Journal articles on the topic 'Glyoxol'
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1
Shangari, N., W. R. Bruce, R. Poon, and P. J. O'Brien. "Toxicity of glyoxals – role of oxidative stress, metabolic detoxification and thiamine deficiency." Biochemical Society Transactions 31, no. 6 (December 1, 2003): 1390–93. http://dx.doi.org/10.1042/bst0311390.
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Glyoxals are reactive α-oxoaldehydes that are formed endogenously from sugars, the levels of which are increased in various pathological conditions associated with hyperglycaemia and thiamine deficiency. However, the molecular cytotoxic mechanisms of glyoxal are not known. Results presented here and in the other studies cited provide a glimpse into the cytotoxicity mechanisms involved and their pathological implications. We found that glyoxal (10 μM) markedly increased the susceptibility of hepatocyte glutathione (GSH) to oxidation by hydrogen peroxide (H2O2) and markedly increased cytotoxicity by compromising the cellular antioxidant enzyme system. At higher concentrations, glyoxal was cytotoxic towards hepatocytes, which can be attributed to GSH depletion, oxidative stress and mitochondrial toxicity. Aminoguanidine or penicillamine protected the hepatocytes. Glyoxal cytotoxicity was prevented by increasing glyoxal metabolism with thiamine or NAD(P)H generators, and was increased in GSH- or thiamine-deficient hepatocytes. It was also found that feeding rats reduced thiamine levels in a diet high in simple sugars increased the number of aberrant crypt foci/colon in the absence of clinical evidence of beriberi. This was associated with decreased plasma thiamine and low erythrocyte transketolase activity. Western diets, which are frequently poor in thiamine and high in sugars, could result in increased levels of endogenous glyoxals, which in turn may lead to a predisposition to AGE (advanced glycation end-product)-related pathologies and neoplastic conditions.
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Stefani, Helio A., Stanley N. S. Vasconcelos, Frederico B. Souza, Flavia Manarin, and Julio Zukerman-Schpector. "ChemInform Abstract: One-Pot Three-Component Synthesis of Indole-3-glyoxyl Derivatives and Indole-3-glyoxal Triazoles." ChemInform 45, no. 8 (February 7, 2014): no. http://dx.doi.org/10.1002/chin.201408132.
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Walker, B., N. McCarthy, A. Healy, T. Ye, and M. A. McKervey. "Peptide glyoxals: a novel class of inhibitor for serine and cysteine proteinases." Biochemical Journal 293, no. 2 (July 15, 1993): 321–23. http://dx.doi.org/10.1042/bj2930321.
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A series of novel synthetic dipeptides, containing a C-terminal glyoxal grouping (-COCHO), have been tested as inhibitors against typical members of the serine- and cysteine-proteinase families. For example, the sequences benzyloxycarbonyl (Cbz)-Pro-Phe-CHO (I) and Cbz-Phe-Ala-CHO (II), which fulfil the known primary and secondary specificity requirements of chymotrypsin and cathepsin B respectively, have been found to be potent reversible inhibitors of their respective target proteinase. Thus I was found to inhibit chymotrypsin with a Ki of approximately 0.8 microM, whereas II exhibits a Ki of approximately 80 nm against cathepsin B. These Ki values are some 10-fold and 3-fold lower than those reported for the corresponding peptide-aldehyde inhibitors of chymotrypsin and cathepsin B upon which the peptidyl-glyoxals were fashioned. Unexpectedly, the sequence Cbz-Pro-Ala-CHO, which was designed to inhibit elastase-like proteinases, exhibited no inhibitory activity towards porcine pancreatic elastase, even when used at concentrations as high as 200 microM.
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Huisman, A. J., J. R. Hottle, M. M. Galloway, J. P. DiGangi, K. L. Coens, W. Choi, I. C. Faloona, et al. "Photochemical modeling of glyoxal at a rural site: observations and analysis from BEARPEX 2007." Atmospheric Chemistry and Physics 11, no. 17 (September 1, 2011): 8883–97. http://dx.doi.org/10.5194/acp-11-8883-2011.
