Atmospheric chemistry of alcohols

Grosjean, Daniel

doi:10.1590/s0103-50531997000500002

Cited by 51 publications

(39 citation statements)

References 32 publications

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“…Moreover, our control experiments indicated the loss of IB after 9 days of continuous incubation. IB can be slowly degraded by photochemically produced hydroxyl radicals in aerobic cyanobacterial cultures (32)(33)(34). Therefore, a system with continuous removal of the synthesized alcohol products would be beneficial (35,36).…”

Section: Resultsmentioning

confidence: 99%

Metabolic Engineering of Synechocystis sp. Strain PCC 6803 for Isobutanol Production

Varman¹,

Xiao²,

Pakrasi

et al. 2013

Appl Environ Microbiol

150

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Global warming and decreasing fossil fuel reserves have prompted great interest in the synthesis of advanced biofuels from renewable resources. In an effort to address these concerns, we performed metabolic engineering of the cyanobacterium Synechocystis sp. strain PCC 6803 to develop a strain that can synthesize isobutanol under both autotrophic and mixotrophic conditions. With the expression of two heterologous genes from the Ehrlich pathway, the engineered strain can accumulate 90 mg/ liter of isobutanol from 50 mM bicarbonate in a gas-tight shaking flask. The strain does not require any inducer (i.e., isopropyl ␤-D-1-thiogalactopyranoside [IPTG]) or antibiotics to maintain its isobutanol production. In the presence of glucose, isobutanol synthesis is only moderately promoted (titer ‫؍‬ 114 mg/liter). Based on isotopomer analysis, we found that, compared to the wild-type strain, the mutant significantly reduced its glucose utilization and mainly employed autotrophic metabolism for biomass growth and isobutanol production. Since isobutanol is toxic to the cells and may also be degraded photochemically by hydroxyl radicals during the cultivation process, we employed in situ removal of the isobutanol using oleyl alcohol as a solvent trap. This resulted in a final net concentration of 298 mg/liter of isobutanol under mixotrophic culture conditions. G lobal energy needs continue to increase rapidly due to industrial and development demands, raising environmental concerns. Much of the worldwide energy consumption comes from the burning of fossil fuels, which produces about 6 gigatons of CO 2 annually (1). Increasing CO 2 levels may act as a feedback loop to increase the soil emissions of other greenhouse gases, such as methane and nitrous oxide, raising the global temperature (2). For energy security and due to environmental concerns, there is an urgent demand for the development of bioenergy. Bioethanol is the most common biofuel, but it also has low energy density and absorbs moisture. Isobutanol (IB) is a better fuel, because it is less water soluble and has an energy density/octane value close to that of gasoline (3, 4). Among the next-generation biofuels synthesized from pyruvate, IB possesses fewer reaction steps (5 reaction steps from pyruvate to IB) than the synthesis of 1-butanol or biodiesel. IB is less toxic to microbes (5), so it may achieve a higher product titer and yield (6, 7). For example, a maximum titer of 50.8 g/liter of IB can be achieved in an engineered Escherichia coli strain (8).On the other hand, cyanobacteria not only can convert CO 2 into bioproducts, but also can play an important role in environmental bioremediation. The photosynthetic efficiency of cyanobacteria (3 to 9%) is high compared to that of higher plants (Յ0.25 to 3%) (9, 10). Furthermore, some species of cyanobacteria are amenable to genetic engineering. Table 1 lists the various biofuels that have been synthesized through the metabolic engineering of cyanobacteria. Autotrophic IB production in cyanobacteria was first demons...

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Section: Resultsmentioning

confidence: 99%

Metabolic Engineering of Synechocystis sp. Strain PCC 6803 for Isobutanol Production

Varman¹,

Xiao²,

Pakrasi

et al. 2013

Appl Environ Microbiol

150

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“…Alcohols are emitted to atmosphere by anthropogenic (fuels additives, industrial solvents) and biogenic (vegetation) sources . The main process that governs their atmospheric lifetimes is their reaction with • OH radicals because photolysis, reaction with ozone, and reaction with nitrate radicals are slow processes .…”

