Release Of Acetaldehyde Research Articles

A note on the chemical fate of the DABCO catalyst in amine-catalyzed hypochlorite bleaching of cellulosic pulps

AbstractHypochlorous acid bleaching under amine catalysis (Hcat bleaching stage) is an optimized bleaching stage variant that is characterized by working at weakly acidic, near-neutral pH, having high bleaching efficiency, and discharging only very small amounts of chloro-organics. This study addressed the chemical fate of the used 1,4-diazabicyclo[2.2.2]octane (DABCO) catalyst. While literature proposed either homolytic or heterolytic breakage of one ethylene bridge and subsequent release of the resulting fragments as two molecules of formaldehyde, we demonstrated the degradation to proceed by ionic elimination of one ethylene bridge starting from mono-N-chlorinated DABCO. The resulting N-vinyl (enamine) derivative adds water under the release of acetaldehyde and formation of piperazine. The generation of acetaldehyde was experimentally confirmed by 2,4-dinitrophenylhydrazine trapping, directly from the processing liquid. The experimental findings agreed superbly with computations which showed the “acetaldehyde mechanism” to be much favored over the previously proposed pathways under C–C bond cleavage and release of formaldehyde. The results of this study add to a better understanding of the novel Hcat bleaching system. Graphical abstract

Transcriptome Analyses in Adult Olive Trees Indicate Acetaldehyde Release and Cyanide-Mediated Respiration Traits as Critical for Tolerance against Xylella fastidiosa and Suggest AOX Gene Family as Marker for Multiple-Resilience.

Xylella fastidiosa (Xf) is a global bacterial threat for a diversity of plants, including olive trees. However, current understanding of host responses upon Xf-infection is limited to allow early disease prediction, diagnosis, and sustainable strategies for breeding on plant tolerance. Recently, we identified a major complex trait for early de novo programming, named CoV-MAC-TED, by comparing early transcriptome data during plant cell survival with SARS-CoV-2-infected human cells. This trait linked ROS/RNS balancing during first hours of stress perception with increased aerobic fermentation connected to alpha-tubulin-based cell restructuration and control of cell cycle progression. Furthermore, our group had advanced concepts and strategies for breeding on plant holobionts. Here, we studied tolerance against Xf-infection by applying a CoV-MAC-TED-related gene set to (1) progress proof-of-principles, (2) highlight the importance of individual host responses for knowledge gain, (3) benefit sustainable production of Xf-threatened olive, (4) stimulate new thinking on principle roles of secondary metabolite synthesis and microbiota for system equilibration and, (5) advance functional marker development for resilience prediction including tolerance to Xf-infections. We performed hypothesis-driven complex analyses in an open access transcriptome of primary target xylem tissues of naturally Xf-infected olive trees of the Xf-tolerant cv. Leccino and the Xf-susceptible cv. Ogliarola. The results indicated that cyanide-mediated equilibration of oxygen-dependent respiration and carbon-stress alleviation by the help of increased glycolysis-driven aerobic fermentation paths and phenolic metabolism associate to tolerance against Xf. Furthermore, enhanced alternative oxidase (AOX) transcript levels through transcription Gleichschaltung linked to quinic acid synthesis appeared as promising trait for functional marker development. Moreover, the results support the idea that fungal endophytes strengthen Xf-susceptible genotypes, which lack efficient AOX functionality. Overall, this proof-of-principles approach supports the idea that efficient regulation of the multi-functional AOX gene family can assist selection on multiple-resilience, which integrates Xf-tolerance, and stimulates future validation across diverse systems.

Study on the Formation Mechanism of Acetaldehyde during the Low-Temperature Oxidation of Coal.