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Abstract. We present roughly one month of high time-resolution, direct, in situ measurements of gas-phase glyoxal acquired during the BEARPEX 2007 field campaign. The research site, located on a ponderosa pine plantation in the Sierra Nevada mountains, is strongly influenced by biogenic volatile organic compounds (BVOCs); thus this data adds to the few existing measurements of glyoxal in BVOC-dominated areas. The short lifetime of glyoxal of ~1 h, the fact that glyoxal mixing ratios are much higher during high temperature periods, and the results of a photochemical model demonstrate that glyoxal is strongly influenced by BVOC precursors during high temperature periods. A zero-dimensional box model using near-explicit chemistry from the Leeds Master Chemical Mechanism v3.1 was used to investigate the processes controlling glyoxal chemistry during BEARPEX 2007. The model showed that MBO is the most important glyoxal precursor (~67 %), followed by isoprene (~26 %) and methylchavicol (~6 %), a precursor previously not commonly considered for glyoxal production. The model calculated a noon lifetime for glyoxal of ~0.9 h, making glyoxal well suited as a local tracer of VOC oxidation in a forested rural environment; however, the modeled glyoxal mixing ratios over-predicted measured glyoxal by a factor 2 to 5. Loss of glyoxal to aerosol was not found to be significant, likely as a result of the very dry conditions, and could not explain the over-prediction. Although several parameters, such as an approximation for advection, were found to improve the model measurement discrepancy, reduction in OH was by far the most effective. Reducing model OH concentrations to half the measured values decreased the glyoxal over-prediction from a factor of 2.4 to 1.1, as well as the overprediction of HO2 from a factor of 1.64 to 1.14. Our analysis has shown that glyoxal is particularly sensitive to OH concentration compared to other BVOC oxidation products. This relationship arises from (i) the predominantly secondary- or higher-generation production of glyoxal from (mainly OH-driven, rather than O3-driven) BVOC oxidation at this site and (ii) the relative importance of photolysis in glyoxal loss as compared to reaction with OH. We propose that glyoxal is a useful tracer for OH-driven BVOC oxidation chemistry.
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Huisman, A. J., J. R. Hottle, M. M. Galloway, J. P. DiGangi, K. L. Coens, W. S. Choi, I. C. Faloona, et al. "Photochemical modeling of glyoxal at a rural site: observations and analysis from BEARPEX 2007." Atmospheric Chemistry and Physics Discussions 11, no. 5 (May 5, 2011): 13655–91. http://dx.doi.org/10.5194/acpd-11-13655-2011.
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Abstract. We present ~one month of high time-resolution, direct, in situ measurements of gas-phase glyoxal acquired during the BEARPEX 2007 field campaign. The research site, located on a ponderosa pine plantation in the Sierra Nevada mountains, is strongly influenced by biogenic volatile organic compounds (BVOCs); thus this data adds to the few existing measurements of glyoxal in BVOC-dominated areas. The short lifetime of glyoxal of ~1 h, the fact that glyoxal mixing ratios are much higher during high temperature periods, and the results of a photochemical model demonstrate that glyoxal is strongly influenced by BVOC precursors during high temperature periods. A zero-dimensional box model using near-explicit chemistry from the Leeds Master Chemical Mechanism v3.1 is used to investigate the processes controlling glyoxal chemistry during BEARPEX 2007. The model shows that MBO is the most important glyoxal precursor (~67%), followed by isoprene (~26%) and methylchavicol (~6%), a precursor previously not commonly considered for glyoxal production. The model calculates a noon lifetime for glyoxal of ~0.9 h, making glyoxal well suited as a local tracer of VOC oxidation in a forested rural environment; however, the modeled glyoxal mixing ratios over-predict measured glyoxal by a factor 2 to 5. Although several parameters, such as an approximation for advection and increased glyoxal loss to aerosol can improve the model measurement discrepancy, reduction in OH is by far the most effective. Reducing OH to half the measured values, which is suggested by preliminary OH measurements using a different technique, decreases the glyoxal over-prediction from a factor of 2.4 to 1.1, as well as the overprediction of HO2 from a factor of 1.64 to 1.14.
