Abstract: Modern yeast living in fleshy fruits rapidly convert sugars into bulk ethanol through pyruvate. Pyruvate loses carbon dioxide to produce acetaldehyde, which is reduced by alcohol dehydrogenase 1 (Adh1) to ethanol, which accumulates. Yeast later consumes the accumulated ethanol, exploiting Adh2, an Adh1 homolog differing by 24 (of 348) amino acids. As many microorganisms cannot grow in ethanol, accumulated ethanol may help yeast defend resources in the fruit1. We report here the resurrection of the last common ancestor2 of Adh1 and Adh2, called AdhA. The kinetic behavior of AdhA suggests that the ancestor was optimized to make (not consume) ethanol. This is consistent with the hypothesis that before the Adh1-Adh2 duplication, yeast did not accumulate ethanol for later consumption but rather used AdhA to recycle NADH generated in the glycolytic pathway. Silent nucleotide dating suggests that the Adh1-Adh2 duplication occurred near the time of duplication of several other proteins involved in the accumulation of ethanol, possibly in the Cretaceous age when fleshy fruits arose. These results help to connect the chemical behavior of these enzymes through systems analysis to a time of global ecosystem change, a small but useful step towards a planetary systems biology.

Abstract: Reaction kinetics studies were conducted for the conversions of ethanol and acetic acid over silica-supported Pt and Pt/Sn catalysts at temperatures from 500 to 600 K. Addition of Sn to Pt catalysts inhibits the decomposition of ethanol to CO, CH4, and C2H6, such that PtSn-based catalysts are active for dehydrogenation of ethanol to acetaldehyde. Furthermore, PtSn-based catalysts are selective for the conversion of acetic acid to ethanol, acetaldehyde, and ethyl acetate, whereas Pt catalysts lead mainly to decomposition products such as CH4 and CO. These results are interpreted using density functional theory (DFT) calculations for various adsorbed species and transition states on Pt(111) and Pt3Sn(111) surfaces. The Pt3Sn alloy slab was selected for DFT studies because results from in situ 119Sn Mossbauer spectroscopy and CO adsorption microcalorimetry of silica-supported Pt/Sn catalysts indicate that Pt−Sn alloy is the major phase present. Accordingly, results from DFT calculations show that transition-...

Abstract: The PtCl2-catalyzed cyclization reaction of o-alkynylphenyl acetals 1 in the presence of 1,5-cyclooctadiene produces 3-(α-alkoxyalkyl)benzofurans 2 in good to high yields. For example, the reaction of acetaldehyde ethyl 2-(1-octynyl)phenyl acetal (1a), acetaldehyde ethyl 2-(cyclohexylethynyl)phenyl acetal (1c), and acetaldehyde ethyl 2-(phenylethynyl)phenyl acetal (1f) in the presence of 2 mol % of platinum(II) chloride and 8 mol % of 1,5-cyclooctadiene in toluene at 30 °C gave the corresponding 2,3-disubstituted benzofurans 2a, 2c, and 2f in 91, 94, and 88% yields, respectively.

Abstract: A new series of Ni-Rh bimetallic catalysts with different Ni and Rh loadings on a high-surface-area CeO2 was developed for the reforming of bio-ethanol at low-temperature (below 450 °C) to produce H2-rich gas for on-site or on-board fuel cell applications. Oxidative steam reforming of ethanol (OSRE) over a Ni-Rh/CeO2 catalyst containing 5 wt% Ni and 1 wt% Rh was found to be more efficient offering about 100% ethanol conversion at 375 °C with high H2 and CO2 selectivity and low CO selectivity compared to the steam reforming of ethanol (SRE) reaction which required a higher temperature of about 450 °C to achieve 100% ethanol conversion. The high temperature SRE reaction favors the formation of large amount of CO, which would make the downsteam CO cleanup more complicated for polymer electrolyte membrane fuel cell (PEMFC). The presence of O2 in the feed gas was found to greatly enhance the conversion of ethanol to produce H2 and CO2 as major products. Increase in Ni content above 5 wt% in the catalyst formulation decreased the H2 selectivity while the selectivity of undesirable CH4 and acetaldehyde increased. The 1 wt% Rh/CeO2 catalyst was twice as active as 10 wt% Ni/CO2 catalyst in terms of ethanol conversion and acetaldehyde selectivity and this indicated that Rh was more effective in C–C bond cleavage than Ni. The reaction was found to proceed through the formation of acetaldehyde intermediate, which subsequently underwent decomposition to produce a mixture of CO and CH4 or reforming with H2O and O2 to produce CO, CO2 and H2. The role of Rh is mainly to cleave the C–C and C–H bonds of ethanol to produce H2 and COx while Ni addition helps converting CO into CO2 and H2 by WGS reaction under the conditions employed.

