyzed kinetic resolution of tertiary homoallyl alcohols via stereoselective carbon-carbon bond cleavage.

PubMed

Shintani, Ryo; Takatsu, Keishi; Hayashi, Tamio

2008-03-20

A nonenzymatic kinetic resolution of tertiary homoallyl alcohols has been developed through a rhodium-catalyzed retro-allylation reaction under simple conditions. Selectivity factors of up to 12 have been achieved by employing (R)-H8-binap as the ligand, and the reaction can be conducted on a preparative scale.

A Dioxane Template for Highly Selective Epoxy Alcohol Cyclizations

PubMed Central

Mousseau, James J.; Morten, Christopher J.

2013-01-01

Ladder polyether natural products are a class of natural products denoted by their high functional group density and large number of well-defined stereocenters. They comprise the toxic component of harmful algal blooms (HABs), having significant negative economic and environmental ramifications. However, their mode of action, namely blocking various cellular ion channels, also denotes their promise as potential anticancer agents. Understanding their potential mode of biosynthesis will not only help with developing ways to limit the damage of HABs, but would also facilitate the synthesis of a range of analogues with interesting biological activity. 1,3-Dioxan-5-ol substrates display remarkable ‘enhanced template effects’ in water-promoted epoxide cyclization processes en route to the synthesis of these ladder polyether natural products. In many cases they provide near complete endo to exo selectivity in the cyclization of epoxy alcohols, thereby strongly favouring the formation of tetrahydropyran (THP) over tetrahydrofuran (THF) rings. The effects of various Brønsted and Lewis acidic and basic conditions are explored to demonstrate the superior selectivity of the template over the previously reported THP-based epoxy alcohols. In addition, the consideration of other synthetic routes are also considered with the goal of gaining rapid access to a plethora of potential starting materials applicable towards the synthesis of ladder polyethers. Finally, cascade sequences with polyepoxides are investigated, further demonstrating the versatility of this new reaction template. PMID:23775936

Dual nickel and Lewis acid catalysis for cross-electrophile coupling: the allylation of aryl halides with allylic alcohols† †Electronic supplementary information (ESI) available. CCDC 1515176. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc03140h

PubMed Central

Jia, Xue-Gong; Guo, Peng; Duan, Jicheng

2017-01-01

Controlling the selectivity in cross-electrophile coupling reactions is a significant challenge, particularly when one electrophile is much more reactive. We report a general and practical strategy to address this problem in the reaction between reactive and unreactive electrophiles by a combination of nickel and Lewis acid catalysis. This strategy is used for the coupling of aryl halides with allylic alcohols to form linear allylarenes selectively. The reaction tolerates a wide range of functional groups (e.g. silanes, boronates, anilines, esters, alcohols, and various heterocycles) and works with various allylic alcohols. Complementary to most current routes for the C3 allylation of an unprotected indole, this method provides access to C2 and C4–C7 allylated indoles. Preliminary mechanistic experiments reveal that the reaction might start with an aryl nickel intermediate, which then reacts with Lewis acid activated allylic alcohols in the presence of Mn. PMID:29629130

Rapid Covalent Modification of Silicon Oxide Surfaces through Microwave-Assisted Reactions with Alcohols.

PubMed

Lee, Austin W H; Gates, Byron D

2016-07-26

We demonstrate the method of a rapid covalent modification of silicon oxide surfaces with alcohol-containing compounds with assistance by microwave reactions. Alcohol-containing compounds are prevalent reagents in the laboratory, which are also relatively easy to handle because of their stability against exposure to atmospheric moisture. The condensation of these alcohols with the surfaces of silicon oxides is often hindered by slow reaction kinetics. Microwave radiation effectively accelerates this condensation reaction by heating the substrates and/or solvents. A variety of substrates were modified in this demonstration, such as silicon oxide films of various thicknesses, glass substrates such as microscope slides (soda lime), and quartz. The monolayers prepared through this strategy demonstrated the successful formation of covalent surface modifications of silicon oxides with water contact angles of up to 110° and typical hysteresis values of 2° or less. An evaluation of the hydrolytic stability of these monolayers demonstrated their excellent stability under acidic conditions. The techniques introduced in this article were successfully applied to tune the surface chemistry of silicon oxides to achieve hydrophobic, oleophobic, and/or charged surfaces.

Optimization of fatty alcohol biosynthesis pathway for selectively enhanced production of C12/14 and C16/18 fatty alcohols in engineered Escherichia coli

PubMed Central

2012-01-01

Background With the increasing stress from oil price and environmental pollution, aroused attention has been paid to the microbial production of chemicals from renewable sources. The C12/14 and C16/18 alcohols are important feedstocks for the production of surfactants and detergents, which are widely used in the most respected consumer detergents, cleaning products and personal care products worldwide. Though bioproduction of fatty alcohols has been carried out in engineered E. coli, several key problems have not been solved in earlier studies, such as the quite low production of C16/18 alcohol, the lack of optimization of the fatty alcohol biosynthesis pathway, and the uncharacterized performance of the engineered strains in scaled-up system. Results We improved the fatty alcohol production by systematically optimizing the fatty alcohol biosynthesis pathway, mainly targeting three key steps from fatty acyl-acyl carrier proteins (ACPs) to fatty alcohols, which are sequentially catalyzed by thioesterase, acyl-coenzyme A (CoA) synthase and fatty acyl-CoA reductase. By coexpression of thioesterase gene BTE, acyl-CoA synthase gene fadD and fatty acyl-CoA reductase gene acr1, 210.1 mg/L C12/14 alcohol was obtained. A further optimization of expression level of BTE, fadD and acr1 increased the C12/14 alcohol production to 449.2 mg/L, accounting for 75.0% of the total fatty alcohol production (598.6 mg/L). In addition, by coexpression of thioesterase gene ‘tesA, acyl-CoA synthase gene fadD and fatty acyl-CoA reductase gene FAR, 101.5 mg/L C16/18 alcohol was obtained, with C16/18 alcohol accounting for 89.2% of the total fatty alcohol production. Conclusions To our knowledge, this is the first report on selective production of C12/14 and C16/18 alcohols by microbial fermentation. This work achieved high-specificity production of both C12/14 and C16/18 alcohols. The encouraging 598.6 mg/L of fatty alcohols represents the highest titer reported so far. In addition, the 101.5 mg/L 89.2% C16/18 alcohol suggests an important breakthrough in C16/18 alcohol production. A more detailed optimization of the expression level of fatty alcohol biosynthesis pathway may contribute to a further improvement of fatty alcohol production. PMID:22607313

High enantioselective Novozym 435-catalyzed esterification of (R,S)-flurbiprofen monitored with a chiral stationary phase.

PubMed

Siódmiak, Tomasz; Mangelings, Debby; Vander Heyden, Yvan; Ziegler-Borowska, Marta; Marszałł, Michał Piotr

2015-03-01

Lipases form Candida rugosa and Candida antarctica were tested for their application in the enzymatic kinetic resolution of (R,S)-flurbiprofen by enantioselective esterification. Successful chromatographic separation with well-resolved peaks of (R)- and (S)-flurbiprofen and their esters was achieved in one run on chiral stationary phases by high-performance liquid chromatography (HPLC). In this study screening of enzymes was performed, and Novozym 435 was selected as an optimal catalyst for obtaining products with high enantiopurity. Additionally, the influence of organic solvents (dichloromethane, dichloroethane, dichloropropane, and methyl tert-butyl ether), primary alcohols (methanol, ethanol, n-propanol, and n-butanol), reaction time, and temperature on the enantiomeric ratio and conversion was tested. The high values of enantiomeric ratio (E in the range of 51.3-90.5) of the esterification of (R,S)-flurbiprofen were obtained for all tested alcohols using Novozym 435, which have a great significance in the field of biotechnological synthesis of drugs. The optimal temperature range for the performed reactions was from 37 to 45 °C. As a result of the optimization, (R)-flurbiprofen methyl ester was obtained with a high optical purity, eep = 96.3 %, after 96 h of incubation. The enantiomeric ratio of the reaction was E = 90.5 and conversion was C = 35.7 %.

Electronic nose screening of ethanol release during sol-gel encapsulation. A novel non-invasive method to test silica polymerisation.

PubMed

Lovino, Magalí; Cardinal, M Fernanda; Zubiri, Diana B V; Bernik, Delia L

2005-12-15

Porous silica matrices prepared by sol-gel process yield biocompatible materials adequate for encapsulation of biomolecules or drugs. The procedure is simple and fast, but when alkoxyde precursors like tetraethoxysilane (TEOS) are used the polymerisation reaction leads to the formation of alcohol as a by-product, which can produce undesirable effects on the activity of entrapped enzymes or modify a drug release kinetic. Therefore, it is critical to determine that no remnant ethanol is left prior using or storing the obtained biomaterial. In this regard, the technique used in the alcohol determination should be non-invasive and non-destructive to preserve the encapsulation device intact and ready to use. In this work we have successfully used a portable electronic nose (e-nose) for the screening of silica polymerisation process during theophylline encapsulation. TEOS reaction was "smelt" since precursor pre-hydrolysis until the end of ethanol release, sensed directly at the headspace of matrices slabs. Measurements showed that ethanol was negligible since 10th day in polymeric slabs of 10 mm width and 2 cm diameter. This first use of e-nose following a polymerisation reaction opens a wide number of putative applications in pharmaceutical and biochemical fields.

Biological Vulnerability to Alcoholism.

ERIC Educational Resources Information Center

Schuckit, Marc A.

1987-01-01

Reviews the role of biological factors in the risk for alcoholism. Notes the importance of the definition of primary alcoholism and highlights data indicating that this disorder is genetically influenced. In studies of men at high risk for the future development of alcoholism, vulnerability shows up in reactions to ethanol brain wave amplitude and…

Synthesis of biodiesel from pongamia oil using heterogeneous ion-exchange resin catalyst.

PubMed

Jaya, N; Selvan, B Karpanai; Vennison, S John

2015-11-01

Biodiesel is a clean-burning renewable substitute fuel for petroleum. Biodiesel could be effectively produced by transesterification reaction of triglycerides of vegetable oils with short-chain alcohols in the presence of homogeneous or heterogeneous catalysts. Conventionally, biodiesel manufacturing processes employ strong acids or bases as catalysts. But, separation of the catalyst and the by-product glycerol from the product ester is too expensive to justify the product use as an automobile fuel. Hence heterogeneous catalysts are preferred. In this study, transesterification of pongamia oil with ethanol was performed using a solid ion-exchange resin catalyst. It is a macro porous strongly basic anion exchange resin. The process parameters affecting the ethyl ester yield were investigated. The reaction conditions were optimized for the maximum yield of fatty acid ethyl ester (FAEE) of pongamia oil. The properties of FAEE were compared with accepted standards of biodiesel. Engine performance was also studied with pongamia oil diesel blend and engine emission characteristics were observed. Copyright © 2015 Elsevier Inc. All rights reserved.

X Chromosome Inactivation in Women with Alcoholism

PubMed Central

Manzardo, Ann M.; Henkhaus, Rebecca; Hidaka, Brandon; Penick, Elizabeth C.; Poje, Albert B.; Butler, Merlin G.

2012-01-01

Background All female mammals with two X chromosomes balance gene expression with males having only one X by inactivating one of their Xs (X chromosome inactivation, XCI). Analysis of XCI in females offers the opportunity to investigate both X-linked genetic factors and early embryonic development that may contribute to alcoholism. Increases in the prevalence of skewing of XCI in women with alcoholism could implicate biological risk factors. Methods The pattern of XCI was examined in DNA isolated in blood from 44 adult females meeting DSM IV criteria for an Alcohol Use Disorder, and 45 control females with no known history of alcohol abuse or dependence. XCI status was determined by analyzing digested and undigested polymerase chain reaction (PCR) products of the polymorphic androgen receptor (AR) gene located on the X chromosome. Subjects were categorized into 3 groups based upon the degree of XCI skewness: random (50:50–64:36), moderately skewed (65:35–80:20) and highly skewed (>80:20). Results XCI status from informative females with alcoholism was found to be random in 59% (n=26), moderately skewed in 27% (n=12) or highly skewed in 14% (n=6). Control subjects showed 60%, 29% and 11%, respectively. The distribution of skewed XCI observed among women with alcoholism did not differ statistically from that of control subjects (χ2 =0.14, 2 df, p=0.93). Conclusions Our data did not support an increase in XCI skewness among women with alcoholism or implicate early developmental events associated with embryonic cell loss or unequal (non-random) expression of X-linked gene(s) or defects in alcoholism among females. PMID:22375556

Status and prospects in higher alcohols synthesis from syngas.

PubMed

Luk, Ho Ting; Mondelli, Cecilia; Ferré, Daniel Curulla; Stewart, Joseph A; Pérez-Ramírez, Javier

2017-03-06

Higher alcohols are important compounds with widespread applications in the chemical, pharmaceutical and energy sectors. Currently, they are mainly produced by sugar fermentation (ethanol and isobutanol) or hydration of petroleum-derived alkenes (heavier alcohols), but their direct synthesis from syngas (CO + H 2 ) would comprise a more environmentally-friendly, versatile and economical alternative. Research efforts in this reaction, initiated in the 1930s, have fluctuated along with the oil price and have considerably increased in the last decade due to the interest to exploit shale gas and renewable resources to obtain the gaseous feedstock. Nevertheless, no catalytic system reported to date has performed sufficiently well to justify an industrial implementation. Since the design of an efficient catalyst would strongly benefit from the establishment of synthesis-structure-function relationships and a deeper understanding of the reaction mechanism, this review comprehensively overviews syngas-based higher alcohols synthesis in three main sections, highlighting the advances recently made and the challenges that remain open and stimulate upcoming research activities. The first part critically summarises the formulations and methods applied in the preparation of the four main classes of materials, i.e., Rh-based, Mo-based, modified Fischer-Tropsch and modified methanol synthesis catalysts. The second overviews the molecular-level insights derived from microkinetic and theoretical studies, drawing links to the mechanisms of Fischer-Tropsch and methanol syntheses. Finally, concepts proposed to improve the efficiency of reactors and separation units as well as to utilise CO 2 and recycle side-products in the process are described in the third section.

Biocatalytic anti-Prelog reduction of prochiral ketones with whole cells of Acetobacter pasteurianus GIM1.158

PubMed Central

2014-01-01

Background Enantiomerically pure alcohols are important building blocks for production of chiral pharmaceuticals, flavors, agrochemicals and functional materials and appropriate whole-cell biocatalysts offer a highly enantioselective, minimally polluting route to these valuable compounds. At present, most of these biocatalysts follow Prelog’s rule, and thus the (S)-alcohols are usually obtained when the smaller substituent of the ketone has the lower CIP priority. Only a few anti-Prelog (R)-specific whole cell biocatalysts have been reported. In this paper, the biocatalytic anti-Prelog reduction of 2-octanone to (R)-2-octanol was successfully conducted with high enantioselectivity using whole cells of Acetobacter pasteurianus GIM1.158. Results Compared with other microorganisms investigated, Acetobacter pasteurianus GIM1.158 was shown to be more effective for the reduction reaction, affording much higher yield, product enantiomeric excess (e.e.) and initial reaction rate. The optimal temperature, buffer pH, co-substrate and its concentration, substrate concentration, cell concentration and shaking rate were 35°C, 5.0, 500 mmol/L isopropanol, 40 mmol/L, 25 mg/mL and 120 r/min, respectively. Under the optimized conditions, the maximum yield and the product e.e. were 89.5% and >99.9%, respectively, in 70 minutes. Compared with the best available data in aqueous system (yield of 55%), the yield of (R)-2-octanol was greatly increased. Additionally, the efficient whole-cell biocatalytic process was feasible on a 200-mL preparative scale and the chemical yield increased to 95.0% with the product e.e. being >99.9%. Moreover, Acetobacter pasteurianus GIM1.158 cells were proved to be capable of catalyzing the anti-Prelog bioreduction of other prochiral carbonyl compounds with high efficiency. Conclusions Via an effective increase in the maximum yield and the product e.e. with Acetobacter pasteurianus GIM1.158 cells, these results open the way to use of whole cells of this microorganism for challenging enantioselective reduction reactions on laboratory and commercial scales. PMID:24916156

Changes in Reactivity as Chemistry Becomes Confined to an Interface. The Case of Free Radical Oxidation of C 30H 62 Alkane by OH

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

Houle, Frances A.; Wiegel, Aaron A.; Wilson, Kevin R.