The threshold dilution ratio of acetaldehyde is much larger than those of other odor compounds generated during the spontaneous combustion process and so it is the most important odorant. Studying the mechanism by which acetaldehyde is generated can provide the necessary theoretical support for acetaldehyde-based odor analysis. In the present work, the release of acetaldehyde was monitored while heating lignite, long-flame coal, and coking coal specimens under either air or nitrogen. The data show that acetaldehyde was primarily produced by the oxidation of active sites in the coal rather than by the pyrolysis of oxygen-containing functional groups. Based on quantum chemistry and coal-oxygen reaction theory, the transition state approach was used to further study the formation of acetaldehyde during the low-temperature oxidation of coal. Using density functional theory, three different coal molecule structures were modeled and optimized structures for acetaldehyde formation and the energies, bond lengths, and virtual frequencies of each reaction stagnation point were obtained at the B3LYP-D3/6-311G** and M062X-D3/Def2-TZVP levels. The results indicate that the low-temperature oxidation of coal to generate acetaldehyde involves the capture of H atoms from aliphatic side chains to generate peroxy radicals. These radicals then attack unsaturated C atoms through complex inversions to generate peroxides. In the third step of this process, the O-O single bonds in the peroxides break in response to thermal energy to form carbonyl groups. Finally, specific C-C or C-O bonds on the aliphatic side chains are thermally cleaved to generate acetaldehyde.

Prediction of spontaneous combustion tendency of coal based on acetaldehyde release

ABSTRACT Acetaldehyde is one of the crucial gases with odor released during the early stage of spontaneous combustion of coal, and it is essential for predicting the spontaneous combustion tendency of coal. In this study, we systematically investigated the effects of coal metamorphic degree, coal temperature, coal particle size, and oxygen concentration on the release of acetaldehyde using three coal samples with different metamorphic degrees and a combination of oxidation and warming processes as well as gas and liquid chromatography. The results showed that with the increase in temperature, the amount of acetaldehyde released first increased and then stabilized or slightly decreased. The amount of acetaldehyde released at low temperatures was linearly related to oxygen consumption. The higher the degree of coal deterioration, the lower the amount of acetaldehyde released. As the particle size decreased, the amount of acetaldehyde released increased and then decreased. Finally, four warning levels were established based on the concentrations and trends of acetaldehyde together with other index gases.

Kinetics and mechanism of the thermal decomposition of the isoxazoline compounds

The decomposition of the isoxazole ring at 160–280°C formed by the addition of ethylene to methyland ethyl–substituted benzonitrile oxides is studied. The reaction consists in the cleavage of the isoxazole ring into acetaldehyde and the corresponding aromatic nitrile. Its rate in the melt and in inert solvents, such as chlorobenzene, only weakly depends on the structure of the aromatic substituent, with the kinetic parameters having low values: E = (104 ± 8) kJ/mol and log(A, s–1) = 7.2 ± 0.8. Only if the benzene ring has three ethyl substituents, the decomposition of the compound in the melt proceeds faster than in solution. The rate of the decomposition of the ring decreases with increasing viscosity of the medium, being higher in solvents with a lower strength of the C–H bond. For compounds with the fully deuterated isoxazole ring, the inverse kinetic H/D isotope effect is observed. The results are explained in terms of the biradical mechanism of the opening of the isoxazole ring that involves an effective recombination of the biradical and its loss through a synchronous rearrangement with acetaldehyde release.

Structure and stability of isoxazoline compounds

Structure of isoxazoline compounds formed via the reaction of alkyl-substituted benzonitrile oxides with ethylene was determined by X-ray diffraction method. Isoxazoline ring is flattened, the bond lengths in it depend slightly on the nature of substituents (CH3, C2H5) and their position in the benzene ring and the angle of rotation relative to the isoxazoline ring. The connection N-O has a length 1.422 A. Thermal decomposition of isoxazolines in a liquid phase (160–280°C) is accompanied by the release of acetaldehyde and aromatic nitrile. Both the structure of the cycle and its stability is practically independent of the structure of an aromatic substituent. The rate constant of the initial stage is characterized by the low significance of kinetic parameters, E = 104°8 kJ mol−1 and log a(A/c) = 7.2±0.8. The results obtained are rationalized in terms of biradical mechanism of isoxazoline ring-opening that includes an efficient recombination of the biradical and its disappearance as a result of synchronous multi-center rearrangement with the release of acetaldehyde.