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Stavrakou, T., J. F. Müller, I. De Smedt, M. Van Roozendael, M. Kanakidou, M. Vrekoussis, F. Wittrock, A. Richter, and J. P. Burrows. "The continental source of glyoxal estimated by the synergistic use of spaceborne measurements and inverse modelling." Atmospheric Chemistry and Physics Discussions 9, no. 3 (June 19, 2009): 13593–628. http://dx.doi.org/10.5194/acpd-9-13593-2009.
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Abstract. Tropospheric glyoxal and formaldehyde columns retrieved from the SCIAMACHY satellite instrument in 2005 are used with the IMAGESv2 global chemistry-transport model and its adjoint in a two-compound inversion scheme designed to estimate the continental source of glyoxal. The formaldehyde observations provide an important constraint on the production of glyoxal from isoprene in the model, since the degradation of isoprene constitutes an important source of both glyoxal and formaldehyde. Current modelling studies underestimate largely the observed glyoxal satellite columns, pointing to the existence of an additional land glyoxal source of biogenic origin. We include an extra glyoxal source in the model and we explore its possible distribution and magnitude through two inversion experiments. In the first case, the additional source is represented as a direct glyoxal emission, and in the second, as a secondary formation through the oxidation of an unspecified glyoxal precursor. Besides this extra source, the inversion scheme optimizes the primary glyoxal and formaldehyde emissions, as well as their secondary production from other identified non-methane volatile organic precursors of anthropogenic, pyrogenic and biogenic origin. In the first inversion experiment, the additional direct source, estimated at 36 Tg/yr, represents 38% of the global continental source, whereas the contribution of isoprene is equally important (30%), the remainder being accounted for by anthropogenic (20%) and pyrogenic fluxes. The inversion succeeds in reducing the underestimation of the glyoxal columns by the model, but it leads to a severe overestimation of glyoxal surface concentrations in comparison with in situ measurements. In the second scenario, the inferred total global continental glyoxal source is estimated at 108 Tg/yr, almost two times higher than the global a priori source. The extra secondary source is the largest contribution to the global glyoxal budget (50%), followed by the production from isoprene (26%) and from anthropogenic NMVOC precursors (14%). A better performance is achieved in this case, as the updated emissions allow for a satisfactory agreement of the model with both satellite and in situ glyoxal observations.
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Stavrakou, T., J. F. Müller, I. De Smedt, M. Van Roozendael, M. Kanakidou, M. Vrekoussis, F. Wittrock, A. Richter, and J. P. Burrows. "The continental source of glyoxal estimated by the synergistic use of spaceborne measurements and inverse modelling." Atmospheric Chemistry and Physics 9, no. 21 (November 5, 2009): 8431–46. http://dx.doi.org/10.5194/acp-9-8431-2009.
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Abstract. Tropospheric glyoxal and formaldehyde columns retrieved from the SCIAMACHY satellite instrument in 2005 are used with the IMAGESv2 global chemistry-transport model and its adjoint in a two-compound inversion scheme designed to estimate the continental source of glyoxal. The formaldehyde observations provide an important constraint on the production of glyoxal from isoprene in the model, since the degradation of isoprene constitutes an important source of both glyoxal and formaldehyde. Current modelling studies underestimate largely the observed glyoxal satellite columns, pointing to the existence of an additional land glyoxal source of biogenic origin. We include an extra glyoxal source in the model and we explore its possible distribution and magnitude through two inversion experiments. In the first case, the additional source is represented as a direct glyoxal emission, and in the second, as a secondary formation through the oxidation of an unspecified glyoxal precursor. Besides this extra source, the inversion scheme optimizes the primary glyoxal and formaldehyde emissions, as well as their secondary production from other identified non-methane volatile organic precursors of anthropogenic, pyrogenic and biogenic origin. In the first inversion experiment, the additional direct source, estimated at 36 Tg/yr, represents 38% of the global continental source, whereas the contribution of isoprene is equally important (30%), the remainder being accounted for by anthropogenic (20%) and pyrogenic fluxes. The inversion succeeds in reducing the underestimation of the glyoxal columns by the model, but it leads to a severe overestimation of glyoxal surface concentrations in comparison with in situ measurements. In the second scenario, the inferred total global continental glyoxal source is estimated at 108 Tg/yr, almost two times higher than the global a priori source. The extra secondary source is the largest contribution to the global glyoxal budget (50%), followed by the production from isoprene (26%) and from anthropogenic NMVOC precursors (14%). A better performance is achieved in this case, as the updated emissions allow for a satisfactory agreement of the model with both satellite and in situ glyoxal observations.