Here, we examine in a simple organic aerosol the transition between heterogeneous chemistry under well-mixed conditions to chemistry under interfacial confinement. A single reaction mechanism, shown to reproduce observed OH oxidation chemistry for liquid and semisolid C 30H 62, is used in reaction-diffusion simulations to explore reactivity over a broad viscosity range. The results show that when internal mixing of the aerosol is fast and the particle interface is enriched in C-H groups, ketone and alcohol products, formed via peroxy radical disproportionation, predominate. As viscosity increases the reactions become confined to a shell at the gas-aerosol interface. The confinement ismore » accompanied by emergence of acyloxy reaction pathways that are particularly active when the shell is 1 nm or less. We quantify this trend using a reaction-diffusion index, allowing the parts of the mechanism that control reactivity as viscosity increases to be identified.« less

Changes in Reactivity as Chemistry Becomes Confined to an Interface. The Case of Free Radical Oxidation of C 30H 62 Alkane by OH

DOE PAGES

Houle, Frances A.; Wiegel, Aaron A.; Wilson, Kevin R.

2018-02-14

Here, we examine in a simple organic aerosol the transition between heterogeneous chemistry under well-mixed conditions to chemistry under interfacial confinement. A single reaction mechanism, shown to reproduce observed OH oxidation chemistry for liquid and semisolid C 30H 62, is used in reaction-diffusion simulations to explore reactivity over a broad viscosity range. The results show that when internal mixing of the aerosol is fast and the particle interface is enriched in C-H groups, ketone and alcohol products, formed via peroxy radical disproportionation, predominate. As viscosity increases the reactions become confined to a shell at the gas-aerosol interface. The confinement ismore » accompanied by emergence of acyloxy reaction pathways that are particularly active when the shell is 1 nm or less. We quantify this trend using a reaction-diffusion index, allowing the parts of the mechanism that control reactivity as viscosity increases to be identified.« less

A comparative analysis of characteristic floral scent compounds in Prunus mume and related species.

PubMed

Hao, Ruijie; Du, Dongliang; Wang, Tao; Yang, Weiru; Wang, Jia; Zhang, Qixiang

2014-01-01

In order to investigate the difference in their characteristic floral scents between Prunus mume Siebold & Zucc. and the related Prunus species, their headspace volatiles and endogenous extraction were analyzed by gas chromatography-mass spectrometry. The efficiency of substrate utilization of the flowers was studied by incubating them with different alcohol substrates. Our results indicated that benzyl acetate is a dominant compound influencing the characteristic floral scent of P. mume. An alcohol substrate concentration of 4 mmol L(-1) and a reaction time of 2 h were constituted the reaction condition for catalysis of exogenous alcohol substrates by the flowers. Under these conditions, Prunus sibirica exhibited the highest utilization efficiency for benzyl alcohol substrate while the utilization efficiency of Prunus persica was the lowest. Comparative analysis of several alcohol substrates indicated that the flowers of the tested species had selective specificity for benzyl alcohol substrates.

[How aliphatic alcohols and ph affect reactional capability of the horse blood serum cholinesterase at its interaction with organophosphorus inhibitors].

PubMed

Basova, N E; Kormilitsin, B N; Perchenok, A Iu; Rozengart, E V; Saakov, V S; Suvorov, A A

2013-01-01

There was studied action of aliphatic alcohols (ethanol, propanol, isopropanol, n-butanol, isobutanol, secbutanol, tretbetanol) and pH on various kinds of reactional capability the serum cholinesterase. At the alcohols-affected inhibition of the cholinesterase hydrolytic activity, the determining role was played not the total number carbon atoms in the alcohol molecule, but by the "effective length" of the carbohydrate chain. The fact that the presence of alcohols did not affect parameters of the reverse cholinesterase inhibition with onium ions tetramethylammonium and choline allows suggesting the absence of effect solvents on specific acetylcholine sorption in the enzyme active center. With aid of two rows of hydrophobic organophosphorus inhibitors (OPI), we have managed to estimate both the degree and the character itself of the modifying action of alcohols and pH on the process of irreversible inhibition of serum cholinesterase.

Pentynyl dextran as a support matrix for immobilization of serine protease subtilisin Carlsberg and its use for transesterification of N-acetyl-L-phenylalanine ethyl ester in organic media.

PubMed

Tahir, Muhammad Nazir; Cho, Eunae; Mischnick, Petra; Lee, Jae Yung; Yu, Jae-Hyuk; Jung, Seunho

2014-04-01

In this study, serine protease (subtilisin Carlsberg) was immobilized on pentynyl dextran (PyD, O-alkynyl ether of dextran, 1) and used for the transesterification of N-acetyl-L-phenylalanine ethyl ester (2) with different aliphatic (1-propanol, 1-butanol, 1-pentanol, 1-hexanol) and aromatic (benzyl alcohol, 2-phenyl ethanol, 4-phenyl-1-butanol) alcohols in tetrahydrofuran (THF). The effect of carbon chain length in aliphatic and aromatic alcohols on initial and average transesterification rate, transesterification activity of immobilized enzyme and yield of the reaction under selected reaction conditions was investigated. The transesterification reactivity of the enzyme and yield of the reaction increased as the chain length of the alcohols decreased. Furthermore, almost no change in yield was observed when the immobilized enzyme was repeatedly used for selected alcohols over six cycles. Intrinsic fluorescence analysis showed that the catalytic activity of the immobilized enzyme in THF was maintained due to retention of the tertiary structure of the enzyme after immobilization on PyD (1).

IR spectral studies of the formation of prebiological organic molecules in ion-bombarded ices

NASA Astrophysics Data System (ADS)

Hudson, R.; Moore, M.

To better understand the formation of C- and CN-containing molecules in cold cosmic environments we have performed a variety of processing experiments on icy mixtures. We will discuss details of condensed-phase synthetic pathways for several acids, alcohols, and aldehydes. For N2 -rich ices containing CH4 , we will show that several CN-bonded acids are easily formed. We will compare carbonic and formic acid production in H O-, CO- and CO2 -dominated ices.2 Condensed-phase pathways for the synthesis of several alcohols including methanol and ethylene glycol, along with several aldehydes including formaldehyde and acetaldehyde, will be discussed. While warming irradiated ices, IR spectra help track the formation of new species from, for example, radical or acid-base reactions, and the loss of species due to vaporization. These experiments demonstrate that condensed-phase reactions lead to cometary and interstellar molecules of varying volatilities. Several newly synthesized species are particularly relevant to recent radio detections, and are of high interest to astronomers and astrobiologists. This research is funded through NRA 344-33-01 and 344-02-57.

Rare sugars and sugar-based synthons by chemo-enzymatic synthesis.

PubMed

Giffhorn; Köpper; Huwig; Freimund

2000-12-01

The unique catalytic potential of the fungal enzyme pyranose oxidase was demonstrated by preparative conversions of a variety of carbohydrates, and by extensive chemical characterization of the reaction products with NMR spectroscopy. The studies revealed that POx not only oxidizes most substrates very efficiently but also that POx possesses a glycosyl-transfer potential, producing disaccharides from beta-glycosides of higher alcohols. Although most substrates are oxidized by POx at the C-2 position, several substrates are converted into the 3-keto-derivatives. On the basis of these products, strategies are developed for the convenient production of sugar-derived synthons, rare sugars and fine chemicals by combining biotechnical and chemical methods.

27 CFR 19.356 - Alcohol content and fill.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 27 Alcohol, Tobacco Products and Firearms 1 2011-04-01 2011-04-01 false Alcohol content and fill. 19.356 Section 19.356 Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO TAX AND TRADE BUREAU... Bottling, Packaging, and Removal of Products § 19.356 Alcohol content and fill. (a) General. At...

27 CFR 19.398 - Alcohol.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 27 Alcohol, Tobacco Products and Firearms 1 2010-04-01 2010-04-01 false Alcohol. 19.398 Section 19.398 Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO TAX AND TRADE BUREAU, DEPARTMENT OF THE... Articles Bottling, Packaging, and Removal of Products § 19.398 Alcohol. (a) Containers. Subject to the...

Modelling of Criegee Intermediates using the 3-D global model, STOCHEM-CRI and investigating their global impacts on Secondary Organic Aerosol formation

NASA Astrophysics Data System (ADS)

Khan, M. Anwar H.; Cooke, Michael; Utembe, Steve; Archibald, Alexander; Derwent, Richard; Jenkin, Mike; Lyons, Kyle; Kent, Adam; Percival, Carl; Shallcross, Dudley E.

2016-04-01

Gas phase reactions of ozone with unsaturated compounds form stabilized Criegee intermediates (sCI) which play an important role in controlling the budgets of many tropospheric species including OH, organic acids and secondary organic aerosols (SOA). Recently sCI has been proposed to play a significant role in atmospheric sulfate and nitrate chemistry by forming sulfuric acid (promoter of aerosol formation) and nitrate radical (a powerful oxidizing agent). sCI can also undergo association reactions with water, alcohols, and carboxylic acids to form hydroperoxides and with aldehydes and ketones to form secondary ozonides. The products from these reactions are low volatility compounds which can contribute to the formation of SOA. The importance of plant emitted alkenes (isoprene, monoterpenes, sesquiterpenes) in the production of SOA through sCI formation have already been investigated in laboratory studies. However, the SOA formation from these reactions are absent in current global models. Thus, the formation of SOA has been incorporated in the global model, STOCHEM-CRI, a 3-D global chemistry transport model and the role of CI chemistry in controlling atmospheric composition and climate, and the influence of water vapor has been discussed in the study.

Reactivity of catecholamine-driven Fenton reaction and its relationships with iron(III) speciation.

PubMed

Melin, Victoria; Henríquez, Adolfo; Freer, Juanita; Contreras, David

2015-03-01

Fenton reaction is the main source of free radicals in biological systems. The reactivity of this reaction can be modified by several factors, among these iron ligands are important. Catecholamine (dopamine, epinephrine, and norepinephrine) are able to form Fe(III) complexes whose extension in the coordination number depends upon the pH. Fe(III)-catecholamine complexes have been related with the development of several pathologies. In this work, the ability of catecholamines to enhance the oxidative degradation of an organic substrate (veratryl alcohol, VA) through Fenton and Fenton-like reactions was studied. The initial VA degradation rate at different pH values and its relationship to the different iron species present in solution were determined. Furthermore, the oxidative degradation of VA after 24 hours of reaction and its main oxidation products were also determined. The catecholamine-driven Fenton and Fenton-like systems showed higher VA degradation compared to unmodified Fenton or Fenton-like systems, which also showed an increase in the oxidation state of the VA degradation product. All of this oxidative degradation takes place at pH values lower than 5.50, where the primarily responsible species would be the Fe(III) mono-complex. The presence of Fe(III) mono-complex is essential in the ability of catecholamines to increase the oxidative capacity of Fenton systems.

A novel method to quantify the activity of alcohol acetyltransferase Using a SnO2-based sensor of electronic nose.

PubMed

Hu, Zhongqiu; Li, Xiaojing; Wang, Huxuan; Niu, Chen; Yuan, Yahong; Yue, Tianli

2016-07-15

Alcohol acetyltransferase (AATFase) extensively catalyzes the reactions of alcohols to acetic esters in microorganisms and plants. In this work, a novel method has been proposed to quantify the activity of AATFase using a SnO2-based sensor of electronic nose, which was determined on the basis of its higher sensitivity to the reducing alcohol than the oxidizing ester. The maximum value of the first-derivative of the signals from the SnO2-based sensor was therein found to be an eigenvalue of isoamyl alcohol concentration. Quadratic polynomial regression perfectly fitted the correlation between the eigenvalue and the isoamyl alcohol concentration. The method was used to determine the AATFase activity in this type of reaction by calculating the conversion rate of isoamyl alcohol. The proposed method has been successfully applied to determine the AATFase activity of a cider yeast strain. Compared with GC-MS, the method shows promises with ideal recovery and low cost. Copyright © 2016 Elsevier Ltd. All rights reserved.

Importance of Unimolecular HO 2 Elimination in the Heterogeneous OH Reaction of Highly Oxygenated Tartaric Acid Aerosol

DOE PAGES

Cheng, Chiu Tung; Chan, Man Nin; Wilson, Kevin R.

2016-07-09

Oxygenated organic molecules are abundant in atmospheric aerosols and are transformed by oxidation reactions near the aerosol surface by gas-phase oxidants such as hydroxyl (OH) radicals. To gain better insights into how the structure of an organic molecule, particularly in the presence of hydroxyl groups, controls the heterogeneous reaction mechanisms of oxygenated organic compounds, this paper investigates the OH-radical initiated oxidation of aqueous tartaric acid (C 4H 6O 6) droplets using an aerosol flow tube reactor. The molecular composition of the aerosols before and after reaction is characterized by a soft atmospheric pressure ionization source (Direct Analysis in Real Time)more » coupled with a high-resolution mass spectrometer. The aerosol mass spectra reveal that four major reaction products are formed: a single C 4 functionalization product (C 4H 4O 6) and three C 3 fragmentation products (C 3H 4O 4, C 3H 2O 4, and C 3H 2O 5). The C 4 functionalization product does not appear to originate from peroxy radical self-reactions but instead forms via an α-hydroxylperoxy radical produced by a hydrogen atom abstraction by OH at the tertiary carbon site. The proximity of a hydroxyl group to peroxy group enhances the unimolecular HO 2 elimination from the α-hydroxylperoxy intermediate. This alcohol-to-ketone conversion yields 2-hydroxy-3-oxosuccinic acid (C 4H 4O 6), the major reaction product. While in general, C–C bond scission reactions are expected to dominate the chemistry of organic compounds with high average carbon oxidation states (OS C), our results show that molecular structure can play a larger role in the heterogeneous transformation of tartaric acid (OS C = 1.5). Finally, these results are also compared with two structurally related dicarboxylic acids (succinic acid and 2,3-dimethylsuccinic acid) to elucidate how the identity and location of functional groups (methyl and hydroxyl groups) alter heterogeneous reaction mechanisms.« less

The effects of energy drink in combination with alcohol on performance and subjective awareness.