Quantification by SIFT-MS of acetaldehyde released by lung cells in a 3D model

Our previous studies have shown that both lung cancer cells and non-malignant lung cells release acetaldehyde in vitro. However, data from other laboratories have produced conflicting results. Furthermore, all these studies have been carried out in 2D models which are less physiological cell growth systems when compared to 3D models. Therefore, we have carried out further work on the release of acetaldehyde by lung cells in 3D collagen hydrogels. Lung cancer cells CALU-1 and non-malignant lung cells NL20 were seeded in these hydrogels at different cell concentrations and the release of acetaldehyde was measured with the Selected Ion Flow Tube Mass Spectrometry (SIFT-MS) technique. The data obtained showed that the amount of acetaldehyde released by both cell types grown in a 3D model is higher when compared to that of the same cells grown in 2D models. More importantly, acetaldehyde from the headspace of lung cancer cells could be measured even at a low cell concentration (10(5) cells per hydrogel). The differential of acetaldehyde release could be, depending on the cell concentration, more than 3 fold higher for cancer cells when compared to non-malignant lung cells. This pilot study is the first to study acetaldehyde emission from albeit only two cell types cultured in 3D scaffolds. Clearly, from such limited data the behaviour of other cell types and of tumour cells in vivo cannot be predicted with confidence. Nevertheless, this work represents another step in the search for volatile biomarkers of tumour cells, the ultimate goal of which is to exploit volatile compounds in exhaled breath and other biological fluids as biomarkers of tumours in vivo.

Alcohol‐Containing Mouthwashes

Alcohol‐Containing Mouthwashes

Release of Acetaldehyde from β-Cyclodextrins Inhibits Postharvest Decay Fungi in Vitro

Many naturally occurring plant volatiles are known to have antifungal properties. However, they have limited use because they diffuse rapidly in air. In this in vitro study, acetaldehyde was chosen as a prototype volatile in order to study the controlled release of antifungal volatiles from cyclodextrins (CD). The major postharvest pathogens Alternaria alternata, Botrytis cinerea, and Colletotrichum acutatum were exposed to the pure volatile for 7 days at 23 degrees C. Acetaldehyde was most effective against A. alternata, followed by C. acutatum, and B. cinerea, with 0.12, 0.56, and 1.72 microL/L in air being required to inhibit fungal growth, respectively, according to the bioassay developed. Second, the effectiveness of the new beta-CD-acetaldehyde release system was evaluated against A. alternata for 7 days at 23 degrees C. Sufficient volatile was released from 0.7 g of beta-CD-acetaldehyde to prevent fungal growth in vitro.

Organ-specific analysis of the anaerobic primary metabolism in rice and wheat seedlings. I: Dark ethanol production is dominated by the shoots

During anaerobiosis in darkness the main route for ATP production in plants is through glycolysis in combination with fermentation. We compared the organ-specific anaerobic fermentation of flooding-tolerant rice (Oryza sativa) and sensitive wheat (Triticum aestivum) seedlings. A sensitive laser-based photoacoustic trace gas detection system was used to monitor emission of ethanol and acetaldehyde by roots and shoots of intact seedlings. Dark-incubated rice seedlings released 3 times more acetaldehyde and 14 times more ethanol than wheat seedlings during anaerobiosis. Ninety percent of acetaldehyde originated from shoots of both species. In comparison to wheat shoots, the high ethanol production of rice shoots correlated with larger amounts of soluble carbohydrates, and higher activities of fermentative enzymes. After 24 h of anaerobiosis in darkness rice shoots still contained 30% of aerated ATP level, which enabled seedlings to survive this period. In contrast, ATP content declined almost to zero in wheat shoots and roots, which were irreversibly damaged after a 24-h anaerobic period. When plants were anaerobically and dark incubated for 4 h and subsequently transferred back to aeration, shoots showed a transient peak of acetaldehyde release indicating prompt re-oxidation of ethanol. Post-anoxic acetaldehyde production was lower in rice seedlings than in wheat. This observation accounts for a more effective acetaldehyde detoxification system in rice. Compared to wheat the greater tolerance of rice seedlings to transient anaerobic periods is explained by a faster fermentation rate of their shoots allowing a sufficient ATP production and an efficient suppression of toxic acetaldehyde formation in the early re-aeration period.