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Myriokefalitakis, S., M. Vrekoussis, K. Tsigaridis, F. Wittrock, A. Richter, C. Brühl, R. Volkamer, J. P. Burrows, and M. Kanakidou. "The influence of natural and anthropogenic secondary sources on the glyoxal global distribution." Atmospheric Chemistry and Physics Discussions 8, no. 1 (January 31, 2008): 1673–708. http://dx.doi.org/10.5194/acpd-8-1673-2008.
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Abstract. Glyoxal, the smallest dicarbonyl, which has recently been observed from space, is expected to provide indications on VOC oxidation and secondary aerosol formation in the troposphere. Glyoxal is known to be mostly of natural origin and is produced during biogenic VOC oxidation. However, a number of anthropogenically emitted hydrocarbons, like acetylene and aromatics, have been positively identified as glyoxal precursors. The present study investigates the contribution of pollution emissions to the glyoxal levels by taking into account only the secondary chemical formation of glyoxal from precursors emitted from biogenic, anthropogenic and biomass burning sources. For this purpose, a global 3-dimensional chemistry transport model of the troposphere (TM4) able to simulate the gas phase chemistry coupled with all major aerosol components is used. The model results are compared with satellite observations of glyoxal columns over hot spot areas. According to TM4 model results, the anthropogenic contribution to the glyoxal columns is found to reach 70% in the industrialized areas of the northern hemisphere and up to 20% in the tropics. It is on average three times larger than the secondary production of glyoxal from biomass burning sources. The chemical production of glyoxal is calculated to equal about 56 Tg y−1 with 70% produced from biogenic hydrocarbons oxidation, 17% from acetylene, 11% from aromatic chemistry, and 2% from ethene and propene. Glyoxal is destroyed by reactions mainly with OH radicals (22%) and by photolysis (65%), but it is also removed from the atmosphere through wet (11%) and dry deposition (6%). Secondary organic aerosol potential formation through glyoxal losses on/in aerosols and clouds was neglected here due to the significant uncertainties associated with the underlying chemistry. The global annual mean glyoxal burden and lifetime in the model domain are estimated at 0.02 Tg and 3 h, respectively.
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Thalman, R., M. T. Baeza-Romero, S. M. Ball, E. Borrás, M. J. S. Daniels, I. C. A. Goodall, S. B. Henry, et al. "Instrument intercomparison of glyoxal, methyl glyoxal and NO<sub>2</sub> under simulated atmospheric conditions." Atmospheric Measurement Techniques 8, no. 4 (April 23, 2015): 1835–62. http://dx.doi.org/10.5194/amt-8-1835-2015.