Abstract: The adsorption and surface reactions of acetaldehyde at 300–673 K on TiO2, CeO2 and Al2O3 were investigated by Fourier transform infrared spectroscopy and mass spectroscopy. Acetaldehyde adsorbs molecularly in two forms on the surfaces: (i) in a less stable H-bridge bonded form and (ii) in a more stable form adsorbed on Lewis sites through one of the oxygen lone pairs. Both forms of molecularly adsorbed acetaldehyde transform into crotonaldehyde (CH3CH–CHCHO) by b-aldolization on the surfaces. The reaction of adsorbed acetaldehyde and crotonaldehyde resulted in the formation of benzene at higher temperature. The formation of crotonaldehyde and benzene depended on the nature and the pre-treatments of the oxides: the amount of crotonaldehyde was higher on H2-pre-treated, while the amount of benzene was higher on O2-pre-treated surfaces. Primarily the more strongly held acetaldehyde underwent dehydrogenation resulting in H2 and acetylene. The formation of ethane was interpreted by hydrogenation of the transitorily formed ethylene and/or by catalytic decomposition of ethanol, which formed from adsorbed ethoxy produced by the surface reduction of acetaldehyde. Acetaldehyde could be oxidized into acetate, the decomposition of which resulted in gas phase methane. No CO and CO2 was detected up to 673 K. # 2005 Elsevier B.V. All rights reserved.

Abstract: Acetaldehyde, a toxic metabolite of ethanol oxidation, is suggested to play a role in the increased risk for gastrointestinal cancers in alcoholics. In the present study, the effect of acetaldehyde...

Abstract: Background: Previously, we created an aldehyde dehydrogenase 2 gene transgenic (Aldh2−/−) mouse as an aldehyde dehydrogenase (ALDH) 2 inactive human model and demonstrated low alcohol preference. In addition, after a free-choice drinking test, no difference in the acetaldehyde level was observed between the Aldh2−/− and wild type (Aldh2+/+) mice. The actual amounts of free-choice drinking were so low that it is uncertain whether these levels are pharmacologically and/or behaviorally relevant in either strain. To elucidate this uncertainty, we compared the ethanol and acetaldehyde concentration in the blood, brain, and liver between the Aldh2−/− and Aldh2+/+ mice after ethanol gavages at the same dose and time. Method: We measured differences in the ethanol and acetaldehyde levels between the Aldh2−/− and Aldh2+/+ mice by headspace gas chromatography-mass spectrometry (GC-MS) after ethanol gavages at the same dose and time. Results: Significantly higher blood acetaldehyde concentrations were found in the Aldh2−/− mice than in the Aldh2+/+ mice 1 hr after the administration of ethanol gavages at doses of 0.5, 1.0, 2.0, and 5.0 g/kg. The blood acetaldehyde concentrations in the two strains were 2.4 vs. 0.5, 17.8 vs. 1.9, 108.3 vs. 4.3, and 247.2 vs. 14.0 (μM), respectively. In contrast, no significant difference was observed in the blood ethanol concentrations between the Aldh2+/+ and Aldh2−/− mice. The aldehyde dehydrogenase 2 enzyme metabolized 94% of the acetaldehyde produced from the ethanol as calculated from the area under the curve (AUC) of acetaldehyde when ethanol was administered at a dose of 5.0 g/kg. Conclusions: These data indicate that mouse ALDH2 is a major enzyme for acetaldehyde metabolism, and the Aldh2−/− mice have significantly high acetaldehyde levels after ethanol gavages.