THEORETICAL STUDY TOWARD UNDERSTANDING THE CATALYTIC MECHANISM OF PYRUVATE DEHYDROGENASE MULTIENZYME COMPLEX E1 COMPONENT

Density functional calculations are employed to investigate the mechanisms of all elementary reaction steps involved in the catalytic reaction of pyruvate dehydrogenase multienzyme complex E1 (PDHc E1). We have obtained the free energy profiles for all reaction steps, and have demonstrated the importance of some key residues (Glu571, Glu522, His640 and a water molecule) near the active center in each individual step. Glu571 plays an essential role in the ylide formation, the addition of pyruvate, and the release of acetaldehyde. Glu522 helps to orientate the carboxyl of pyruvate in favor of the addition reaction of pyruvate. The protonation of the enamine is found to proceed through a concerted double proton transfer transition state involving His640 and a water molecule. All reaction steps are calculated to be thermodynamically favorable, except for the release of acetaldehyde which is slightly endothermic. The protonation of the enamine is a rate-limiting step with a barrier of 24.5 kcal/mol in the protein environment. Comparing the energetics of the catalytic reaction in PDHc E1 with that in PDC, we find that the relative orientation of some conserved residues and the conformation of the cofactor ThDP have a significant impact on the reaction rates of individual steps.

Theoretical Study toward Understanding the Catalytic Mechanism of Pyruvate Decarboxylase

Density functional calculations are employed to explore the mechanisms of all elementary reaction steps involved in the catalytic cycle of pyruvate decarboxylase (PDC). Different models are constructed for mimicking the involvement of some key residues in a certain step. The effect of the protein framework on the potential energy profiles of active site models is approximately modeled by fixing some freedoms, based on the crystal structure of the PDC enzyme from Saccharomyces cerevisiae (ScPDC). Our calculations confirm that Glu51 is the most important residue in the formation of the ylide and the release of acetaldehyde via the proton relay between Glu51, N1', and the 4'-amino group of thiamine diphosphate. The presence of Glu477 and Asp28 residues makes the decarboxylation of lactylthiamin diphosphate (LThDP) an endothermic process with a significant free energy barrier. The protonation of the alpha-carbanion to form 2-(1-hydroxyethyl)-thiamin diphosphate is found to go through a concerted double proton transfer transition state involving both Asp28 and His115 residues. The final step, acetaldehyde release, is likely to proceed through a concerted transition state involving carbon-carbon bond-breaking and the deprotonation of the alpha-hydroxyl group. The decarboxylation of LThDP and the protonation of the alpha-carbanion are two rate-limiting steps, relative to the facile occurrence of the ylide formation and acetaldehyde release. The catalytic roles of residues Glu51, Glu477, Asp28, and Gly417 in the active site of ScPDC in individual steps elucidated from the present study are in good agreement with those derived from site-directed mutagenesis.

Kinetics of Ethanol and Acetaldehyde Release Suggest a Role for Acetaldehyde Production in Tolerance of Rice Seedlings to Micro-aerobic Conditions