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Abstract. The α-dicarbonyl compounds glyoxal (CHOCHO) and methyl glyoxal (CH3C(O)CHO) are produced in the atmosphere by the oxidation of hydrocarbons and emitted directly from pyrogenic sources. Measurements of ambient concentrations inform about the rate of hydrocarbon oxidation, oxidative capacity, and secondary organic aerosol (SOA) formation. We present results from a comprehensive instrument comparison effort at two simulation chamber facilities in the US and Europe that included nine instruments, and seven different measurement techniques: broadband cavity enhanced absorption spectroscopy (BBCEAS), cavity-enhanced differential optical absorption spectroscopy (CE-DOAS), white-cell DOAS, Fourier transform infrared spectroscopy (FTIR, two separate instruments), laser-induced phosphorescence (LIP), solid-phase micro extraction (SPME), and proton transfer reaction mass spectrometry (PTR-ToF-MS, two separate instruments; for methyl glyoxal only because no significant response was observed for glyoxal). Experiments at the National Center for Atmospheric Research (NCAR) compare three independent sources of calibration as a function of temperature (293–330 K). Calibrations from absorption cross-section spectra at UV-visible and IR wavelengths are found to agree within 2% for glyoxal, and 4% for methyl glyoxal at all temperatures; further calibrations based on ion–molecule rate constant calculations agreed within 5% for methyl glyoxal at all temperatures. At the European Photoreactor (EUPHORE) all measurements are calibrated from the same UV-visible spectra (either directly or indirectly), thus minimizing potential systematic bias. We find excellent linearity under idealized conditions (pure glyoxal or methyl glyoxal, R2 > 0.96), and in complex gas mixtures characteristic of dry photochemical smog systems (o-xylene/NOx and isoprene/NOx, R2 > 0.95; R2 ∼ 0.65 for offline SPME measurements of methyl glyoxal). The correlations are more variable in humid ambient air mixtures (RH > 45%) for methyl glyoxal (0.58 < R2 < 0.68) than for glyoxal (0.79 < R2 < 0.99). The intercepts of correlations were insignificant for the most part (below the instruments' experimentally determined detection limits); slopes further varied by less than 5% for instruments that could also simultaneously measure NO2. For glyoxal and methyl glyoxal the slopes varied by less than 12 and 17% (both 3-σ) between direct absorption techniques (i.e., calibration from knowledge of the absorption cross section). We find a larger variability among in situ techniques that employ external calibration sources (75–90%, 3-σ), and/or techniques that employ offline analysis. Our intercomparison reveals existing differences in reports about precision and detection limits in the literature, and enables comparison on a common basis by observing a common air mass. Finally, we evaluate the influence of interfering species (e.g., NO2, O3 and H2O) of relevance in field and laboratory applications. Techniques now exist to conduct fast and accurate measurements of glyoxal at ambient concentrations, and methyl glyoxal under simulated conditions. However, techniques to measure methyl glyoxal at ambient concentrations remain a challenge, and would be desirable.
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Thalman, R., M. T. Baeza-Romero, S. M. Ball, E. Borrás, M. J. S. Daniels, I. C. A. Goodall, S. B. Henry, et al. "Instrument inter-comparison of glyoxal, methyl glyoxal and NO<sub>2</sub> under simulated atmospheric conditions." Atmospheric Measurement Techniques Discussions 7, no. 8 (August 19, 2014): 8581–642. http://dx.doi.org/10.5194/amtd-7-8581-2014.
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Abstract. The α-dicarbonyl compounds glyoxal (CHOCHO) and methyl glyoxal (CH3C(O)CHO) are produced in the atmosphere by the oxidation of hydrocarbons, and emitted directly from pyrogenic sources. Measurements of ambient concentrations inform about the rate of hydrocarbon oxidation, oxidative capacity, and secondary organic aerosol (SOA) formation. We present results from a comprehensive instrument comparison effort at 2 simulation chamber facilities in the US and Europe that included 9 instruments, and 7 different measurement techniques: Broadband Cavity Enhanced Absorption Spectroscopy (BBCEAS), Cavity Enhanced Differential Optical Absorption Spectroscopy (CE-DOAS), White-cell DOAS, Fourier Transform Infra-Red Spectroscopy (FTIR, two separate instruments), Laser Induced Phosphoresence (LIP), Solid Phase Micro Extraction (SPME), and Proton Transfer Reaction Mass