PubMed

Alford, Chris; Hamilton-Morris, Jennifer; Verster, Joris C

2012-08-01

This study investigated the coadministration of an energy drink with alcohol to study the effects on subjective intoxication and objective performance. This study aims to evaluate the objective and subjective effects of alcohol versus placebo at two alcohol doses, alone and in combination with an energy drink, in a balanced order, placebo-controlled, double-blind design. Two groups of ten healthy volunteers, mean (SD) age of 24 (6.5), participated in the study. One group consumed energy drink containing 80 mg of caffeine and the other consumed a placebo drink, with both receiving two alcohol doses (0.046 and 0.087% breathalyser alcohol concentration). Tests included breath alcohol assessment, objective measures of performance (reaction time, word memory and Stroop task) and subjective visual analogue mood scales. Participants showed significantly impaired reaction time and memory after alcohol compared to the no alcohol condition and had poorer memory after the higher alcohol dose. Stroop performance was improved with the energy drink plus alcohol combination compared to the placebo drink plus alcohol combination. Participants felt significant subjective dose-related impairment after alcohol compared to no alcohol. Neither breath alcohol concentration nor the subjective measures showed a significant difference between the energy drink and the placebo energy drink when combined with alcohol. Subjective effects reflected awareness of alcohol intoxication and sensitivity to increasing alcohol dose. There were no overall significant group differences for subjective measures between energy drink and placebo groups in the presence of alcohol and no evidence that the energy drink masked the subjective effects of alcohol at either dose.

Oxygenates vs. synthesis gas

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

Kamil Klier; Richard G. Herman; Alessandra Beretta

1999-04-01

Methanol synthesis from H{sub 2}/CO has been carried out at 7.6 MPa over zirconia-supported copper catalysts. Catalysts with nominal compositions of 10/90 mol% and 30/70 mol% Cu/ZrO{sub 2} were used in this study. Additionally, a 3 mol% cesium-doped 10/90 catalyst was prepared to study the effect of doping with heavy alkali, and this promoter greatly increased the methanol productivity. The effects of CO{sub 2} addition, water injection, reaction temperature, and H{sub 2}/C0 ratio have been investigated. Both CO{sub 2} addition to the synthesis gas and cesium doping of the catalyst promoted methanol synthesis, while inhibiting the synthesis of dimethyl ether.more » Injection of water, however, was found to slightly suppress methanol and dimethyl ether formation while being converted to CO{sub 2} via the water gas shift reaction over these catalysts. There was no clear correlation between copper surface area and catalyst activity. Surface analysis of the tested samples revealed that copper tended to migrate and enrich the catalyst surface. The concept of employing a double-bed reactor with a pronounced temperature gradient to enhance higher alcohol synthesis was explored, and it was found that utilization of a Cs-promoted Cu/ZnO/Cr{sub 2}O{sub 3} catalyst as a first lower temperature bed and a Cs-promoted ZnO/Cr{sub 2}O{sub 3} catalyst as a second high-temperature bed significantly promoted the productivity of 2-methyl-1-propanol (isobutanol) from H{sub 2}/CO synthesis gas mixtures. While the conversion of CO to C{sub 2+} oxygenates over the double-bed configuration was comparable to that observed over the single Cu-based catalyst, major changes in the product distribution occurred by the coupling to the zinc chromite catalyst; that is, the productivity of the C{sub 1}-C{sub 3} alcohols decreased dramatically, and 2-methyl branched alcohols were selectively formed. The desirable methanol/2-methyl oxygenate molar ratios close to 1 were obtained in the present double-bed system that provides the feedstock for the synthesis of high octane and high cetane ethers, where the isobutanol productivity was as high as 139 g/kg cat/hr. Higher alcohol synthesis has been investigated over a Cs/Cu/ZnO/Cr{sub 2}O{sub 3} catalyst at temperatures higher (up to 703K) than those previously utilized, and no sintering of the catalyst was observed during the short-term testing. However, the higher reaction temperatures led to lower CO conversion levels and lower yield of alcohols, especially of methanol, because of equilibrium limitations. With the double catalyst bed configuration, the effect of pressure in the range of 7.6--12.4 MPa on catalyst activity and selectivity was studied. The upper bed was composed of the copper-based catalyst at 598K, and the lower bed consisted of a copper-free Cs-ZnO/Cr{sub 2}O{sub 3} catalyst at a high temperature of 678K. High pressure was found to increase CO conversion to oxygenated products, although the increase in isobutanol productivity did not keep pace with that of methanol. It was also shown that the Cs/Cu/ZnO/Cr{sub 2}O{sub 3} catalyst could be utilized to advantage as the second-bed catalyst at 613--643K instead of the previously used copper-free Cs-ZnO/ Cr{sub 2}O{sub 3} catalyst at higher temperature, With double Cs/Cu/ZnO/Cr{sub 2}O{sub 3} catalysts, high space time yields of up to 202 g/kg cat/hr, with high selectivity to isobutanol, were achieved.« less

Problematic Internet Use, Excessive Alcohol Consumption, Their Comorbidity and Cardiovascular and Cortisol Reactions to Acute Psychological Stress in a Student Population

PubMed Central

Bibbey, Adam; Phillips, Anna C.; Ginty, Annie T.; Carroll, Douglas

2015-01-01

Background and Aims Problematic Internet use and excessive alcohol consumption have been associated with a host of maladaptive outcomes. Further, low (blunted) cardiovascular and stress hormone (e.g. cortisol) reactions to acute psychological stress are a feature of individuals with a range of adverse health and behavioural characteristics, including dependencies such as tobacco and alcohol addiction. The present study extended this research by examining whether behavioural dependencies, namely problematic Internet use, excessive alcohol consumption, and their comorbidity would also be associated with blunted stress reactivity. Methods A large sample of university students (N = 2313) were screened using Internet and alcohol dependency questionnaires to select four groups for laboratory testing: comorbid Internet and alcohol dependence (N = 17), Internet dependence (N = 17), alcohol dependence (N = 28), and non-dependent controls (N = 26). Cardiovascular activity and salivary cortisol were measured at rest and in response to a psychological stress protocol comprising of mental arithmetic and public speaking tasks. Results Neither problematic Internet behaviour nor excessive alcohol consumption, either individually or in combination, were associated with blunted cardiovascular or cortisol stress reactions. Discussion It is possible that problematic Internet behaviour and excessive alcohol consumption in a student population were not related to physiological reactivity as they may not reflect ingrained addictions but rather an impulse control disorder and binging tendency. Conclusions The present results serve to indicate some of the limits of the developing hypothesis that blunted stress reactivity is a peripheral marker of the central motivational dysregulation in the brain underpinning a wide range of health and behavioural problems. PMID:26014670

Process for producing biodiesel, lubricants, and fuel and lubricant additives in a critical fluid medium

DOEpatents

Ginosar, Daniel M.; Fox, Robert V.

2005-05-03

A process for producing alkyl esters useful in biofuels and lubricants by transesterifying glyceride- or esterifying free fatty acid-containing substances in a single critical phase medium is disclosed. The critical phase medium provides increased reaction rates, decreases the loss of catalyst or catalyst activity and improves the overall yield of desired product. The process involves the steps of dissolving an input glyceride- or free fatty acid-containing substance with an alcohol or water into a critical fluid medium; reacting the glyceride- or free fatty acid-containing substance with the alcohol or water input over either a solid or liquid acidic or basic catalyst and sequentially separating the products from each other and from the critical fluid medium, which critical fluid medium can then be recycled back in the process. The process significantly reduces the cost of producing additives or alternatives to automotive fuels and lubricants utilizing inexpensive glyceride- or free fatty acid-containing substances, such as animal fats, vegetable oils, rendered fats, and restaurant grease.

Conversion of cellulosic materials to sugar

DOEpatents

Wilke, Charles R.; Mitra, Gautam

1976-08-03

A process for the production of sugar, mainly glucose, by the enzymatic degradation of cellulosic materials, particularly cellulosic wastes, which comprises hydrolyzing the cellulosic material in the presence of cellulase enzyme to produce a sugar solution and recovering from the hydrolysis products a major proportion of the cellulase enzyme used in the hydrolysis reaction for re-use. At least a portion of the required makeup cellulase enzyme is produced in a two-stage operation wherein, in the first stage, a portion of the output sugar solution is utilized to grow a cellulase-secreting microorganism, and, in the second stage, cellulase enzyme formation is induced in the microorganism-containing culture medium by the addition of an appropriate inducer, such as a cellulosic material. Cellulase enzyme is precipitated from the culture liquid by the addition of an organic solvent material, such as a low molecular weight alkyl ketone or alcohol, and the cellulase precipitate is then fed to the hydrolysis reaction.

Alcoholysis: A Promising Technology for Conversion of Lignocellulose and Platform Chemicals.

PubMed

Zhu, Shanhui; Guo, Jing; Wang, Xun; Wang, Jianguo; Fan, Weibin

2017-06-22

In the catalytic conversion of lignocellulose to valuable products, the first entry point is to break down these biopolymers to sugar units or aromatic monomers, which is conventionally achieved by hydrolysis in water medium. Recent years have seen tremendous progress in the alcoholysis process, which has remarkable advantages, such as the avoidance of treating waste water, suppression of humins or chars, and enhancement of reaction rate and product yield. Advances have been focused on the alcoholysis of cellulose, hemicellulose, and lignin to alkyl glucosides, xylosides, and aromatic monomers, respectively. Alcoholysis of the platform molecule furfuryl alcohol (FAL) to alkyl levulinate (AL) and integrated alcoholysis of cellulose and furfural into AL are also summarized. This Minireview highlights the comparisons between alcoholysis and hydrolysis, the reaction mechanism of alcoholysis, and future challenges for industrial applications. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Continuous Flow Aerobic Alcohol Oxidation Reactions Using a Heterogeneous Ru(OH)x/Al2O3 Catalyst

PubMed Central

2015-01-01

Ru(OH)x/Al2O3 is among the more versatile catalysts for aerobic alcohol oxidation and dehydrogenation of nitrogen heterocycles. Here, we describe the translation of batch reactions to a continuous-flow method that enables high steady-state conversion and single-pass yields in the oxidation of benzylic alcohols and dehydrogenation of indoline. A dilute source of O2 (8% in N2) was used to ensure that the reaction mixture, which employs toluene as the solvent, is nonflammable throughout the process. A packed bed reactor was operated isothermally in an up-flow orientation, allowing good liquid–solid contact. Deactivation of the catalyst during the reaction was modeled empirically, and this model was used to achieve high conversion and yield during extended operation in the aerobic oxidation of 2-thiophene methanol (99+% continuous yield over 72 h). PMID:25620869

Protective Action of Se-Supplement Against Acute Alcoholism Is Regulated by Selenoprotein P (SelP) in the Liver.

PubMed

Zhang, Zhenbiao; Guo, Yingfang; Qiu, Changwei; Deng, Ganzhen; Guo, Mengyao

2017-02-01

Acute alcoholism is a major cause of cirrhosis and liver failure around the world. Selenium (Se) is an essential micronutrient promoting liver health in humans and animals. Selenoprotein P (SelP) is a glycoprotein secreted within the liver, which interacts with cytokines and the growth factor pathway to provide protection for hepatic cells. The present study was conducted to confirm the effect and mechanism of Se and SelP action in livers affected by acute alcoholism. In this study, a mouse model of acute alcoholism, as well as a hepatocyte model, was successfully established. The Se content of the liver was detected by atomic fluorescence spectrophotometry. The expression of messenger RNA (mRNA) was analyzed by quantitative polymerase chain reaction (qPCR). The protein expression of inflammatory factors was detected by ELISA. The other proteins were analyzed by western blotting. The results showed that pathological damage to the liver was gradually weakened by Se-supplementation, which was evaluated by hematoxylin and eosin (H&E) and TUNEL staining. Se-supplementation inhibited expression of pro-inflammatory factors TNF-α and IL-1β and promoted production of anti-inflammatory cytokine IL-10 in the liver with acute alcoholism. Se-supplementation also prevented the apoptosis of hepatocytes by suppressing the cleavage of caspases-9, 3, 6, 7, and poly(ADP-ribose) polymerase (PARP). Through correlational analysis, it was determined that the effects of Se-supplement were closely related to SelP expression, inflammatory cytokines, and apoptosis molecule production. The sienna of SelP further confirmed the protective action of Se-supplementation on the liver and that the mechanism of SelP involves the regulation of inflammatory cytokines and apoptosis molecules in acute alcoholism. These findings provide information regarding a new potential target for the treatment of acute alcoholism.

Proton mediated control of biochemical reactions with bioelectronic pH modulation

NASA Astrophysics Data System (ADS)

Deng, Yingxin; Miyake, Takeo; Keene, Scott; Josberger, Erik E.; Rolandi, Marco

2016-04-01

In Nature, protons (H+) can mediate metabolic process through enzymatic reactions. Examples include glucose oxidation with glucose dehydrogenase to regulate blood glucose level, alcohol dissolution into carboxylic acid through alcohol dehydrogenase, and voltage-regulated H+ channels activating bioluminescence in firefly and jellyfish. Artificial devices that control H+ currents and H+ concentration (pH) are able to actively influence biochemical processes. Here, we demonstrate a biotransducer that monitors and actively regulates pH-responsive enzymatic reactions by monitoring and controlling the flow of H+ between PdHx contacts and solution. The present transducer records bistable pH modulation from an “enzymatic flip-flop” circuit that comprises glucose dehydrogenase and alcohol dehydrogenase. The transducer also controls bioluminescence from firefly luciferase by affecting solution pH.

Dispersion Polymerization of Polystyrene Particles Using Alcohol as Reaction Medium

NASA Astrophysics Data System (ADS)

Cho, Young-Sang; Shin, Cheol Hwan; Han, Sujin

2016-02-01

In this study, monodisperse polystyrene nanospheres were prepared by dispersion polymerization using alcohol as reaction medium to prepare colloidal clusters of the latex beads. Polyvinylpyrrolidone (PVP) and 2-(methacryloyloxy)ethyltrimethylammonium chloride (MTC) were used as dispersion stabilizer and comonomer, respectively. The particle size could be controlled by adjusting the reactant compositions such as the amount of stabilizer, comonomer, and water in the reactant mixture. The size and monodispersity of the polymeric particles could be also controlled by changing the reaction medium with different alcohols other than ethanol or adjusting the polymerization temperature. The synthesized particles could be self-organized inside water-in-oil emulsion droplets by evaporation-driven self-assembly to produce colloidal clusters of the polymeric nanospheres.

Reaction of H rad with H 2O 2 as observed by optical absorption of perhydroxyl radicals or aliphatic alcohol radicals and of rad OH with H 2O 2. A pulse radiolysis study

NASA Astrophysics Data System (ADS)

Alam, M. S.; Kelm, M.; Rao, B. S. M.; Janata, E.

2004-12-01

Two new procedures were employed for studying the reaction of hydrogen atoms with hydrogen peroxide. The absorption in the UV-range was observed either for an acidic aqueous solution containing only hydrogen peroxide or for a similar solution but also containing an aliphatic alcohol. From the increase in absorption of various alcohol radicals, a rate constant of 3.5×10 7 dm 3 mol -1 s -1 was determined. In addition, the rate constant for the reaction of hydroxyl radicals with hydrogen peroxide was determined to be 3.0×10 7 dm 3 mol -1 s -1.

X chromosome inactivation in women with alcoholism.