This paper examines the basis of the greater tolerance of an indica rice cultivar FR13A to complete submergence compared with relatively intolerant japonica rice CT6241. We study whether this superior tolerance is related to its greater tolerance to O2 shortage and to an ability to run a more favourable rate of alcoholic fermentation during and after O2 deprivation. METHODS Fermentation products were analysed using sensitive laser-based photoacoustics at high time resolution to establish patterns and rates of ethanol and acetaldehyde emission by intact rice seedlings exposed to micro-aerobic (0.05-0.5 % O2) or zero O2 supply, and also during their return to air. Oxygen and CO2 emission or uptake was also quantified. In the dark, no acetaldehyde and ethanol emission was observed until external O2 concentration in a gas phase decreased to <or=0.3% O2. The ethanol production rate was maximal in 0% O2, similar in both cultivars and gradually diminished with increasing O2 concentration. Lag time for induction of fermentation increased with O2 up to 0.3% and was shorter in CT6241. Light strongly suppressed fermentation. In contrast to that of ethanol, emission of acetaldehyde in the dark under micro-aerobic conditions (<or=0.15% O2 gas phase) exceeded that under anaerobiosis, was maximal in 0.05% O2 and was greater in FR13A than in CT6241. A drop in acetaldehyde emission to about half its value immediately followed a switch to anaerobic conditions after 6.5 h treatment under 0.05% O2, while ethanol release showed a further increase. A large peak in acetaldehyde emission immediately followed the return of seedlings to air after treatment with <or=0.15% O2. The emission from FR13A was up to three times larger than from CT6241. Tolerance to submergence in FR13A appears not to be connected to its rate of ethanol production during anaerobiosis, but to the increased acetaldehyde output during and after experiencing micro-aerobic conditions (0.05-0.15% O2). Extra acetaldehyde production from ethanol may be a consequence of diversion of the reactive oxygen species away from the damaging lipid peroxidation pathway.

Transient release of oxygenated volatile organic compounds during light-dark transitions in Grey poplar leaves.

In this study, we investigated the prompt release of acetaldehyde and other oxygenated volatile organic compounds (VOCs) from leaves of Grey poplar [Populus x canescens (Aiton) Smith] following light-dark transitions. Mass scans utilizing the extremely fast and sensitive proton transfer reaction-mass spectrometry technique revealed the following temporal pattern after light-dark transitions: hexenal was emitted first, followed by acetaldehyde and other C(6)-VOCs. Under anoxic conditions, acetaldehyde was the only compound released after switching off the light. This clearly indicated that hexenal and other C(6)-VOCs were released from the lipoxygenase reaction taking place during light-dark transitions under aerobic conditions. Experiments with enzyme inhibitors that artificially increased cytosolic pyruvate demonstrated that the acetaldehyde burst after light-dark transition could not be explained by the recently suggested pyruvate overflow mechanism. The simulation of light fleck situations in the canopy by exposing leaves to alternating light-dark and dark-light transitions or fast changes from high to low photosynthetic photon flux density showed that this process is of minor importance for acetaldehyde emission into the Earth's atmosphere.

Reversal of DNA alkylation damage by two human dioxygenases.

The Escherichia coli AlkB protein protects against the cytotoxicity of methylating agents by repair of the DNA lesions 1-methyladenine and 3-methylcytosine, which are generated in single-stranded stretches of DNA. AlkB is an alpha-ketoglutarate- and Fe(II)-dependent dioxygenase that oxidizes the relevant methyl groups and releases them as formaldehyde. Here, we identify two human AlkB homologs, ABH2 and ABH3, by sequence and fold similarity, functional assays, and complementation of the E. coli alkB mutant phenotype. The levels of their mRNAs do not appear to correlate with cell proliferation but tissue distributions are different. Both enzymes remove 1-methyladenine and 3-methylcytosine from methylated polynucleotides in an alpha-ketoglutarate-dependent reaction, and act by direct damage reversal with the regeneration of the unsubstituted bases. AlkB, ABH2, and ABH3 can also repair 1-ethyladenine residues in DNA with the release of acetaldehyde.

Vitamin B12: Insights into Biosynthesis's Mount Improbable

The biosynthesis of the corrin ring component of cobalamin (vitamin B12) is reviewed with regard to how two separate though broadly similar pathways may have evolved. The more ancient “anaerobic” pathway is characterized by the early chelation of cobalt and the release of acetaldehyde whereas the “aerobic” pathway is characterized by an absolute dependency on molecular oxygen, the late chelation of cobalt and the release of acetic acid. Both pathways require the addition of 8S-adenosyl-L-methionine-derived methyl groups to the periphery of the tetrapyrrole framework. The sequences of these enzymes reveal that they are clearly related, most likely having evolved from an ancestral methylase gene. The three-dimensional structure of one of these methyltransferases is highlighted and discussed in light of a common mechanism for this family of enzymes. Moreover, the aerobic and anaerobic chelatases are described and parallels with the chelatases found in heme and chlorophyll synthesis are drawn.