Section: Introductionmentioning

confidence: 99%

“…However, reactions of volalile organic compounds (VOCs) with chlorine atoms are important and must be taken into account in coastal and marine environments, particularly to determine their lifetime, because the ratio [Cl]/[ • OH] is higher than the global averaged value . On the other hand, several authors have informed about the oxidation of VOCs initiated by chlorine atoms, used as surrogates for • OH radicals, due to the ease way which they can be generated, the similarity in the H atom abstraction reactions, and the simplicity of the monitoring of the whole process …”

Section: Introductionmentioning

confidence: 99%

“…Alcohols are emitted to atmosphere by anthropogenic (fuels additives, industrial solvents) and biogenic (vegetation) sources. [1][2][3][4] The main process that governs their atmospheric lifetimes is their reaction with • OH radicals because photolysis, reaction with ozone, and reaction with nitrate radicals are slow processes. 5 However, reactions of volalile organic compounds (VOCs) with chlorine atoms are important and must be taken into account in coastal and marine environments, particularly to determine their lifetime, because the ratio [Cl]/[ • OH] is higher than the global averaged value.…”

Section: Introductionmentioning

confidence: 99%

“…[6][7][8] On the other hand, several authors have informed about the oxidation of VOCs initiated by chlorine atoms, used as surrogates for • OH radicals, due to the ease way which they can be generated, the similarity in the H atom abstraction reactions, and the simplicity of the monitoring of the whole process. 3 Kinetic studies for many alcohols have been carried out by several authors. Ballesteros et al 7 performed the kinetic study of 2-methyl-2-butanol, 3-methyl-2-butanol, 2,3-dimethyl-2butanol, and 2-pentanol with chlorine atoms.…”

Section: Introductionmentioning

confidence: 99%

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Kinetics studies of 5‐methyl‐2‐hexanol, 2,2‐dimethyl‐3‐hexanol, and 2,4,4‐trimethyl‐1‐pentanol with chlorine atoms: Photooxidation mechanism of 2,4,4‐trimethyl‐1‐pentanol

Vila

Argüello

Malanca

2019

Int J of Chemical Kinetics

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The rate constants for the reaction between chlorine atoms and either 5‐methyl‐2‐hexanol, 2,2‐dimethyl‐3‐hexanol, or 2,4,4‐trimethyl‐1‐pentanol at 298 K were determined using the relative method with 2‐butanol and 1‐pentanol as reference compounds. The values obtained for 5‐methyl‐2‐hexanol, 2,2‐dimethyl‐3‐hexanol, and 2,4,4‐trimethyl‐1‐pentanol (k × 1010 cm3 molec−1 s−1) were, respectively, (2.64 ± 0.5), (2.72 ± 0.5), and (2.50 ± 0.4), in agreement with the values of the rate constants reported in bibliography for similar alcohols and the values estimated by structure activity relationship methods. The photooxidation products of 2,4,4‐trimethyl‐1‐pentanol initiated by chlorine atoms were identified (formaldehyde, 2‐propanone, 2,2‐dimethyl propanal, 4,4,‐dimethyl‐2‐pentanone, and 3,3‐dimethylbutanal), and the reaction mechanism was determined.

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Products of the gas-phase photooxidation reactions of 1-propanol with OH radicals

Azad

Andino

1999

Int J Chem Kinet

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An experimental investigation of the hydroxyl radical initiated gas-phase photooxidation of 1-propanol in the presence of NO was carried out in a reaction chamber using gas chromatography mass spectrometry. The products identified in the OH radical reactions of 1-propanol were propionaldehyde and acetaldehyde, with corresponding formation yields of 0.719 Ϯ 0.058 and 0.184 Ϯ 0.030, respectively. Errors represent Ϯ2. The experimental product yields were compared to predictions made using chemical mechanisms.

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Atmospheric chemistry of alcohols

Cited by 51 publications

References 32 publications

Metabolic Engineering of Synechocystis sp. Strain PCC 6803 for Isobutanol Production

Metabolic Engineering of Synechocystis sp. Strain PCC 6803 for Isobutanol Production

Kinetics studies of 5‐methyl‐2‐hexanol, 2,2‐dimethyl‐3‐hexanol, and 2,4,4‐trimethyl‐1‐pentanol with chlorine atoms: Photooxidation mechanism of 2,4,4‐trimethyl‐1‐pentanol

Products of the gas-phase photooxidation reactions of 1-propanol with OH radicals

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