Spectrometry (PTR-ToF-MS, two separate instruments; only methyl glyoxal as no significant response was observed for glyoxal). Experiments at the National Center for Atmospheric Research (NCAR) compare 3 independent sources of calibration as a function of temperature (293 K to 330 K). Calibrations from absorption cross-section spectra at UV-visible and IR wavelengths are found to agree within 2% for glyoxal, and 4% for methyl glyoxal at all temperatures; further calibrations based on ion-molecule rate constant calculations agreed within 5% for methyl glyoxal at all temperatures. At the EUropean PHOtoREactor (EUPHORE) all measurements are calibrated from the same UV-visible spectra (either directly or indirectly), thus minimizing potential systematic bias. We find excellent linearity under idealized conditions (pure glyoxal or methyl glyoxal, R2 > 0.96), and in complex gas mixtures characteristic of dry photochemical smog systems (o-xylene/NOx and isoprene/NOx, R2 > 0.95; R2 ~ 0.65 for offline SPME measurements of methyl glyoxal). The correlations are more variable in humid ambient air mixtures (RH > 45%) for methyl glyoxal (0.58 < R2 < 0.68) than for glyoxal (0.79 < R2 < 0.99). The intercepts of correlations were insignificant for the most part; slopes varied by less than 5% for instruments that also measure NO2. For glyoxal and methyl glyoxal the slopes varied by less than 12% and 17% (both 3-sigma) between inherently calibrated instruments (i.e., calibration from knowledge of the absorption cross-section). We find a larger variability among in situ techniques that employ external calibration sources (75% to 90%, 3-sigma), and/or techniques that employ offline analysis. Our inter-comparison reveal existing differences in reports about precision and detection limits in the literature, and enables comparison on a common basis by observing a common airmass. Finally, we evaluate the influence of interfering species (e.g., NO2, O3 and H2O) of relevance in field and laboratory applications. Techniques now exist to conduct fast and accurate measurements of glyoxal at ambient concentrations, and methyl glyoxal under simulated conditions. However, techniques to measure methyl glyoxal at ambient concentrations remain a challenge, and would be desirable.
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Nakao, S., Y. Liu, P. Tang, C. L. Chen, J. Zhang, and D. Cocker III. "Role of glyoxal in SOA formation from aromatic hydrocarbons: gas-phase reaction trumps reactive uptake." Atmospheric Chemistry and Physics Discussions 11, no. 11 (November 15, 2011): 30599–625. http://dx.doi.org/10.5194/acpd-11-30599-2011.
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Abstract. This study evaluates the significance of glyoxal acting as an intermediate species leading to SOA formation from aromatic hydrocarbon photooxidation under humid conditions. Rapid SOA formation from glyoxal uptake onto aqueous (NH4)2SO4 seed particles is observed; however, glyoxal did not partition to SOA or SOA coated aqueous seed during all aromatic hydrocarbon experiments (RH up to 80%). Glyoxal is found to only influence SOA formation by raising hydroxyl (OH) radical concentrations. Four experimental approaches supporting this conclusion are presented in this paper: (1) increased SOA formation and decreased SOA volatility in the toluene + NOx photooxidation system with additional glyoxal was reproduced by matching OH radical concentrations through H2O2 addition; (2) glyoxal addition to SOA seed formed from toluene + NOx photooxidation did not increase observed SOA volume; (3) SOA formation from toluene + NOx photooxidation with and without deliquesced (NH4)2SO4 seed resulted in similar SOA growth, consistent with a coating of SOA preventing glyoxal uptake onto deliquesced (NH4)2SO4 seed; and (4) the fraction of a C4H9+ fragment (observed by Aerodyne High Resolution Time-of-Flight Aerosol Mass Spectrometer, HR-ToF-AMS) from SOA formed by 2-tert-butylphenol (BP) oxidation was unchanged in the presence of additional glyoxal despite enhanced SOA formation. This study suggests that glyoxal uptake onto aerosol is minor when the surface (and near-surface) of aerosols are primarily composed of secondary organic compounds.
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Zarzana, Kyle J., Vanessa Selimovic, Abigail R. Koss, Kanako Sekimoto, Matthew M. Coggon, Bin Yuan, William P. Dubé, et al. "Primary emissions of glyoxal and methylglyoxal from laboratory measurements of open biomass burning." Atmospheric Chemistry and Physics 18, no. 20 (October 26, 2018): 15451–70. http://dx.doi.org/10.5194/acp-18-15451-2018.