PubMed

Manzardo, Ann M; Henkhaus, Rebecca; Hidaka, Brandon; Penick, Elizabeth C; Poje, Albert B; Butler, Merlin G

2012-08-01

All female mammals with 2 X chromosomes balance gene expression with males having only 1 X by inactivating one of their X chromosomes (X chromosome inactivation [XCI]). Analysis of XCI in females offers the opportunity to investigate both X-linked genetic factors and early embryonic development that may contribute to alcoholism. Increases in the prevalence of skewing of XCI in women with alcoholism could implicate biological risk factors. The pattern of XCI was examined in DNA isolated in blood from 44 adult women meeting DSM-IV criteria for an alcohol use disorder and 45 control women with no known history of alcohol abuse or dependence. XCI status was determined by analyzing digested and undigested polymerase chain reaction (PCR) products of the polymorphic androgen receptor (AR) gene located on the X chromosome. Subjects were categorized into 3 groups based upon the degree of XCI skewness: random (50:50 to 64:36%), moderately skewed (65:35 to 80:20%), and highly skewed (>80:20%). XCI status from informative women with alcoholism was found to be random in 59% (n = 26), moderately skewed in 27% (n = 12), or highly skewed in 14% (n = 6). Control subjects showed 60, 29, and 11%, respectively. The distribution of skewed XCI observed among women with alcoholism did not differ statistically from that of control subjects (χ(2) test = 0.14, 2 df, p = 0.93). Our data did not support an increase in XCI skewness among women with alcoholism or implicate early developmental events associated with embryonic cell loss or unequal (nonrandom) expression of X-linked gene(s) or defects in alcoholism among women. Copyright © 2012 by the Research Society on Alcoholism.

27 CFR 19.386 - Alcohol content and fill.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 27 Alcohol, Tobacco Products and Firearms 1 2010-04-01 2010-04-01 false Alcohol content and fill. 19.386 Section 19.386 Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO TAX AND TRADE BUREAU... Manufacture of Articles Bottling, Packaging, and Removal of Products § 19.386 Alcohol content and fill. (a...

Rules for biocatalyst and reaction engineering to implement effective, NAD(P)H-dependent, whole cell bioreductions

PubMed Central

Kratzer, Regina; Woodley, John M.; Nidetzky, Bernd

2016-01-01

Access to chiral alcohols of high optical purity is today frequently provided by the enzymatic reduction of precursor ketones. However, bioreductions are complicated by the need for reducing equivalents in the form of NAD(P)H. The high price and molecular weight of NAD(P)H necessitate in situ recycling of catalytic quantities, which is mostly accomplished by enzymatic oxidation of a cheap co-substrate. The coupled oxidoreduction can be either performed by free enzymes in solution or by whole cells. Reductase selection, the decision between cell-free and whole cell reduction system, coenzyme recycling mode and reaction conditions represent design options that strongly affect bioreduction efficiency. In this paper, each option was critically scrutinized and decision rules formulated based on well-described literature examples. The development chain was visualized as a decision-tree that can be used to identify the most promising route towards the production of a specific chiral alcohol. General methods, applications and bottlenecks in the set-up are presented and key experiments required to “test” for decision-making attributes are defined. The reduction of o-chloroacetophenone to (S)-1-(2-chlorophenyl)ethanol was used as one example to demonstrate all the development steps. Detailed analysis of reported large scale bioreductions identified product isolation as a major bottleneck in process design. PMID:26343336

Fragrance allergy could be missed without patch testing with 26 individual fragrance allergens.

PubMed

Vejanurug, Patnapa; Tresukosol, Poohglin; Sajjachareonpong, Praneet; Puangpet, Pailin

2016-04-01

In 2003, the EU Cosmetics Directive stated that 26 fragrance substances must be listed on the cosmetic product ingredient labels. Not all of these 26 fragrance substances are detected by the usual screening markers comprising fragrance mix I, fragrance mix II, and Myroxylon pereirae. To evaluate the usefulness of testing with the 26 individual fragrance substances in addition to the standard fragrance screening markers. Three hundred and twelve consecutive patients were patch tested with our baseline series and the 26 specific fragrance substances required to be declared on cosmetic product ingredient labels in accordance with the EU Cosmetics Directive. Positive reactions to at least either one of the 26 individual fragrance substances or the usual fragrance screening markers were seen in 84 of 312 patients (26.9%). Fifteen of these 84 patients (17.8%) reacted negatively to the fragrance screening markers. The most common individual fragrance allergens were cinnamyl alcohol (11.2%), cinnamal (9%), and hydroxycitronellal (3.8%). Sixty-two of 312 patients (19.8%) had at least one positive reaction to the fragrance screening markers. Additional patch testing with the 26 individual fragrance allergens, or with the commonest fragrance allergens identified within these 26, should be performed to optimize the detection of fragrance allergy. Cinnamyl alcohol and cinnamal are important fragrance allergens in Thailand. © 2016 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

Tandem Cu-catalyzed ketenimine formation and intramolecular nucleophile capture: Synthesis of 1,2-dihydro-2-iminoquinolines from 1-(o-acetamidophenyl)propargyl alcohols

PubMed Central

Kant, Ruchir

2014-01-01

Summary The copper-catalyzed ketenimine formation reaction of 1-(o-acetamidophenyl)propargyl alcohols with various sulfonyl azides is found to undergo a concomitant intramolecular nucleophile attack to generate 1,2-dihydro-2-iminoquinolines after aromatization (via elimination of acetyl and hydroxy groups) and tautomerization. The reaction produces 4-substituted and 3,4-unsubstituted title compounds in moderate to good yields under mild reaction conditions. PMID:24991276

[Comparative assessment of Cladophora, Spirogyra and Oedogonium biomass for the production of fatty acid methyl esters].

PubMed

Haq, I; Muhammad, A; Hameed, U

2014-01-01

The use of alternative fuels for the mitigation of ecological impacts by use of diesel has been focus of intensive research. In the present work, algal oils extracted from cultivated biomass of Cladophora sp., Spirogyra sp. and Oedogonium sp. were evaluated for the lipase-mediated synthesis of fatty acid monoalkyl esters (FAME, biodiesel). To optimize the transesterification of these oils, different parameters such as the alkyl group donor, reaction temperature, stirring time and oil to alcohol ratio were investigated. Four different alcohols i.e. methanol, ethanol, n-propanol and n-butanol were tested as alkyl group donor for the biosynthesis FAME and methanol was found to be the best. Similarly, temperature 50 C and stirring time of 6 h were optimized for the transesterification of oils with methanol. The maximum biodiesel conversions from Cladophora (75.0%), Spirogyra (87.5%) and Oedogonium (92.0%) were obtained when oil to alcohol ratio was 1 : 8.

27 CFR 18.52 - Production of high-proof concentrate.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 27 Alcohol, Tobacco Products and Firearms 1 2013-04-01 2013-04-01 false Production of high-proof concentrate. 18.52 Section 18.52 Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO TAX AND TRADE BUREAU, DEPARTMENT OF THE TREASURY ALCOHOL PRODUCTION OF VOLATILE FRUIT-FLAVOR CONCENTRATE Operations...

27 CFR 18.52 - Production of high-proof concentrate.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 27 Alcohol, Tobacco Products and Firearms 1 2014-04-01 2014-04-01 false Production of high-proof concentrate. 18.52 Section 18.52 Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO TAX AND TRADE BUREAU, DEPARTMENT OF THE TREASURY ALCOHOL PRODUCTION OF VOLATILE FRUIT-FLAVOR CONCENTRATE Operations...

Carbene-catalysed reductive coupling of nitrobenzyl bromides and activated ketones or imines via single-electron-transfer process

NASA Astrophysics Data System (ADS)

Li, Bao-Sheng; Wang, Yuhuang; Proctor, Rupert S. J.; Zhang, Yuexia; Webster, Richard D.; Yang, Song; Song, Baoan; Chi, Yonggui Robin

2016-09-01

Benzyl bromides and related molecules are among the most common substrates in organic synthesis. They are typically used as electrophiles in nucleophilic substitution reactions. These molecules can also be activated via single-electron-transfer (SET) process for radical reactions. Representative recent progress includes α-carbon benzylation of ketones and aldehydes via photoredox catalysis. Here we disclose the generation of (nitro)benzyl radicals via N-heterocyclic carbene (NHC) catalysis under reductive conditions. The radical intermediates generated via NHC catalysis undergo formal 1,2-addition with ketones to eventually afford tertiary alcohol products. The overall process constitutes a formal polarity-inversion of benzyl bromide, allowing a direct coupling of two initially electrophilic carbons. Our study provides a new carbene-catalysed reaction mode that should enable unconventional transformation of (nitro)benzyl bromides under mild organocatalytic conditions.

Catalytic Synthesis of Oxygenates: Mechanisms, Catalysts and Controlling Characteristics

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

Klier, Kamil; Herman, Richard G

2005-11-30

This research focused on catalytic synthesis of unsymmetrical ethers as a part of a larger program involving oxygenated products in general, including alcohols, ethers, esters, carboxylic acids and their derivatives that link together environmentally compliant fuels, monomers, and high-value chemicals. The catalysts studied here were solid acids possessing strong Brnsted acid functionalities. The design of these catalysts involved anchoring the acid groups onto inorganic oxides, e.g. surface-grafted acid groups on zirconia, and a new class of mesoporous solid acids, i.e. propylsulfonic acid-derivatized SBA-15. The former catalysts consisted of a high surface concentration of sulfate groups on stable zirconia catalysts. Themore » latter catalyst consists of high surface area, large pore propylsulfonic acid-derivatized silicas, specifically SBA-15. In both cases, the catalyst design and synthesis yielded high concentrations of acid sites in close proximity to one another. These materials have been well-characterization in terms of physical and chemical properties, as well as in regard to surface and bulk characteristics. Both types of catalysts were shown to exhibit high catalytic performance with respect to both activity and selectivity for the bifunctional coupling of alcohols to form ethers, which proceeds via an efficient SN2 reaction mechanism on the proximal acid sites. This commonality of the dual-site SN2 reaction mechanism over acid catalysts provides for maximum reaction rates and control of selectivity by reaction conditions, i.e. pressure, temperature, and reactant concentrations. This research provides the scientific groundwork for synthesis of ethers for energy applications. The synthesized environmentally acceptable ethers, in part derived from natural gas via alcohol intermediates, exhibit high cetane properties, e.g. methylisobutylether with cetane No. of 53 and dimethylether with cetane No. of 55-60, or high octane properties, e.g. diisopropylether with blending octane No. of 105, and can replace aromatics in liquid fuels.« less

Chronic Alcohol Ingestion Delays T Cell Activation and Effector Function in Sepsis.

PubMed

Margoles, Lindsay M; Mittal, Rohit; Klingensmith, Nathan J; Lyons, John D; Liang, Zhe; Serbanescu, Mara A; Wagener, Maylene E; Coopersmith, Craig M; Ford, Mandy L

2016-01-01

Sepsis is the leading cause of death in intensive care units in the US, and it is known that chronic alcohol use is associated with higher incidence of sepsis, longer ICU stays, and higher mortality from sepsis. Both sepsis and chronic alcohol use are associated with immune deficits such as decreased lymphocyte numbers, impaired innate immunity, delayed-type hypersensitivity reactions, and susceptibility to infections; however, understanding of specific pathways of interaction or synergy between these two states of immune dysregulation is lacking. This study therefore sought to elucidate mechanisms underlying the immune dysregulation observed during sepsis in the setting of chronic alcohol exposure. Using a murine model of chronic ethanol ingestion followed by sepsis induction via cecal ligation and puncture, we determined that while CD4+ and CD8+ T cells isolated from alcohol fed mice eventually expressed the same cellular activation markers (CD44, CD69, and CD43) and effector molecules (IFN-γ, TNF) as their water fed counterparts, there was an overall delay in the acquisition of these phenotypes. This early lag in T cell activation was associated with significantly reduced IL-2 production at a later timepoint in both the CD4+ and CD8+ T cell compartments in alcohol sepsis, as well as with a reduced accumulation of CD8dim activated effectors. Taken together, these data suggest that delayed T cell activation may result in qualitative differences in the immune response to sepsis in the setting of chronic alcohol ingestion.

Determining the thickness of aliphatic alcohol monolayers covalently attached to silicon oxide surfaces using angle-resolved X-ray photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Lee, Austin W. H.; Kim, Dongho; Gates, Byron D.

2018-04-01

The thickness of alcohol based monolayers on silicon oxide surfaces were investigated using angle-resolved X-ray photoelectron spectroscopy (ARXPS). Advantages of using alcohols as building blocks for the formation of monolayers include their widespread availability, ease of handling, and stability against side reactions. Recent progress in microwave assisted reactions demonstrated the ease of forming uniform monolayers with alcohol based reagents. The studies shown herein provide a detailed investigation of the thickness of monolayers prepared from a series of aliphatic alcohols of different chain lengths. Monolayers of 1-butanol, 1-hexanol, 1-octanol, 1-decanol, and 1-dodecanol were each successfully formed through microwave assisted reactions and characterized by ARXPS techniques. The thickness of these monolayers consistently increased by ∼1.0 Å for every additional methylene (CH2) within the hydrocarbon chain of the reagents. Tilt angles of the molecules covalently attached to silicon oxide surfaces were estimated to be ∼35° for each type of reagent. These results were consistent with the observations reported for thiol based or silane based monolayers on either gold or silicon oxide surfaces, respectively. The results of this study also suggest that the alcohol based monolayers are uniform at a molecular level.

Exposure to alcohol advertisements and teenage alcohol-related problems.

PubMed

Grenard, Jerry L; Dent, Clyde W; Stacy, Alan W

2013-02-01

This study used prospective data to test the hypothesis that exposure to alcohol advertising contributes to an increase in underage drinking and that an increase in underage drinking then leads to problems associated with drinking alcohol. A total of 3890 students were surveyed once per year across 4 years from the 7th through the 10th grades. Assessments included several measures of exposure to alcohol advertising, alcohol use, problems related to alcohol use, and a range of covariates, such as age, drinking by peers, drinking by close adults, playing sports, general TV watching, acculturation, parents' jobs, and parents' education. Structural equation modeling of alcohol consumption showed that exposure to alcohol ads and/or liking of those ads in seventh grade were predictive of the latent growth factors for alcohol use (past 30 days and past 6 months) after controlling for covariates. In addition, there was a significant total effect for boys and a significant mediated effect for girls of exposure to alcohol ads and liking of those ads in 7th grade through latent growth factors for alcohol use on alcohol-related problems in 10th grade. Younger adolescents appear to be susceptible to the persuasive messages contained in alcohol commercials broadcast on TV, which sometimes results in a positive affective reaction to the ads. Alcohol ad exposure and the affective reaction to those ads influence some youth to drink more and experience drinking-related problems later in adolescence.

Exposure to Alcohol Advertisements and Teenage Alcohol-Related Problems

PubMed Central

Dent, Clyde W.; Stacy, Alan W.

2013-01-01

OBJECTIVE: This study used prospective data to test the hypothesis that exposure to alcohol advertising contributes to an increase in underage drinking and that an increase in underage drinking then leads to problems associated with drinking alcohol. METHODS: A total of 3890 students were surveyed once per year across 4 years from the 7th through the 10th grades. Assessments included several measures of exposure to alcohol advertising, alcohol use, problems related to alcohol use, and a range of covariates, such as age, drinking by peers, drinking by close adults, playing sports, general TV watching, acculturation, parents’ jobs, and parents’ education. RESULTS: Structural equation modeling of alcohol consumption showed that exposure to alcohol ads and/or liking of those ads in seventh grade were predictive of the latent growth factors for alcohol use (past 30 days and past 6 months) after controlling for covariates. In addition, there was a significant total effect for boys and a significant mediated effect for girls of exposure to alcohol ads and liking of those ads in 7th grade through latent growth factors for alcohol use on alcohol-related problems in 10th grade. CONCLUSIONS: Younger adolescents appear to be susceptible to the persuasive messages contained in alcohol commercials broadcast on TV, which sometimes results in a positive affective reaction to the ads. Alcohol ad exposure and the affective reaction to those ads influence some youth to drink more and experience drinking-related problems later in adolescence. PMID:23359585

Reaction of gas phase OH with unsaturated self-assembled monolayers and relevance to atmospheric organic oxidations.