Abstract: Microcalorimetric and infrared studies of ethanol and acetaldehyde adsorption were carried out on fresh and deactivated ZnO-supported cobalt catalysts (Co/ZnO and Co/ZnO(d), respectively) as well as on ZnO support alone. The results were used to analyze the catalytic behavior of these materials for ethanol and acetaldehyde steam-reforming reactions. The Co/ZnO(d) sample contained extensive carbon deposition as shown by Raman spectroscopy and transmission electron microscopy. On fresh Co/ZnO, the adsorption energetics of ethanol and acetaldehyde (an intermediate in the ethanol reforming reaction) were similar. Under steam-reforming conditions at low conversion values of ethanol, acetaldehyde was selectively yielded. The presence of surface acetate species was shown from IR spectra following acetaldehyde adsorption. Besides that, the Co/ZnO catalyst was active and showed a high selectivity toward the reforming products, H2 and CO2, when the steam reforming of acetaldehyde was carried out at low conversion v...

Abstract: . Using new in-situ field observations of the most abundant oxygenated VOCs (methanol, acetaldehyde, acetone, C3/C4 carbonyls, MVK+MAC and acetic acid) we were able to constrain emission and deposition patterns above and within a loblolly pine (Pinus taeda) plantation with a sweetgum (Liquidambar styraciflua) understory. During the day canopy scale measurements showed significant emission of methanol and acetone, while methyl vinyl ketone and methacrolein, acetaldehyde and acetic acid were mainly deposited during the day. All oxygenated compounds exhibited strong losses during the night that could not be explained by conventional dry deposition parameterizations. Accompanying leaf level measurements indicated substantial methanol and acetone emissions from loblolly pine. The exchange of acetaldehyde was more complex. Laboratory measurements made on loblolly pine needles indicated that acetaldehyde may be either emitted or taken up depending on ambient concentrations, with the compensation point increasing exponentially with temperature, and that mature needles tended to emit more acetaldehyde than younger needles. Canopy scale measurements suggested mostly deposition. Short-term (approx. 2 h) ozone fumigation in the laboratory had no detectable impact on post-exposure emissions of methanol and acetone, but decreased the exchange rates of acetaldehyde. The emission of a variety of oxygenated compounds (e.g. carbonyls and alcohols) was triggered or significantly enhanced during laboratory ozone fumigation experiments. These results suggest that higher ambient ozone levels in the future might enhance the biogenic contribution of some oxygenated compounds. Those with sufficiently low vapor pressures may potentially influence secondary organic aerosol growth. Compounds recently hypothesized to be primarily produced in the canopy atmosphere via ozone plus terpenoid-type reactions can also originate from the oxidation reaction of ozone with leaf surfaces and inside the leaf. This needs to be taken into account when scaling up very reactive biogenic compounds.

Abstract: Raney nickel can be plated with a high loading of copper (28%) to produce a novel copper−nickel catalyst, which retains a Raney-type structure. A simple two-step aqueous procedure was used. The catalyst exhibits high activity for low-temperature (250−300 °C) reforming of ethanol to methane, carbon monoxide, and hydrogen. Stable activity for over 400 h was achieved with no detectable methanation. The catalyst is significantly less active for methanol reforming and has low water−gas shift activity. The kinetics fit a two-step model in which ethanol is dehydrogenated to acetaldehyde in a first-order reaction with an activation energy of 149 kJ/mol followed by the decarbonylation of acetaldehyde, which is also first-order. The low-temperature ethanol reforming pathway has not previously been considered as a route to hydrogen for fuel cell vehicles because it leads to formation of only 2 mol of hydrogen/mol of ethanol versus 6 mol of hydrogen for traditional, high-temperature reforming. We suggest that capturi...