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Abstract. We report the emissions of glyoxal and methylglyoxal from the open burning of biomass during the NOAA-led 2016 FIREX intensive at the Fire Sciences Laboratory in Missoula, MT. Both compounds were measured using cavity-enhanced spectroscopy, which is both more sensitive and more selective than methods previously used to determine emissions of these two compounds. A total of 75 burns were conducted, using 33 different fuels in 8 different categories, providing a far more comprehensive dataset for emissions than was previously available. Measurements of methylglyoxal using our instrument suffer from spectral interferences from several other species, and the values reported here are likely underestimates, possibly by as much as 70 %. Methylglyoxal emissions were 2–3 times higher than glyoxal emissions on a molar basis, in contrast to previous studies that report methylglyoxal emissions lower than glyoxal emissions. Methylglyoxal emission ratios for all fuels averaged 3.6±2.4 ppbv methylglyoxal (ppmv CO)−1, while emission factors averaged 0.66±0.50 g methylglyoxal (kg fuel burned)−1. Primary emissions of glyoxal from biomass burning were much lower than previous laboratory measurements but consistent with recent measurements from aircraft. Glyoxal emission ratios for all fuels averaged 1.4±0.7 ppbv glyoxal (ppmv CO)−1, while emission factors averaged 0.20±0.12 g glyoxal (kg fuel burned)−1, values that are at least a factor of 4 lower than assumed in previous estimates of the global glyoxal budget. While there was significant variability in the glyoxal emission ratios and factors between the different fuel groups, glyoxal and formaldehyde were highly correlated during the course of any given fire, and the ratio of glyoxal to formaldehyde, RGF, was consistent across many different fuel types, with an average value of 0.068±0.018. While RGF values for fresh emissions were consistent across many fuel types, further work is required to determine how this value changes as the emissions age.
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Nakao, S., Y. Liu, P. Tang, C. L. Chen, J. Zhang, and D. R. Cocker III. "Chamber studies of SOA formation from aromatic hydrocarbons: observation of limited glyoxal uptake." Atmospheric Chemistry and Physics 12, no. 9 (May 3, 2012): 3927–37. http://dx.doi.org/10.5194/acp-12-3927-2012.
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Abstract. This study evaluates the significance of glyoxal acting as an intermediate species leading to secondary organic aerosol (SOA) formation from aromatic hydrocarbon photooxidation under humid conditions. Rapid SOA formation from glyoxal uptake onto aqueous (NH4)2SO4 seed particles is observed in agreement with previous studies; however, glyoxal did not partition significantly to SOA (with or without aqueous seed) during aromatic hydrocarbon photooxidation within an environmental chamber (RH less than 80%). Rather, glyoxal influences SOA formation by raising hydroxyl (OH) radical concentrations. Four experimental approaches supporting this conclusion are presented in this paper: (1) increased SOA formation and decreased SOA volatility in the toluene + NOx photooxidation system with additional glyoxal was reproduced by matching OH radical concentrations through H2O2 addition; (2) glyoxal addition to SOA seed formed from toluene + NOx photooxidation did not increase SOA volume under dark; (3) SOA formation from toluene + NOx photooxidation with and without deliquesced (NH4)2SO4 seed resulted in similar SOA growth, consistent with a minor contribution from glyoxal uptake onto deliquesced seed and organic coatings; and (4) the fraction of a C4H9+ fragment (observed by Aerodyne High Resolution Time-of-Flight Aerosol Mass Spectrometer, HR-ToF-AMS) in SOA from 2-tert-butylphenol (BP) oxidation was unchanged in the presence of additional glyoxal despite enhanced SOA formation. This study suggests that glyoxal uptake onto aerosol during the oxidation of aromatic hydrocarbons is more limited than previously thought.
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Goudarzi, M., H. Kalantari, and M. Rezaei. "Glyoxal toxicity in isolated rat liver mitochondria." Human & Experimental Toxicology 37, no. 5 (June 22, 2017): 532–39. http://dx.doi.org/10.1177/0960327117715900.