PubMed

Moussa, Samar G; Finlayson-Pitts, Barbara J

2010-08-28

The kinetics and mechanisms of the reaction of gas phase OH radicals with organics on surfaces are of fundamental chemical interest, as well as relevant to understanding the degradation of organics on tropospheric surfaces or when they are components of airborne particles. We report here studies of the oxidation of a terminal alkene self-assembled monolayer (7-octenyltrichlorosilane, C8= SAM) on a germanium attenuated total reflectance crystal by OH radicals at a concentration of 2.1 x 10(5) cm(-3) at 1 atm total pressure and 298 K in air. Loss of the reactant SAM and the formation of surface products were followed in real time using infrared spectroscopy. From the rate of loss of the C=C bond, a reaction probability within experimental error of unity was derived. The products formed on the surface include organic nitrates and carbonyl compounds, with yields of 10 +/- 4% and < or = 7 +/- 4%, respectively, and there is evidence for the formation of organic products with C-O bonds such as alcohols, ethers and/or alkyl peroxides and possibly peroxynitrates. The yield of organic nitrates relative to carbonyl compounds is higher than expected based on analogous gas phase mechanisms, suggesting that the branching ratio for the RO(2) + NO reaction is shifted to favor the formation of organic nitrates when the reaction occurs on a surface. Water uptake onto the surface was only slightly enhanced upon oxidation, suggesting that oxidation per se cannot be taken as a predictor of increased hydrophilicity of atmospheric organics. These experiments indicate that the mechanisms for the surface reactions are different from gas phase reactions, but the OH oxidation of surface species will still be a significant contributor to determining their lifetimes in air.

Response inhibition toward alcohol-related cues using an alcohol go/no-go task in problem and non-problem drinkers.

PubMed

Kreusch, Fanny; Vilenne, Aurélie; Quertemont, Etienne

2013-10-01

Previous results suggested that alcohol abusers and alcohol dependent patients show cognitive biases in the treatment of alcohol-related cues, especially approach and inhibition deficit biases. Response inhibition was often tested using the go/no-go task in which the participants had to respond as quickly as possible to a class of stimuli (go stimuli) while refraining from responding to another class of stimuli (no-go stimuli). Previous studies assessing specific response inhibition deficits in the process of alcohol-related cues obtained conflicting results. The aims of the present study were to clarify response inhibition for alcohol cues in problem and non-problem drinkers, male and female and to test the effect of alcohol brand logos. Thirty-six non-problem drinker and thirty-five problem drinker undergraduate students completed a modified alcohol go/no-go task using alcohol and neutral object pictures, with or without brand logos, as stimuli. An additional control experiment was carried out to check whether participants' awareness that the study tested their response to alcohol might have biased the results. All participants, whether problem or non-problem drinkers, showed significantly shorter mean reaction times when alcohol pictures are used as go stimuli and significantly higher percentages of commission errors (false alarms) when alcohol pictures are used as no-go stimuli. Identical effects were obtained in the control experiment when participants were unaware that the study focused on alcohol. Shorter reaction times to alcohol-related cues were observed in problem drinkers relative to non-problem drinkers but only in the experimental condition with no brand logos on alcohol pictures. The addition of alcohol brand logos further reduced reaction times in light drinkers, thereby masking group differences. There was a tendency for female problem drinkers to show higher rates of false alarms for alcohol no-go stimuli, although this effect was only very close to statistical significance. All participants exhibited a cognitive bias in the treatment of alcohol cues that might be related to the positive emotional value of such alcohol-related cues. Stronger cognitive biases in the treatment of alcohol cues were observed in problem drinkers, although differences between problem and non-problem drinkers were relatively small-scale and required specific experimental parameters to be uncovered. In particular, the presence of alcohol brand logos on visual alcohol cues was an important experimental parameter that significantly affected behavioral responses to such stimuli. Copyright © 2013 Elsevier Ltd. All rights reserved.

"New" Compounds from Old Plastics: Recycling PET Plastics via Depolymerization. An Activity for the Undergraduate Organic Lab

NASA Astrophysics Data System (ADS)

Kaufman, Don; Wright, Geoff; Kroemer, Ryan; Engel, Josh

1999-11-01

This paper describes work done to develop a meaningful undergraduate organic lab activity that illustrates chemistry of the real world while utilizing reactions typically included in the organic lecture and lab. We show how a common plastic can be converted into several compounds using ester hydrolysis and SN2 reactions. Contributing to the critical shortage of landfill space faced by many communities is the large quantity of plastic refuse. Thus, there is a real need to recycle plastic products. One way to recycle plastics such as polyethyleneterephthalate (PET), the polyester from which numerous consumer products such as 2-liter soda bottles are made, is to depolymerize them and then to use the resulting monomers to produce new products. PET is industrially depolymerized via an acid-catalyzed transesterification reaction conducted under conditions of high temperature and pressure that are not feasible in the undergraduate lab. Despite literature reports that PET is remarkably resistant to hydrolysis, we found that PET can be readily hydrolyzed by refluxing with potassium hydroxide or potassium tert-butoxide in amyl alcohol to give terephthalic acid in high yield. It is then possible to readily synthesize terephthalate diesters via SN2 reactions of ammonium terephthalate salts with alkyl halides. Fischer esterification can also be used to prepare the diesters, but yields are significantly lower.

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

PubMed

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

2009-01-01

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

Method of cross-linking polyvinyl alcohol and other water soluble resins

NASA Technical Reports Server (NTRS)

Phillipp, W. H.; May, C. E.; Hsu, L. C.; Sheibley, D. W. (Inventor)

1980-01-01

A self supporting sheet structure comprising a water soluble, noncrosslinked polymer such as polyvinyl alcohol which is capable of being crosslinked by reaction with hydrogen atom radicals and hydroxyl molecule radicals is contacted with an aqueous solution having a pH of less than 8 and containing a dissolved salt in an amount sufficient to prevent substantial dissolution of the noncrosslinked polymer in the aqueous solution. The aqueous solution is then irradiated with ionizing radiation to form hydrogen atom radicals and hydroxyl molecule radicals and the irradiation is continued for a time sufficient to effect crosslinking of the water soluble polymer to produce a water insoluble polymer sheet structure. The method has particular application in the production of battery separators and electrode envelopes for alkaline batteries.

Reactive Precipitation of Anhydrous Alkali Sulfide Nanocrystals with Concomitant Abatement of Hydrogen Sulfide and Cogeneration of Hydrogen.

PubMed

Li, Xuemin; Zhao, Yangzhi; Brennan, Alice; McCeig, Miranda; Wolden, Colin A; Yang, Yongan

2017-07-21

Anhydrous alkali sulfide (M 2 S, M=Li or Na) nanocrystals (NCs) are important materials central to the development of next generation cathodes and solid-state electrolytes for advanced batteries, but not commercially available at present. This work reports an innovative method to directly synthesize M 2 S NCs through alcohol-mediated reactions between alkali metals and hydrogen sulfide (H 2 S). In the first step, the alkali metal is complexed with alcohol in solution, forming metal alkoxide (ROM) and releasing hydrogen (H 2 ). Next, H 2 S is bubbled through the ROM solution, where both chemicals are completely consumed to produce phase-pure M 2 S NC precipitates and regenerate alcohol that can be recycled. The M 2 S NCs morphology may be tuned through the choice of the alcohol and solvent. Both synthetic steps are thermodynamically favorable (ΔG m o <-100 kJ mol -1 ), proceeding rapidly to completion at ambient temperature with almost 100 % atom efficiency. The net result, H 2 S+2 m→M 2 S+H 2 , makes good use of a hazardous chemical (H 2 S) and delivers two value-added products that naturally phase separate for easy recovery. This scalable approach provides an energy-efficient and environmentally benign solution to the production of nanostructured materials required in emerging battery technologies. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

7 CFR Appendix C to Subpart E of... - Guidelines for Loan Guarantees for Alcohol Fuel Production Facilities

Code of Federal Regulations, 2014 CFR

2014-01-01

... beverage purposes, is manufactured from biomass. (2) The alcohol production facility includes all... Production Facilities C Appendix C to Subpart E of Part 1980 Agriculture Regulations of the Department of...—Guidelines for Loan Guarantees for Alcohol Fuel Production Facilities (1) Alcohol production facility. An...

7 CFR Appendix C to Subpart E of... - Guidelines for Loan Guarantees for Alcohol Fuel Production Facilities

Code of Federal Regulations, 2013 CFR

2013-01-01

... beverage purposes, is manufactured from biomass. (2) The alcohol production facility includes all... Production Facilities C Appendix C to Subpart E of Part 1980 Agriculture Regulations of the Department of...—Guidelines for Loan Guarantees for Alcohol Fuel Production Facilities (1) Alcohol production facility. An...

Tandem catalysis by palladium nanoclusters encapsulated in metal–organic frameworks

DOE PAGES

Li, Xinle; Guo, Zhiyong; Xiao, Chaoxian; ...

2014-08-25

A bifunctional Zr-MOF catalyst containing palladium nanoclusters (NCs) has been developed. The formation of Pd NCs was confirmed by transmission electron microscopy (TEM) and extended X-ray absorption fine structure (EXAFS). Combining the oxidation activity of Pd NCs and the acetalization activity of the Lewis acid sites in UiO-66-NH 2, this catalyst (Pd@UiO-66-NH 2) exhibits excellent catalytic activity and selectivity in a one-pot tandem oxidation-acetalization reaction. This catalyst shows 99.9% selectivity to benzaldehyde ethylene acetal in the tandem reaction of benzyl alcohol and ethylene glycol at 99.9% conversion of benzyl alcohol. We also examined various substituted benzyl alcohols and found thatmore » alcohols with electron-donating groups showed better conversion and selectivity compared to those with electron-withdrawing groups. As a result, we further proved that there was no leaching of active catalytic species during the reaction and the catalyst can be recycled at least five times without significant deactivation.« less

Emission of volatile organic compounds from silage: Compounds, sources, and implications

NASA Astrophysics Data System (ADS)

Hafner, Sasha D.; Howard, Cody; Muck, Richard E.; Franco, Roberta B.; Montes, Felipe; Green, Peter G.; Mitloehner, Frank; Trabue, Steven L.; Rotz, C. Alan

2013-10-01

Silage, fermented cattle feed, has recently been identified as a significant source of volatile organic compounds (VOCs) to the atmosphere. A small number of studies have measured VOC emission from silage, but not enough is known about the processes involved to accurately quantify emission rates and identify practices that could reduce emissions. Through a literature review, we have focused on identifying the most important compounds emitted from corn silage (the most common type of silage in the US) and the sources of these compounds by quantifying their production and emission potential in silage and describing production pathways. We reviewed measurements of VOC emission from silage and assessed the importance of individual silage VOCs through a quantitative analysis of VOC concentrations within silage. Measurements of VOC emission from silage and VOCs present within silage indicated that alcohols generally make the largest contribution to emission from corn silage, in terms of mass emitted and potential ozone formation. Ethanol is the dominant alcohol in corn silage; excluding acids, it makes up more than half of the mean mass of VOCs present. Acids, primarily acetic acid, may be important when emission is high and all VOCs are nearly depleted by emission. Aldehydes and esters, which are more volatile than acids and alcohols, are important when exposure is short, limiting emission of more abundant but less volatile compounds. Variability in silage VOC concentrations is very high; for most alcohols and acids, tolerance intervals indicate that 25% of silages have concentrations a factor of two away from median values, and possibly much further. This observation suggests that management practices can significantly influence VOC concentrations. Variability also makes prediction of emissions difficult. The most important acids, alcohols, and aldehydes present in silage are probably produced by bacteria (and, in the case of ethanol, yeasts) during fermentation and storage of silage. Aldehydes may also be produced aerobically by spoilage microorganisms through the oxidation of alcohols. Abiotic reactions may be important for production of methanol and esters. Although silage additives appear to affect VOC production in individual studies, bacterial inoculants have not shown a consistent effect on ethanol, and effects on other VOCs have not been studied. Production of acetic acid is understood, and production could be minimized, but a decrease could lead to an increase in other, more volatile and more reactive, VOCs. Chemical additives designed for controlling yeasts and undesirable bacteria show promise for reducing ethanol production in corn silage. More work is needed to understand silage VOC production and emission from silage, including: additional measurements of VOC concentrations or production in silage of all types, and an exploration of the causes of variability; accurate on-farm measurements of VOC emission, including an assessment of the importance of individual ensiling stages and practices that could reduce emission of existing VOCs; and work on understanding the sources of silage VOCs and possible approaches for reducing production.

Coupling and reactions of 5- hydroxyconiferyl alcohol in lignin formation

Treesearch

Thomas Elder; Laura Berstis; Gregg T. Beckham; Michael F. Crowley

2016-01-01

The catechol alcohols, caffeyl and 5-hydroxyconiferyl alcohol, may be incorporated into lignin either naturally or through genetic manipulation. Due to the presence of o-OH groups, these compounds form benzodioxanes, a departure from the interunit connections found in lignins derived from the cinnamyl alcohols. In nature, lignins composed of caffeyl and 5-...

Effects of low doses of alcohol on driving-related skills : a review of the evidence

DOT National Transportation Integrated Search

1988-07-01

A large scale review of the experimental literature on alcohol effects on skills related to driving, considered 177 citations and explored the evidence of alcohol effects on reaction time, tracking, concentrated attention, divided attention performan...

Applications of Iridium-Catalyzed Asymmetric Allylic Substitution Reactions in Target-Oriented Synthesis.

PubMed

Qu, Jianping; Helmchen, Günter

2017-10-17

Metal catalyzed allylic substitution is a cornerstone of organometallic and synthetic chemistry. Enantioselective versions have been developed with catalysts derived from transition metals, most notably molybdenum, nickel, ruthenium, rhodium, iridium, palladium, and copper. The palladium- and the iridium-catalyzed versions have turned out to be particularly versatile in organic synthesis because of the very broad scope of the nucleophile and great functional group compatibility. Assets of the iridium-catalyzed reaction are the formation of branched, chiral products from simple monosubstituted allylic substrates, high degrees of regio- and enantioselectivity, and use of modular, readily available chiral ligands. The possibility to use carbon, nitrogen, oxygen, and sulfur compounds as well as fluoride as nucleophiles allows a wide range of chiral building blocks to be prepared. Our Account begins with the presentation of fundamental reaction schemes and chiral ligands. We will focus our discussion on reactions promoted by phosphoramidite ligands, though numerous chiral ligands have been employed. The subsequent section presents a brief overview of reaction mechanism and experimental conditions. Two versions of the iridium-catalyzed allylic substitution have emerged. In type 1 reactions (introduced in 1997), linear allylic esters are commonly used as substrates under basic reaction conditions. In type 2 reactions (introduced in 2007), environmentally friendly branched allylic alcohols can be reacted under acidic conditions; occasionally, derivatives of allylic alcohols have also been applied. A unique feature of the type 2 reactions is that highly electrophilic allylic intermediates can be brought to reaction with weakly activated alkenes. The subsequent text is ordered according to the strategies followed to transform allylic substitution products to desired targets, most of which are natural products or drugs. Syntheses starting with an intermolecular allylic substitution are discussed first. Some fairly complex targets, for example, the potent nitric oxide inhibitor (-)-nyasol and the drug (-)-protrifenbute, have been synthesized via less than five steps from simple starting materials. Most targets discussed are cyclic compounds. Intermolecular allylic substitution with subsequent ring closing metathesis is a powerful strategy for their synthesis. Highlights are stereodivergent syntheses of Δ 9 -tetrahydrocannabinols (THC), wherein iridium- and organocatalysis are combined (dual catalysis). The combination of allylic alkylation with a Diels-Alder reaction was utilized to synthesize the ketide apiosporic acid and the drug fesoterodine (Toviaz). Sequential allylic amination, hydroboration and Suzuki-Miyaura coupling generates enones suitable for conjugate addition reactions; this strategy was employed in syntheses of a variety of alkaloids, for example, the poison frog alkaloid (+)-cis-195A (pumiliotoxin C). Intramolecular substitutions offer interesting possibilities to build up stereochemical complexity via short synthetic routes. For example, in diastereoselective cyclizations of chiral compounds, substrate control can be overruled by catalyst control in order to generate cis- and trans-isomers selectively from a given precursor. This approach was used to prepare a variety of piperidine and pyrrolidine alkaloids. Finally, complex polycyclic structures, including the structurally unusual indolosesquiterpenoid mycoleptodiscin A, have been generated diastereo- and enantioselectively from olefins by polyene cyclizations and from electron-rich arenes, such as indoles, in dearomatization reactions.