Acetaldehyde in Mineral Water Stored in Polyethylene Terephthalate (PET) Bottles: Odour Threshold and Quantification

The use of PET bottles for packaging soft drinks and mineral waters is still growing world wide. The production process for these bottles is improving constantly. These improvements are focussed on bottles with better barrier properties, higher inertness and higher heat stability. One of the factors determining the quality of PET bottles is the release of acetaldehyde into the product during storage. A literature survey was conducted on the odour and taste detection threshold of acetaldehyde in water. A method is described to rapidly determine the concentration of acetaldehyde in water up to a level of 1 μg/l. This method was used to determine the concentration of acetaldehyde in mineral water during storage in PET bottles. In still water no acetaldehyde could be found, whereas the concentration of acetaldehyde in carbonated mineral water increased steadily upon storage. Model experiments were performed to find an explanation.

Acetaldehyde in Mineral Water Stored in Polyethylene Terephthalate (PET) Bottles: Odour Threshold and Quantification

The use of PET bottles for packaging soft drinks and mineral waters is still growing world wide. The production process for these bottles is improving constantly. These improvements are focussed on bottles with better barrier properties, higher inertness and higher heat stability. One of the factors determining the quality of PET bottles is the release of acetaldehyde into the product during storage. A literature survey was conducted on the odour and taste detection threshold of acetaldehyde in water. A method is described to rapidly determine the concentration of acetaldehyde in water up to a level of 1 μg/l. This method was used to determine the concentration of acetaldehyde in mineral water during storage in PET bottles. In still water no acetaldehyde could be found, whereas the concentration of acetaldehyde in carbonated mineral water increased steadily upon storage. Model experiments were performed to find an explanation.

CIRCULATING CYTOTOXIC PROTEIN GENERATED AFTER ETHANOL CONSUMPTION: IDENTIFICATION AND MECHANISM OF REACTION WITH CELLS

Serum obtained from healthy volunteers 6-7 h after consumption of 60-95 g of ethanol contained cytotoxic activity against mouse A9 cells and all of six human cell lines tested. Affinity chromatography of such sera demonstrated that at least some of the cytotoxic molecules consisted of altered albumin. Complexes formed by the reaction of 14C-acetaldehyde with 125I-labelled human serum albumin in vitro were also cytotoxic. After treatment with a reducing agent, sodium borohydride, the cytotoxicity of both post-alcohol serum and the acetaldehyde-albumin complexes fell sharply, suggesting that the cytotoxic activity resided in the unstable Schiff bases formed during the first stage of reaction between the acetaldehyde and proteins. A detailed analysis of the reaction between the double-labelled acetaldehyde-albumin complexes and K562 cells revealed that the cytotoxic activity resulted from the release of acetaldehyde from such complexes and the preferential binding of the free acetaldehyde to the target cells.

Brewers' yeast pyruvate decarboxylase produces acetoin from acetaldehyde: a novel tool to study the mechanism of steps subsequent to carbon dioxide loss.

A gas-liquid chromatographic technique was developed for the determination of both acetaldehyde and the 3-4% acetoin side product that results from the brewers' yeast pyruvate decarboxylase (EC 4.1.1.1) catalyzed reaction of pyruvic acid. Employing this method enabled the demonstration of the catalysis of acetaldehyde condensation to acetoin by the enzyme. It was found that the acetoin produced enzymatically from pyruvic acid or from acetaldehyde was optically active, thus providing stereochemical information about the reaction. Deuterium kinetic isotope effects (employing CH3CHO and CH3CDO) were determined on the steady-state kinetic parameters to be 4.5 (Vmax) and 3.2 (Vmax/Kappm), respectively. This enabled, for the first time, the estimation of relative kinetic barriers for steps past decarboxylation. It could be concluded that (a) C-H bond scission was part of rate limitation in the enzyme-catalyzed condensation of acetaldehyde to acetoin and that (b) among the steps leading to the release of acetaldehyde, protonation of the key enamine intermediate was part of rate limitation. This latter finding is also directly applicable to the mechanism of pyruvate decarboxylation.