Abstract: A box model is used to explore the detailed chemistry of C2 and C3 organic compounds in the marine troposphere by tracing the individual reaction paths resulting from the oxidation of ethane, ethene, acetylene, propane, propene and acetic acid. The mechanisms include chemical reactions in the gas phase and in the aqueous phase of clouds and aerosol particles at cloud level under conditions resembling those in the northern hemisphere. Organic hydroperoxides are found to be important intermediate products, with subsequent reactions leading partly to the formation of mixed hydroxy or carbonyl hydroperoxides that are readily absorbed into cloud water, where they contribute significantly to the formation of multifunctional organic compounds and organic acids. Organic hydroperoxides add little to the oxidation of sulfur dioxide dissolved in the aqueous phase, which is dominated by H2O2. Next to acetaldehyde and acetone, glycol aldehyde, glyoxal, methyl glyoxal and hydroxy propanone are prominent oxidation products in the gas and the aqueous phase. Acetaldehyde is not efficiently converted to acetic acid in clouds; the major local sources of acetic acid are gas-phase reactions. Other acids produced include hydroperoxy acetic, glycolic, glyoxylic, oxalic, pyruvic, and lactic acid. The mechanism of Schuchmann et al. (1985), which derives glycolic and glyoxylic acid from the oxidation of acetate, is found unimportant in the marine atmosphere. The principal precursors of glyoxylic acid are glyoxal and glycolic acid. The former derives mainly from acetylene and ethene, the latter from glycolaldehyde, also an oxidation product of ethene. The oxidation of glyoxylic acid leads to oxalic acid, which accumulates and is predicted to reach steady state concentrations in the range 30–90 ng m−3. This is greater, yet of the same magnitude, than the concentrations observed over the remote Pacific Ocean.

Abstract: A bifunctional alcohol/acetaldehyde dehydrogenase (AdhE) gene (adhE) was cloned from Leuconostoc mesenteroides C7 (LMC7), which is the dominant lactic acid bacterium produced during heterofermentation of kimchi. The nucleotide sequence of the DNA fragment containing putative adhE, which is 2685 bp long and encodes an 886 amino acid polypeptide, exhibits 99% homology with Leu. mesenteroides sp. cremoris. The deduced AdhE comprises two conserved domains: alcohol dehydrogenase (Adh) and acetaldehyde dehydrogenase (Aldh). Moreover, two NAD-binding sites were observed, based on the presence of the GXGXXG motif. A pADHE containing the adhE gene expressed AdhE at the translational level in Escherichia coli BL21, which was at a higher level than in E. coli DH5α and E. coli JM109. The AdhE of LMC7 showed Adh and Aldh activities that, when expressed in E. coli. BL21, were 7.5 and 5.7 U mg-1 , respectively.

Abstract: Alcohol drinking during pregnancy results in abnormal fetal development, including fetal alcohol syndrome (FAS) in humans and experimental animals. FAS is characterized by two major effects, including central nervous system (CNS) dysfunction and multiple anomalies recognizable mainly as a typical face. However, the mechanisms of alcohol-induced embryotoxicity have not been clearly demonstrated. The aim of the present study was to investigate the possible mechanisms underlying ethanol-induced FAS in the developing embryo. First, ethanol-induced developmental abnormalities were investigated in vitro. Postimplantation embryos at gestation day (GD) 9.5 were cultured for 48 h and observed for morphological changes. Ethanol-mediated changes in proteins regulated apoptosis (p53 and bcl-2), antioxidant (vitamin E and catalase) activities, generation of reactive oxygen species (ROS), and oxidative DNA damage shown as 8-hydroxy-2'-deoxyguanosine (8-OHdG) were measured in embryonic midbrain cells. Alcohol or acetaldehyde significantly induced cytotoxicity in cultured rat embryonic midbrain cells. The levels of p53, bcl-2, and 8-OHdG were concomitantly changed by alcohol and acetaldehyde treatment in midbrain cells. Injured cells induced by ROS were increased by alcohol or acetaldehyde treatment in midbrain cells. Cotreatment with alcohol or acetaldehyde and catalase decreased cytotoxicity in midbrain cells. In postimplantation embryo culture, alcohol or acetaldehyde-treated embryos showed retardation of embryonic growth and development in a concentration-dependent manner. These results indicate that alcohol and its metabolite acetaldehyde induce fetal developmental abnormalities by disrupting cellular differentiation and growth. Data demonstrate that some antioxidants can partially protect against the alcohol-induced embryonic developmental toxicity.