27 CFR 26.37 - Alcohol and Tobacco Tax and Trade Bureau Officers.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 27 Alcohol, Tobacco Products and Firearms 1 2014-04-01 2014-04-01 false Alcohol and Tobacco Tax and Trade Bureau Officers. 26.37 Section 26.37 Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO TAX AND TRADE BUREAU, DEPARTMENT OF THE TREASURY ALCOHOL LIQUORS AND ARTICLES FROM PUERTO RICO AND THE VIRGIN ISLANDS Products Coming Into the...

Elucidation of Active Sites for the Reaction of Ethanol on TiO 2 /Au(111)

DOE PAGES

Boyle, David T.; Wilke, Jeremy A.; Palomino, Robert M.; ...

2017-03-17

Obtaining a molecular-level understanding of the reaction of alcohols with heterogeneous model catalysts is critical for improving industrial catalytic processes, such as the production of H 2 from alcohols. Gold has been shown to be an excellent oxidation catalyst once oxygen is added to it. The use of reducible oxides provides a source of oxygen on Au(111) for the reaction of ethanol, which is easily regenerated in the presence of an oxygen background. In this work, ethanol operates as a probe molecule to investigate the role of Au(111), TiO 2 nanoparticles, and TiO 2/Au interfacial surface sites on the catalyticmore » properties of TiO 2/Au(111). Ultrahigh vacuum temperature-programmed desorption (TPD) studies with ethanol/Au(111) elucidate previously unreported adsorption sites for ethanol. Ethanol molecularly adsorbs to Au terrace sites, step edges, and undercoordinated kink sites with adsorption energies of -51.7, -55.8, and -65.1 kJ/mol, respectively. In a TPD coverage study of ethanol on TiO 2/Au(111) indicates ethanol undergoes dissociative adsorption to form H*(a) and CH 3CH 2O*(a) on the inverse model catalyst surface. The desorption temperature of low coverages of ethanol from TiO2/Au(111) (Tdes ≈ 235 K) is at an intermediate temperature between the desorption temperatures from bulk Au(111) and TiO 2(110), indicating both Au and TiO 2 play a role in the adsorption of ethanol. Both low-temperature adsorption and high-temperature reactions are studied and indicate that ethanol-derived products such as acetaldehyde and ethylene desorb from TiO 2/Au(111) at ~500 K. Here, we report the identification of catalytically active sites on TiO 2/Au(111) as interfacial sites between the oxide and Au(111) surface through the use of temperature-programmed desorption and infrared reflection absorption spectroscopy.« less

Elucidation of Active Sites for the Reaction of Ethanol on TiO 2 /Au(111)

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

Boyle, David T.; Wilke, Jeremy A.; Palomino, Robert M.

Obtaining a molecular-level understanding of the reaction of alcohols with heterogeneous model catalysts is critical for improving industrial catalytic processes, such as the production of H 2 from alcohols. Gold has been shown to be an excellent oxidation catalyst once oxygen is added to it. The use of reducible oxides provides a source of oxygen on Au(111) for the reaction of ethanol, which is easily regenerated in the presence of an oxygen background. In this work, ethanol operates as a probe molecule to investigate the role of Au(111), TiO 2 nanoparticles, and TiO 2/Au interfacial surface sites on the catalyticmore » properties of TiO 2/Au(111). Ultrahigh vacuum temperature-programmed desorption (TPD) studies with ethanol/Au(111) elucidate previously unreported adsorption sites for ethanol. Ethanol molecularly adsorbs to Au terrace sites, step edges, and undercoordinated kink sites with adsorption energies of -51.7, -55.8, and -65.1 kJ/mol, respectively. In a TPD coverage study of ethanol on TiO 2/Au(111) indicates ethanol undergoes dissociative adsorption to form H*(a) and CH 3CH 2O*(a) on the inverse model catalyst surface. The desorption temperature of low coverages of ethanol from TiO2/Au(111) (Tdes ≈ 235 K) is at an intermediate temperature between the desorption temperatures from bulk Au(111) and TiO 2(110), indicating both Au and TiO 2 play a role in the adsorption of ethanol. Both low-temperature adsorption and high-temperature reactions are studied and indicate that ethanol-derived products such as acetaldehyde and ethylene desorb from TiO 2/Au(111) at ~500 K. Here, we report the identification of catalytically active sites on TiO 2/Au(111) as interfacial sites between the oxide and Au(111) surface through the use of temperature-programmed desorption and infrared reflection absorption spectroscopy.« less

Alcohols as hydrogen-donor solvents for treatment of coal

DOEpatents

Ross, David S.; Blessing, James E.

1981-01-01

A method for the hydroconversion of coal by solvent treatment at elevated temperatures and pressure wherein an alcohol having an .alpha.-hydrogen atom, particularly a secondary alcohol such as isopropanol, is utilized as a hydrogen donor solvent. In a particular embodiment, a base capable of providing a catalytically effective amount of the corresponding alcoholate anion under the solvent treatment conditions is added to catalyze the alcohol-coal reaction.

The effects of alcohol expectancy and intake on slot machine gambling behavior.

PubMed

Sagoe, Dominic; Mentzoni, Rune Aune; Leino, Tony; Molde, Helge; Haga, Sondre; Gjernes, Mikjel Fredericson; Hanss, Daniel; Pallesen, Ståle

2017-06-01

Background and aims Although alcohol intake and gambling often co-occur in related venues, there is conflicting evidence regarding the effects of alcohol expectancy and intake on gambling behavior. We therefore conducted an experimental investigation of the effects of alcohol expectancy and intake on slot machine gambling behavior. Methods Participants were 184 (females = 94) individuals [age range: 18-40 (mean = 21.9) years] randomized to four independent conditions differing in information/expectancy about beverage (told they received either alcohol or placebo) and beverage intake [actually ingesting low (target blood alcohol concentration [BAC] < 0.40 mg/L) vs. moderate (target BAC > 0.40 mg/L; ≈0.80 mg/L) amounts of alcohol]. All participants completed self-report questionnaires assessing demographic variables, subjective intoxication, alcohol effects (stimulant and sedative), and gambling factors (behavior and problems, evaluation, and beliefs). Participants also gambled on a simulated slot machine. Results A significant main effect of beverage intake on subjective intoxication and alcohol effects was detected as expected. No significant main or interaction effects were detected for number of gambling sessions, bet size and variation, remaining credits at termination, reaction time, and game evaluation. Conclusion Alcohol expectancy and intake do not affect gambling persistence, dissipation of funds, reaction time, or gambling enjoyment.

Creatine Supplementation Does Not Prevent the Development of Alcoholic Steatosis.

PubMed

Ganesan, Murali; Feng, Dan; Barton, Ryan W; Thomes, Paul G; McVicker, Benita L; Tuma, Dean J; Osna, Natalia A; Kharbanda, Kusum K

2016-11-01

Alcohol-induced reduction in the hepatocellular S-adenosylmethionine (SAM):S-adenosylhomocysteine (SAH) ratio impairs the activities of many SAM-dependent methyltransferases. These impairments ultimately lead to the generation of several hallmark features of alcoholic liver injury including steatosis. Guanidinoacetate methyltransferase (GAMT) is an important enzyme that catalyzes the final reaction in the creatine biosynthetic process. The liver is a major site for creatine synthesis which places a substantial methylation burden on this organ as GAMT-mediated reactions consume as much as 40% of all the SAM-derived methyl groups. We hypothesized that dietary creatine supplementation could potentially spare SAM, preserve the hepatocellular SAM:SAH ratio, and thereby prevent the development of alcoholic steatosis and other consequences of impaired methylation reactions. For these studies, male Wistar rats were pair-fed the Lieber-DeCarli control or ethanol (EtOH) diet with or without 1% creatine supplementation. At the end of 4 to 5 weeks of feeding, relevant biochemical and histological analyses were performed. We observed that creatine supplementation neither prevented alcoholic steatosis nor attenuated the alcohol-induced impairments in proteasome activity. The lower hepatocellular SAM:SAH ratio seen in the EtOH-fed rats was also not normalized or SAM levels spared when these rats were fed the creatine-supplemented EtOH diet. However, a >10-fold increased level of creatine was observed in the liver, serum, and hearts of rats fed the creatine-supplemented diets. Overall, dietary creatine supplementation did not prevent alcoholic liver injury despite its known efficacy in preventing high-fat-diet-induced steatosis. Betaine, a promethylating agent that maintains the hepatocellular SAM:SAH, still remains our best option for treating alcoholic steatosis. Copyright © 2016 by the Research Society on Alcoholism.

Proton mediated control of biochemical reactions with bioelectronic pH modulation

DOE PAGES

Deng, Yingxin; Miyake, Takeo; Keene, Scott; ...

2016-04-07

In Nature, protons (H +) can mediate metabolic process through enzymatic reactions. Examples include glucose oxidation with glucose dehydrogenase to regulate blood glucose level, alcohol dissolution into carboxylic acid through alcohol dehydrogenase, and voltage-regulated H + channels activating bioluminescence in firefly and jellyfish. Artificial devices that control H + currents and H + concentration (pH) are able to actively influence biochemical processes. Here, we demonstrate a biotransducer that monitors and actively regulates pH-responsive enzymatic reactions by monitoring and controlling the flow of H + between PdH x contacts and solution. The present transducer records bistable pH modulation from an “enzymaticmore » flip-flop” circuit that comprises glucose dehydrogenase and alcohol dehydrogenase. Furthermore, the transducer also controls bioluminescence from firefly luciferase by affecting solution pH.« less

Proton mediated control of biochemical reactions with bioelectronic pH modulation

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

Deng, Yingxin; Miyake, Takeo; Keene, Scott

In Nature, protons (H +) can mediate metabolic process through enzymatic reactions. Examples include glucose oxidation with glucose dehydrogenase to regulate blood glucose level, alcohol dissolution into carboxylic acid through alcohol dehydrogenase, and voltage-regulated H + channels activating bioluminescence in firefly and jellyfish. Artificial devices that control H + currents and H + concentration (pH) are able to actively influence biochemical processes. Here, we demonstrate a biotransducer that monitors and actively regulates pH-responsive enzymatic reactions by monitoring and controlling the flow of H + between PdH x contacts and solution. The present transducer records bistable pH modulation from an “enzymaticmore » flip-flop” circuit that comprises glucose dehydrogenase and alcohol dehydrogenase. Furthermore, the transducer also controls bioluminescence from firefly luciferase by affecting solution pH.« less

Syngas Conversion to Hydrocarbon Fuels through Mixed Alcohol Intermediates

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

Dagle, Robert A.; Lebarbier, Vanessa M.; Albrecht, Karl O.

2013-05-13

Synthesis gas (syngas) can be used to synthesize a variety of fuels and chemicals. Domestic transportation and military operational interests have driven continued focus on domestic syngas-based fuels production. Liquid transportation fuels may be made from syngas via four basic processes: 1) higher alcohols, 2) Fischer-Tropsch (FT), 3) methanol-to-gasoline (MTG), and 4) methanol-to-olefins (MTO) and olefins-to-gasoline/distillate (MOGD). Compared to FT and higher alcohols, MTG and MTO-MOGD have received less attention in recent years. Due to the high capital cost of these synthetic fuel plants, the production cost of the finished fuel cannot compete with petroleum-derived fuel. Pacific Northwest National Laboratorymore » has recently evaluated one way to potentially reduce capital cost and overall production cost for MTG by combining the methanol and MTG syntheses in a single reactor. The concept consists of mixing the conventional MTG catalyst (i.e. HZSM-5) with an alcohol synthesis catalyst. It was found that a methanol synthesis catalyst, stable at high temperature (i.e. Pd/ZnO/Al2O3) [1], when mixed with ZSM-5, was active for syngas conversion. Relatively high syngas conversion can be achieved as the equilibrium-driven conversion limitations for methanol and dimethyl ether are removed as they are intermediates to the final hydrocarbon product. However, selectivity control was difficult to achieve as formation of undesirable durene and light hydrocarbons was problematic [2]. The objective of the present study was thus to evaluate other potential composite catalyst systems and optimize the reactions conditions for the conversion of syngas to hydrocarbon fuels, through the use of mixed alcohol intermediates. Mixed alcohols are of interest as they have recently been reported to produce higher yields of gasoline compared to methanol [3]. 1. Lebarbier, V.M., Dagle, R.A., Kovarik, L., Lizarazo-Adarme, J.A., King, D.L., Palo, D.R., Catalyst Science & Technology, 2012, 2, 2116-2127. 2. Zhu, Y., Jones, S.B., Biddy, M.J., Dagle, R.A., Palo, D.P., Bioresource Technology, 2012, 117, 341-351. 3. Gujar, A.C., Guda, V.K., Nolan, M., Yan W., Toghiani, H., White, M.G., Applied Catalysis A: General, 2009, 363, 115-121.« less

ReaxFF Study of the Oxidation of Softwood Lignin in View of Carbon Fiber Production

DOE PAGES

Beste, Ariana

2014-10-06

We investigate the oxidative, thermal conversion of softwood lignin by performing molecular dynamics simulations based on a reactive force field (ReaxFF). The lignin samples are constructed from coniferyl alcohol units, which are connected through linkages that are randomly selected from a natural distribution of linkages in softwood. The goal of this work is to simulate the oxidative stabilization step during carbon fiber production from lignin precursor. We find that at simulation conditions where stabilization reactions occur, the lignin fragments have already undergone extensive degradation. The 5-5 linkage shows the highest reactivity towards cyclization and dehydrogenation.

Cue avoidance training and inhibitory control training for the reduction of alcohol consumption: a comparison of effectiveness and investigation of their mechanisms of action.

PubMed

Di Lemma, Lisa C G; Field, Matt

2017-08-01

Both cue avoidance training (CAT) and inhibitory control training (ICT) reduce alcohol consumption in the laboratory. However, these interventions have never been directly compared and their mechanisms of action are poorly understood. We compared the effects of both types of training on alcohol consumption and investigated if they led to theoretically predicted changes in alcohol avoidance (CAT) or alcohol inhibition (ICT) associations and changes in evaluation of alcohol cues. Heavy drinking young adults (N = 120) were randomly assigned to one of four groups: (1) CAT (repeatedly pushing alcohol cues away with a joystick), (2) sham (control) CAT; (3) ICT (repeatedly inhibiting behaviour in response to alcohol cues); or (4) sham (control) ICT. Changes in reaction times and automatic evaluations of alcohol cues were assessed before and after training using assessment versions of tasks used in training and the implicit association test (IAT), respectively. Finally, participants completed a bogus taste test as a measure of ad libitum alcohol consumption. Compared to sham conditions, CAT and ICT both led to reduced alcohol consumption although there was no difference between the two. Neither intervention affected performance on the IAT, and changes in reaction time did not suggest the formation of robust alcohol avoidance (CAT) or alcohol inhibition (ICT) associations after training. CAT and ICT yielded equivalent reductions in alcohol consumption in the laboratory. However, these behavioural effects were not accompanied by devaluation of stimuli or the formation of alcohol avoidance or alcohol inhibition associations.

27 CFR 4.36 - Alcoholic content.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 27 Alcohol, Tobacco Products and Firearms 1 2013-04-01 2013-04-01 false Alcoholic content. 4.36 Section 4.36 Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO TAX AND TRADE BUREAU, DEPARTMENT OF THE TREASURY ALCOHOL LABELING AND ADVERTISING OF WINE Labeling Requirements for Wine § 4.36 Alcoholic content. (a) Alcoholic content shall be...

27 CFR 4.36 - Alcoholic content.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 27 Alcohol, Tobacco Products and Firearms 1 2014-04-01 2014-04-01 false Alcoholic content. 4.36 Section 4.36 Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO TAX AND TRADE BUREAU, DEPARTMENT OF THE TREASURY ALCOHOL LABELING AND ADVERTISING OF WINE Labeling Requirements for Wine § 4.36 Alcoholic content. (a) Alcoholic content shall be...

27 CFR 7.71 - Alcoholic content.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 27 Alcohol, Tobacco Products and Firearms 1 2014-04-01 2014-04-01 false Alcoholic content. 7.71 Section 7.71 Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO TAX AND TRADE BUREAU, DEPARTMENT OF THE TREASURY ALCOHOL LABELING AND ADVERTISING OF MALT BEVERAGES Interim Regulations for Alcoholic Content Statements § 7.71 Alcoholic content. ...

27 CFR 7.71 - Alcoholic content.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 27 Alcohol, Tobacco Products and Firearms 1 2013-04-01 2013-04-01 false Alcoholic content. 7.71 Section 7.71 Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO TAX AND TRADE BUREAU, DEPARTMENT OF THE TREASURY ALCOHOL LABELING AND ADVERTISING OF MALT BEVERAGES Interim Regulations for Alcoholic Content Statements § 7.71 Alcoholic content. ...

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

PubMed

Alsafadi, Diya; Alsalman, Safaa; Paradisi, Francesca

2017-11-07

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

Synthesis and characterization of sulfolane-based amino alcohols: A combined experimental and computational study

NASA Astrophysics Data System (ADS)

Palchykov, Vitalii A.; Zarovnaya, Iryna S.; Tretiakov, Serhii V.; Reshetnyak, Alyona V.; Omelchenko, Iryna V.; Shishkin, Oleg V.; Okovytyy, Sergiy I.

2018-04-01

Aminolysis of 3,4-epoxysulfolane in aqueous media leads to a very complex mixture of products with unresolved stereochemistry. Herein, we report a detailed theoretical and experimental mechanistic investigation of this reaction along with extensive spectroscopic characterization of the resulting amino alcohols, using 1D and 2D NMR techniques (1H, 13C, NOE, NOESY, COSY, HSQC, HMBC) as well as XRD analysis. In addition to simple amines such as ammonia and benzylamine, our study also employed the more sterically hindered endo-bicyclo[2.2.1]hept-5-en-2-ylmethanamine. The mechanism of the aminolysis of 3,4-epoxysulfolane by aqueous ammonia was studied in more detail using quantum chemical calculations at the M06-2X/6-31++G** level of theory. The computational results led us to conclude that the most probable way of initial epoxide transformation is base-catalyzed rearrangement to a corresponding allylic alcohol. Subsequent formation of vicinal amino alcohols and diols proceeds via addition of ammonia or hydroxy-anions to activated double Cdbnd C bond with some preference of a cis-attack. Detailed analytical data obtained in the course of our work will be useful for the stereochemical identification of new sulfolane derivatives.

Effects of alcohol intoxication on parenting behavior in interactions with child confederates exhibiting normal or deviant behaviors.

PubMed

Lang, A R; Pelham, W E; Atkeson, B M; Murphy, D A

1999-06-01

Experimental analogue methods were used to study how acute alcohol intoxication in parents influences their perceptions of and reactions to child behaviors, as well as their strategies for management of those behaviors. All participating parents had a grade school-aged son, but in half the cases this target child had a diagnosed externalizing disorder, whereas for the remaining half neither the target son nor any other offspring of the parents evidenced any psychopathology. Equal numbers of married fathers, married mothers, and single mothers from each of these groups received either alcoholic or nonalcoholic beverages prior to videotaped interactions with male child confederates who, depending on condition, enacted behaviors characteristic of either normal boys or boys with attention deficit hyperactivity/conduct/oppositional defiant disorders (ADHD/CD/ODD). Results indicated that intoxicated parents rated their ADHD/CD/ODD child partners as less deviant than did sober parents. Alcohol intoxication caused all participant groups to exhibit less attention and productive work and more commands, indulgences, and off-task talk in the interactions. Implications for better understanding of the role of psychosocial factors in the correlation between adult drinking problems and childhood behavior disorders are discussed.

Three-Component Reactions of Diazoesters, Aldehydes, and Imines Using a Dual Catalytic System Consisting of a Rhodium(II) Complex and a Lewis Acid.

PubMed

Toda, Yasunori; Kaku, Wakatake; Tsuruoka, Makoto; Shinogaki, Sho; Abe, Tomoka; Kamiya, Hideaki; Kikuchi, Ayaka; Itoh, Kennosuke; Suga, Hiroyuki

2018-05-04

A dual catalytic system, dirhodium tetrapivalate/ytterbium(III) triflate, enables the three-component reactions of α-alkyl-α-diazoesters, aromatic aldehydes, and N-benzylidenebenzylamine derivatives to afford the corresponding β-amino alcohols in good yields after hydrolysis of the oxazolidine cycloadducts, whereas no β-amino alcohols are obtained in the absence of ytterbium(III) triflate. A similar dual catalytic system, dirhodium tetraacetate/ytterbium(III) triflate, is found to be effective in accelerating the reactions of α-aryl-α-diazoesters in high yields. Furthermore, the reactions using dimethyl diazomalonate are described.

27 CFR 25.53 - Submissions of samples of fermented products.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 27 Alcohol, Tobacco Products and Firearms 1 2014-04-01 2014-04-01 false Submissions of samples of fermented products. 25.53 Section 25.53 Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO TAX AND TRADE BUREAU, DEPARTMENT OF THE TREASURY ALCOHOL BEER Miscellaneous Provisions Samples § 25.53...

27 CFR 19.121 - Change in production procedure.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 27 Alcohol, Tobacco Products and Firearms 1 2013-04-01 2013-04-01 false Change in production procedure. 19.121 Section 19.121 Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO TAX AND TRADE BUREAU, DEPARTMENT OF THE TREASURY ALCOHOL DISTILLED SPIRITS PLANTS Changes to Registrations and Permits...

27 CFR 19.121 - Change in production procedure.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 27 Alcohol, Tobacco Products and Firearms 1 2014-04-01 2014-04-01 false Change in production procedure. 19.121 Section 19.121 Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO TAX AND TRADE BUREAU, DEPARTMENT OF THE TREASURY ALCOHOL DISTILLED SPIRITS PLANTS Changes to Registrations and Permits...

Development and Pilot Trial of an Intervention to Reduce Disclosure Recipients Negative Social Reactions and Victims Psychological Distress and Problem Drinking

ClinicalTrials.gov

2018-04-06

Social Skills; Self-Criticism; Post-traumatic Stress Disorder; Depression; Alcohol Abuse; Drinking, College; Alcohol Drinking; Alcohol; Harmful Use; Social Stigma; Social Norms; Social Responsibility; Social Behavior; Empathy; Coping Skills; Coping Behavior

Process for fullerene functionalization

DOEpatents

Cahill, Paul A.; Henderson, Craig C.

1995-01-01

Di-addended and tetra-addended Buckminster fullerenes are synthesized through the use of novel organoborane intermediates. The C.sub.60, C.sub.70, or higher fullerene is reacted with a borane such as BH.sub.3 in a solvent such as toluene to form an organoborane intermediate. Reaction of the organoborane such as hydrolysis with water or alcohol results in the product di-addended and tetra-addended fullerene in up to 30% yields. Dihydrofullerenes and tetrahydrofullerenes are produced by the process of the invention.

Process for fullerene functionalization

DOEpatents

Cahill, P.A.; Henderson, C.C.

1995-12-12

Di-addended and tetra-addended Buckminster fullerenes are synthesized through the use of novel organoborane intermediates. The C{sub 60}, C{sub 70}, or higher fullerene is reacted with a borane such as BH{sub 3} in a solvent such as toluene to form an organoborane intermediate. Reaction of the organoborane such as hydrolysis with water or alcohol results in the product di-addended and tetra-addended fullerene in up to 30% yields. Dihydrofullerenes and tetrahydrofullerenes are produced by the process of the invention. 7 figs.

Acylation of Chiral Alcohols: A Simple Procedure for Chiral GC Analysis.

PubMed

Oromí-Farrús, Mireia; Torres, Mercè; Canela, Ramon

2012-01-01

The use of iodine as a catalyst and either acetic or trifluoroacetic acid as a derivatizing reagent for determining the enantiomeric composition of acyclic and cyclic aliphatic chiral alcohols was investigated. Optimal conditions were selected according to the molar ratio of alcohol to acid, the reaction time, and the reaction temperature. Afterwards, chiral stability of chiral carbons was studied. Although no isomerization was observed when acetic acid was used, partial isomerization was detected with the trifluoroacetic acid. A series of chiral alcohols of a widely varying structural type were then derivatized with acetic acid using the optimal conditions. The resolution of the enantiomeric esters and the free chiral alcohols was measured using a capillary gas chromatograph equipped with a CP Chirasil-DEX CB column. The best resolutions were obtained with 2-pentyl acetates (α = 3.00) and 2-hexyl acetates (α = 1.95). This method provides a very simple and efficient experimental workup procedure for analyzing chiral alcohols by chiral-phase GC.

The production of aromatic alcohols in non-Saccharomyces wine yeast is modulated by nutrient availability.

PubMed

González, Beatriz; Vázquez, Jennifer; Morcillo-Parra, M Ángeles; Mas, Albert; Torija, María Jesús; Beltran, Gemma

2018-09-01

Aromatic alcohols (tryptophol, phenylethanol, tyrosol) positively contribute to organoleptic characteristics of wines, and are also described as bioactive compounds and quorum sensing molecules. These alcohols are produced by yeast during alcoholic fermentation via the Erhlich pathway, although in non-Saccharomyces this production has been poorly studied. We studied how different wine yeast species modulate the synthesis patterns of aromatic alcohol production depending on glucose, nitrogen and aromatic amino acid availability. Nitrogen limitation strongly promoted the production of aromatic alcohols in all strains, whereas low glucose generally inhibited it. Increased aromatic amino acid concentrations stimulated the production of aromatic alcohols in all of the strains and conditions tested. Thus, there was a clear association between the nutrient conditions and production of aromatic alcohols in most of the wine yeast species analysed. Additionally, the synthesis pattern of these alcohols has been evaluated for the first time in Torulaspora delbrueckii, Metschnikowia pulcherrima and Starmellera bacillaris. Copyright © 2018 Elsevier Ltd. All rights reserved.

Free radical generation by non-equilibrium atmospheric pressure plasma in alcohol-water mixtures: an EPR-spin trapping study

NASA Astrophysics Data System (ADS)

Uchiyama, Hidefumi; Ishikawa, Kenji; Zhao, Qing-Li; Andocs, Gabor; Nojima, Nobuyuki; Takeda, Keigo; Krishna, Murali C.; Ishijima, Tatsuo; Matsuya, Yuji; Hori, Masaru; Noguchi, Kyo; Kondo, Takashi

2018-03-01

Free radical species in aqueous solution—various alcohol-water reaction mixtures—by exposure to non-equilibrium cold atmospheric pressure Ar plasma (CAP), were monitored using electron paramagnetic resonance spin-trapping techniques with 3, 5-dibromo-4-nitrosobenzene sulfonate as a water soluble nitroso spin trap. The major radical species were formed by H-abstraction from alcohol molecules due to ·OH radicals. In the ethanol-water mixture ·CH2CH2OH produced by H abstraction from CH3 group of the ethanol and ·CH3 radicals were detected. The latter was due to the decomposition of unstable CH3·CHOH to form the ·CH3 radicals and the stable formaldehyde by C-C bond fission. These intermediates are similar to those observed by reaction with ·OH radicals generation in the H2O2-UV photolysis of the reaction mixtures. The evidence of ·CH3 radical formation in the pyrolytic decomposition of the reaction mixtures by exposure to ultrasound or in methane irradiated with microwave plasma have been reported previously. However, the pyrolytic ·CH3 radicals were not found in both plasma and H2O2-UV photolysis condition. These results suggests that free radicals produced by Ar-CAP are most likely due to the reaction between abundant ·OH radicals and alcohol molecules.

Impulsivity Moderates the Effects of Movie Alcohol Portrayals on Adolescents’ Willingness to Drink

PubMed Central

Gibbons, Frederick X.; Kingsbury, John H.; Wills, Thomas A.; Finneran, Stephanie D.; Cin, Sonya Dal; Gerrard, Meg

2016-01-01

This study examined impulsivity as a moderator of adolescents’ reactions to positive vs. negative portrayals of drinking in American movie clips. Impulsivity, along with willingness and intentions to drink in the future, were assessed in a pretest session. In the experimental sessions, adolescents viewed a series of clips that showed drinking associated with either positive outcomes (e.g., social facilitation) or negative outcomes (fights, arguments). A third group viewed clips with similar positive or negative outcomes, but no alcohol consumption. All participants then responded to an implicit measure of attentional bias regarding alcohol (a dot probe), followed by explicit alcohol measures (self-reports of willingness and intentions to drink). Hypotheses, based on dual-processing theories, were: a) high-impulsive adolescents would respond more favorably than low-impulsive adolescents to the positive clips, but not the negative clips; and b) this difference in reactions to the positive clips would be larger on the willingness than the intention measures. Results supported the hypotheses: Adolescents high in impulsivity reported the highest willingness to drink in the positive-clip condition, but were slightly less willing than others in the negative-clip condition. In addition, results on the dot probe task indicated that reaction times to alcohol words were negatively correlated with changes in alcohol willingness, but not intention; i.e., the faster their response to the alcohol words, the more their willingness increased. The results highlight the utility of a dual-processing perspective on media influence. PMID:27099959

Organic Analysis of Catalytic Fischer-Tropsch Synthesis Products and Ordinary Chondrite Meteorites by Stepwise Pyrolysis-GCMS: Organics in the Early Solar Nebula

NASA Technical Reports Server (NTRS)

Locke, Darren R.; Yazzie, Cyriah A.; Burton, Aaron S.; Niles, Paul B.; Johnson, Natasha M.