Abstract: Mlikota Gabler, F., Smilanick, J. L., Ghosoph, J. M., and Margosan, D. A. 2005. Impact of postharvest hot water or ethanol treatment of table grapes on gray mold incidence, quality, and ethanol content. Plant Dis. 89:309-316. The influence of brief immersion of grape berries in water or ethanol at ambient or higher temperatures on the postharvest incidence of gray mold (caused by Botrytis cinerea) was evaluated. The incidence of gray mold among grape berries that were untreated, or immersed for 1 min in ethanol (35% vol/vol) at 25 or 50°C, was 78.7, 26.2, and 3.4 berries/kg, respectively, after 1 month of storage at 0.5°C and 2 days at 25°C. Heated ethanol was effective up to 24 h after inoculation, but less effective when berry pedicels were removed before inoculation. Rachis appearance, epicuticular wax content and appearance, and berry shatter were unchanged by heated ethanol treatments, whereas berry color changed slightly and treated grape berries were more susceptible to subsequent infection. Ethanol and acetaldehyde contents of grape berries were determined 1, 7, and 14 days after storage at 0.5°C following treatment for 30 or 90 s at 30, 40, or 50°C with water, or 35% ethanol. Highest residues (377 µg/g of ethanol and 13.3 µg/g of acetaldehyde) were in berries immersed for 90 s at 50°C in ethanol. Among ethanol-treated grape berries, the ethanol content declined during storage, whereas acetaldehyde content was unchanged or increased. Untreated grape berries initially contained ethanol at 62 µg/g, which then declined. Acetaldehyde content was 0.6 µg/g initially and changed little during storage.

Abstract: Objective: Individuals with alcohol dependence are less likely to possess variant alleles of the alcohol-metabolizing genes, aldehyde dehydrogenase (ALDH2*2) and alcohol dehydrogenase (ADH1B*2), than non-alcohol-dependent controls. It is hypothesized that the mechanism through which these alleles protect against alcohol dependence is by causing elevations in acetaldehyde, which in turn cause an increased response to alcohol. Previous research has shown that individuals with ALDH2*2 demonstrate enhanced reactions to alcohol compared with those without this genetic variant, but evidence that ADH1B*2 is associated with a greater alcohol response is mixed. This study was designed to determine whether the ADH1B genotype is associated with more intense reactions to alcohol after controlling for the ALDH2 genotype. Method: Participants (N = 101) were Asian American college students. Each was evaluated using objective and subjective measures before and after ingestion of alcohol and placebo beverages. Results: Pa...

Abstract: Two alcohol dehydrogenase genes (ADHIB and ADH1C on chromosome 4) and one aldehyde dehydrogenase gene (ALDH2 on chromosome 12) exhibit functional polymorphisms that are associated with lower rates of alcohol dependence. The ALDH2*2 allele,found almost exclusively in Asian populations, has the strongest relationship. The ADH1B*2, ADH1B*3, and ADHlC*i alleles, found in varying prevalence in different ethnic groups, have also been associated with lower rates of alcohol dependence. Studies of the ADHIBand ADH1C haplotypes, however, have shown that ADH1C*I is in linkage disequilibrium with ADHiB*2, and the ADH1C*i allele does not appear to have significant unique associations with alcohol dependence. The hypothesized mechanism underlying the associations of the ADH1B and ALDH2 polymorphisms with alcohol dependence is that the isoenzymes encoded by these alleles lead to an accumulation of acetaldehyde during alcohol metabolism. Based on their kinetic properties, ALDH2 *2 theoretically should lead to a slower removal of acetaldehyde than ALDH2*1, whereas ADH1B*2 and ADH1B*3 should lead to a more rapid production of acetaldehyde than ADHIB*I. It is further hypothesized that elevations in acetaldehyde cause more intense reactions to alcohol and lead to lower levels of alcohol intake. Data are consistent with the hypothesis that elevations in acetaldehyde, increased sensitivity to alcohol, and lower levels of drinking reflect the mechanism by which the ALDH2*2 allele reduces risk for alcohol dependence. There is also some evidence supporting this mechanism for the ADH1B*2 and ADHIB*3 alleles, but the results are less consistent. These findings highlight the value of trying to elucidate the mechanism by which genes ultimately give rise to differences in alcohol dependence through the examination of mediating behaviors.