2014-01-01

Abiotic generation of complex organic compounds, in the early solar nebula that formed our solar system, is hypothesized by some to occur via Fischer-Tropsch (FT) synthesis. In its simplest form, FT synthesis involves the low temperature (<300degC) catalytic reaction of hydrogen and carbon monoxide gases to form more complex hydrocarbon compounds, primarily n-alkanes, via reactive nano-particulate iron, nickel, or cobalt, for example. Industrially, this type of synthesis has been utilized in the gas-to-liquid process to convert syngas, produced from coal, natural gas, or biomass, into paraffin waxes that can be cracked to produce liquid diesel fuels. In general, the effect of increasing reaction temperature (>300degC) produces FT products that include lesser amounts of n-alkanes and greater alkene, alcohol, and polycyclic aromatic hydrocarbon (PAH) compounds. We have begun to experimentally investigate FT synthesis in the context of abiotic generation of organic compounds in the early solar nebula. It is generally thought that the early solar nebula included abundant hydrogen and carbon monoxide gases and nano-particulate matter such as iron and metal silicates that could have catalyzed the FT reaction. The effect of FT reaction temperature, catalyst type, and experiment duration on the resulting products is being investigated. These solid organic products are analyzed by thermal-stepwise pyrolysis-GCMS and yield the types and distribution of hydrocarbon compounds released as a function of temperature. We show how the FT products vary by reaction temperature, catalyst type, and experimental duration and compare these products to organic compounds found to be indigenous to ordinary chondrite meteorites. We hypothesize that the origin of organics in some chondritic meteorites, that represent an aggregation of materials from the early solar system, may at least in part be from FT synthesis that occurred in the early solar nebula.

Expression Levels of the Yeast Alcohol Acetyltransferase Genes ATF1, Lg-ATF1, and ATF2 Control the Formation of a Broad Range of Volatile Esters

PubMed Central

Verstrepen, Kevin J.; Van Laere, Stijn D. M.; Vanderhaegen, Bart M. P.; Derdelinckx, Guy; Dufour, Jean-Pierre; Pretorius, Isak S.; Winderickx, Joris; Thevelein, Johan M.; Delvaux, Freddy R.

2003-01-01

Volatile aroma-active esters are responsible for the fruity character of fermented alcoholic beverages such as beer and wine. Esters are produced by fermenting yeast cells in an enzyme-catalyzed intracellular reaction. In order to investigate and compare the roles of the known Saccharomyces cerevisiae alcohol acetyltransferases, Atf1p, Atf2p and Lg-Atf1p, in volatile ester production, the respective genes were either deleted or overexpressed in a laboratory strain and a commercial brewing strain. Subsequently, the ester formation of the transformants was monitored by headspace gas chromatography and gas chromatography combined with mass spectroscopy (GC-MS). Analysis of the fermentation products confirmed that the expression levels of ATF1 and ATF2 greatly affect the production of ethyl acetate and isoamyl acetate. GC-MS analysis revealed that Atf1p and Atf2p are also responsible for the formation of a broad range of less volatile esters, such as propyl acetate, isobutyl acetate, pentyl acetate, hexyl acetate, heptyl acetate, octyl acetate, and phenyl ethyl acetate. With respect to the esters analyzed in this study, Atf2p seemed to play only a minor role compared to Atf1p. The atf1Δ atf2Δ double deletion strain did not form any isoamyl acetate, showing that together, Atf1p and Atf2p are responsible for the total cellular isoamyl alcohol acetyltransferase activity. However, the double deletion strain still produced considerable amounts of certain other esters, such as ethyl acetate (50% of the wild-type strain), propyl acetate (50%), and isobutyl acetate (40%), which provides evidence for the existence of additional, as-yet-unknown ester synthases in the yeast proteome. Interestingly, overexpression of different alleles of ATF1 and ATF2 led to different ester production rates, indicating that differences in the aroma profiles of yeast strains may be partially due to mutations in their ATF genes. PMID:12957907

27 CFR 19.392 - Converting denatured alcohol to a different formula.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 27 Alcohol, Tobacco Products and Firearms 1 2011-04-01 2011-04-01 false Converting denatured alcohol to a different formula. 19.392 Section 19.392 Alcohol, Tobacco Products and Firearms ALCOHOL AND... denatured alcohol to a different formula. (a) General. A proprietor may convert specially denatured alcohol...

27 CFR 19.608 - Cases of industrial alcohol.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 27 Alcohol, Tobacco Products and Firearms 1 2010-04-01 2010-04-01 false Cases of industrial alcohol. 19.608 Section 19.608 Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO TAX AND TRADE... Cases of industrial alcohol. (a) Mandatory marks. Each case, including encased containers, of alcohol...

On the Stereoselective Synthesis of (+)-Pinoresinol in Forsythia Suspensa from its Achiral Precursor, Coniferyl Alcohol

NASA Technical Reports Server (NTRS)

Davin, Laurence B.; Bedgar, Diana L.; Katayama, Takeshi; Lewis, Norman G.

1992-01-01

The residue from Forsythia suspensa stems, upon removal of soluble enzymes, has provided the first evidence for a stereoselective coupling enzyme in lignan biosynthesis. This preparation catalyses the preferred formation (ca 65%) of (+)-[8,8'- C-14] pinoresinol from [8-C-14]coniferyl alcohol in the absence of exogenously provided cofactors; addition of H2O2 had little effect on enantiomeric composition. However, when NAD and malate were supplied, the stereoselectivity of the coupling reaction was significantly enhanced and pinoresinol consisting of ca 80% of the (+)-antipode was obtained. Clearly, the insoluble residue contains a specific coupling enzyme which catalyses (+)-pinoresinol formation from coniferyl alcohol. By contrast, when [8- C-14] sinapyl alcohol was employed as substrate, only racemic syringaresinols were formed: this non-stereoselective peroxidase-catalysed coupling reaction presumably accounts for the low levels of (-)-pinoresinol encountered in this system when coniferyl alcohol is used as a substrate.

Hydrogenation of carbon dioxide catalyzed by ruthenium trimethylphosphine complexes: the accelerating effect of certain alcohols and amines.

PubMed

Munshi, Pradip; Main, A Denise; Linehan, John C; Tai, Chih-Cheng; Jessop, Philip G

2002-07-10

A trace amount of alcohol cocatalyst and a stoichiometric amount of base are required during the hydrogenation of CO(2) to formic acid catalyzed by ruthenium trimethylphosphine complexes. Variation of the choice of alcohol and base causes wide variation in the rate of reaction. Acidic, nonbulky alcohols and triflic acid increase the rate of hydrogenation an order of magnitude above that which can be obtained with traditionally used methanol or water. Similarly, use of DBU rather than NEt(3) increases the rate of reaction by an order of magnitude. Turnover frequencies up to 95,000 h(-1) have now been obtained, and even higher rates should be possible using the cocatalyst and amine combinations identified herein. Preliminary in situ NMR spectroscopic observations are described, and the possible roles of the alcohol and base are discussed.

THERMAL DESORPTION MASS SPECTROMETRIC ANALYSIS OF ORGANIC AEROSOL FORMED FROM REACTIONS OF 1-TETRADECENE AND O3 IN THE PRESENCE OF ALCOHOLS AND CARBOXYLIC ACIDS. (R826235)

EPA Science Inventory

The chemistry of secondary organic aerosol formation from reactions of
1-tetradecene and O₃ in dry air in the presence of excess alcohols
and carboxylic acids was investigated in an environmental chamber using a
thermal desorption particle beam mass spec...

Cognitive impairments of alcoholic cirrhotic patients: correlation with endogenous benzodiazepine receptor ligands and increased affinity of platelet receptors.

PubMed Central

Kapczinski, F; Curran, H V; Przemioslo, R; Williams, R; Fluck, E; Fernandes, C; File, S E

1996-01-01

OBJECTIVES--To determine whether differences in cognitive function between alcoholic and non-alcoholic cirrhotic patients relate to differences in endogenous ligands for the benzodiazepine receptor and/or benzodiazepine binding. METHODS--Seventeen grade-I hepatic encephalopathic patients (nine alcoholic, eight non-alcoholic) were compared with 10 matched controls on plasma concentrations of endogenous ligands for the neuronal benzodiazepine receptor, benzodiazepine binding in platelets, and performance on tests of cognitive function. RESULTS--Both groups of patients were impaired on verbal recall and on reaction time tasks compared with controls; alcoholic patients were also impaired on Reitan's trails test and digit cancellation. Four of the 17 patients had detectable concentrations of endogenous benzodiazepine ligands and they were more impaired than other patients on trails and cancellation tests. The groups did not differ in the density of benzodiazepine platelet receptors, but receptor affinity was higher in alcoholic patients than in controls; furthermore, receptor affinity correlated with the time to complete the cancellation task and with reaction time. CONCLUSION--Alcoholic cirrhotic patients may have enhanced concentrations of ligands for neuronal and peripheral benzodiazepine receptors and these may contribute to cognitive impairments in these patients. PMID:8648337

Feeling safe but appearing anxious: Differential effects of alcohol on anxiety and social performance in individuals with social anxiety disorder.

PubMed

Stevens, Stephan; Cooper, Ruth; Bantin, Trisha; Hermann, Christiane; Gerlach, Alexander L

2017-07-01

Social anxiety disorder (SAD) and alcohol use disorders (AUD) co-occur frequently and there is preliminary evidence that alcohol might reduce social anxiety. It is, however, unclear which mechanisms contribute to the anxiety reducing effect, particularly regarding key aspects of social anxiety such as deficits in social performance. We compared self-rated and physiological measures of anxiety as well as self- and observer-rated social performance in a sample of 62 individuals with SAD and 60 nonanxious control participants during a speech task after receiving either alcohol, an alcohol-free placebo drink or orange juice. SAD patients reported more anxiety during the speech task than did control participants. Furthermore, SAD patients underestimated their performance in comparison to observer ratings. Alcohol reduced self-report anxiety only in SAD patients, while observers rated all participants as less competent when intoxicated. Although individuals with SAD experience a reduction in anxiety when drinking alcohol, simultaneous decreases in social performance might contribute to negative reactions from others and consequently increase the risk of further alcohol use to cope with these negative reactions. Copyright © 2017 Elsevier Ltd. All rights reserved.

Chemical reactions in perfume ageing.

PubMed

Blakeway, J M; Frey, M L; Lacroix, S; Salerno, M S

1987-10-01

Summary The interactions between a typical range of perfume materials, alcohol, water, air, elevated temperatures and daylight have been studied. The changes of composition, acidity, peroxide content and the formation of new molecules were followed. The stabilizing effects of UV absorbers, antioxidants and sequestering agents were examined; - the formation of acid reaction products was accelerated by air, temperature, daylight and the presence of natural products; - peroxide formation was accelerated by heat and light and the presence of air; as the acidity increased, the peroxides decomposed; - the acetalization of other aldehydes was accelerated by temperature and daylight and the presence of natural products up to 40% of certain aldehydes may be converted into acetals after 3 months at 37 degrees C; - many stereoisomerizations occur, e.g., transisoeugenol is converted up to 10% into the cis isomer after 3 months at 37 degrees C and 58% in daylight; - evaluation of antioxidants UV absorbers and sequestering agents showed a significant protection against deterioration only by EDTA dipotassium salt; - ethanol was converted into acetaldehyde and its diethylacetal by peroxides present and formed on ageing up to 0.08%. Natural products accelerated this formation; - the reaction between benzoyl peroxide and ethanol was shown to yield up to 63% of acetaldehyde+diethyl acetal whilst di-t-butyl peroxide gave only 23% under the same conditions. These results go some way to explaining odour changes in perfume ageing.

27 CFR 11.38 - Discontinued products.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 27 Alcohol, Tobacco Products and Firearms 1 2010-04-01 2010-04-01 false Discontinued products. 11.38 Section 11.38 Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO TAX AND TRADE BUREAU... products. When a producer or importer discontinues the production or importation of a product, a trade...

Ceria-based model catalysts: fundamental studies on the importance of the metal–ceria interface in CO oxidation, the water–gas shift, CO 2 hydrogenation, and methane and alcohol reforming

DOE PAGES

Rodriguez, José A.; Grinter, David C.; Liu, Zongyuan; ...

2017-02-17

Model metal/ceria and ceria/metal catalysts have been shown to be excellent systems for studying fundamental phenomena linked to the operation of technical catalysts. In the last fifteen years, many combinations of well-defined systems involving different kinds of metals and ceria have been prepared and characterized using the modern techniques of surface science. So far most of the catalytic studies have been centered on a few reactions: CO oxidation, the hydrogenation of CO 2, and the production of hydrogen through the water–gas shift reaction and the reforming of methane or alcohols. By using model catalysts it is been possible to examinemore » in detail correlations between the structural, electronic and catalytic properties of ceria–metal interfaces. In situ techniques (X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, infrared spectroscopy, scanning tunneling microscopy) have been combined to study the morphological changes under reaction conditions and investigate the evolution of active phases involved in the cleavage of C–O, C–H and C–C bonds. Several studies with model ceria catalysts have shown the importance of strong metal–support interactions. Generally, a substantial body of knowledge has been acquired and concepts have been developed for a more rational approach to the design of novel technical catalysts containing ceria.« less

Surface engineering of hierarchical platinum-cobalt nanowires for efficient electrocatalysis

DOE PAGES

Bu, Lingzheng; Guo, Shaojun; Zhang, Xu; ...

2016-06-29

Despite intense research in past decades, the lack of high-performance catalysts for fuel cell reactions remains a challenge in realizing fuel cell technologies for transportation applications. Here we report a facile strategy for synthesizing hierarchical platinum-cobalt nanowires with high-index, platinum-rich facets and ordered intermetallic structure. These structural features enable unprecedented performance for the oxygen reduction and alcohol oxidation reactions. The specific/mass activities of the platinum-cobalt nanowires for oxygen reduction reaction are 39.6/33.7 times higher than commercial Pt/C catalyst, respectively. Density functional theory simulations reveal that the active threefold hollow sites on the platinum-rich high-index facets provide an additional factor inmore » enhancing oxygen reduction reaction activities. The nanowires are stable in the electrochemical conditions and also thermally stable. Furthermore, this work may represent a key step towards scalable production of high performance platinum-based nanowires for applications in catalysis and energy conversion.« less

A glycerol-free process to produce biodiesel by supercritical methyl acetate technology: an optimization study via Response Surface Methodology.

PubMed

Tan, Kok Tat; Lee, Keat Teong; Mohamed, Abdul Rahman

2010-02-01

In this study, fatty acid methyl esters (FAME) have been successfully produced from transesterification reaction between triglycerides and methyl acetate, instead of alcohol. In this non-catalytic supercritical methyl acetate (SCMA) technology, triacetin which is a valuable biodiesel additive is produced as side product rather than glycerol, which has lower commercial value. Besides, the properties of the biodiesel (FAME and triacetin) were found to be superior compared to those produced from conventional catalytic reactions (FAME only). In this study, the effects of various important parameters on the yield of biodiesel were optimized by utilizing Response Surface Methodology (RSM) analysis. The mathematical model developed was found to be adequate and statistically accurate to predict the optimum yield of biodiesel. The optimum conditions were found to be 399 degrees C for reaction temperature, 30 mol/mol of methyl acetate to oil molar ratio and reaction time of 59 min to achieve 97.6% biodiesel yield.