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Glyoxal is a physiological metabolite formed by lipid peroxidation, ascorbate autoxidation, oxidative degradation of glucose, and degradation of glycated proteins. Glyoxal has been linked to oxidative stress and can cause a number of cellular damages, including covalent modification of amino and thiol groups of proteins to form advanced glycation end products. However, the mechanism of glyoxal toxicity has not been fully understood. In this study, we have focused on glyoxal toxicity in isolated rat liver mitochondria. Isolated mitochondria (0.5 mg protein per milliliter) were prepared from the Wistar rat liver using differential centrifugation and incubated with various concentrations of glyoxal (1, 2.5, 5, 7.5, and 10 mM) for 30 min. The activity of mitochondrial complex II was determined by measurement of MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide) conversion. The mitochondrial membrane potential (MMP), lipid peroxidation (MDA), reactive oxygen species (ROS) formation, glutathione (GSH) content, and protein carbonylation were also assessed. After an incubation of isolated liver mitochondria with glyoxal, disrupted electron transport chain, increased mitochondrial ROS formation, lipid peroxidation, mitochondrial membrane damage, GSH oxidation, and protein carbonylation ensued as compared to the control group ( p < 0.05). Glyoxal toxicity in isolated rat liver mitochondria was dose-dependent. In conclusion, glyoxal impaired the electron transport chain, which is the cause of increased ROS and MDA production, depletion of GSH, and disruption of MMP. Mitotoxicity of glyoxal might be related to the pathomechanisms involved in diabetes and its complications.
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Qi, Weining, Yifan Zhang, Minxia Shen, Lu Li, Wenting Dai, Yukun Chen, Yali Liu, et al. "Comparison of Gas–Particle Partitioning of Glyoxal and Methylglyoxal in the Summertime Atmosphere at the Foot and Top of Mount Hua." Molecules 28, no. 13 (July 7, 2023): 5276. http://dx.doi.org/10.3390/molecules28135276.
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Glyoxal and methylglyoxal are important volatile organic compounds in the atmosphere. The gas–particle partitioning of these carbonyl compounds makes significant contributions to O3 formation. In this study, both the gas- and particle-phase glyoxal and methylglyoxal concentrations at the foot and top of Mount Hua were determined simultaneously. The results showed that the gaseous-phase glyoxal and methylglyoxal concentrations at the top were higher than those at the foot of the mountain. However, the concentrations for the particle phase showed the opposite trend. The average theoretical values of the gas–particle partitioning coefficients of the glyoxal and methylglyoxal concentrations (4.57 × 10−10 and 9.63 × 10−10 m3 μg−1, respectively) were lower than the observed values (3.79 × 10−3 and 6.79 × 10−3 m3 μg−1, respectively). The effective Henry’s law constants (eff.KH) of the glyoxal and methylglyoxal were in the order of 108 to 109 mol/kgH2O/atm, and they were lower at the foot than they were at the top. The particle/gas ratios (P/G ratios) of the glyoxal and methylglyoxal were 0.039 and 0.055, respectively, indicating more glyoxal and methylglyoxal existed in the gas phase. The factors influencing the partitioning coefficients of the glyoxal and methylglyoxal were positively correlated with the relative humidity (RH) and negatively correlated with the PM2.5 value. Moreover, the partitioning coefficient of the glyoxal and methylglyoxal was more significant at the top than at the foot of Mount Hua.
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Kluge, Flora, Tilman Hüneke, Christophe Lerot, Simon Rosanka, Meike K. Rotermund, Domenico Taraborrelli, Benjamin Weyland, and Klaus Pfeilsticker. "Airborne glyoxal measurements in the marine and continental atmosphere: comparison with TROPOMI observations and EMAC simulations." Atmospheric Chemistry and Physics 23, no. 2 (January 25, 2023): 1369–401. http://dx.doi.org/10.5194/acp-23-1369-2023.
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Abstract. We report on airborne limb and nadir measurements of vertical profiles and total vertical column densities (VCDs) of glyoxal (C2H2O2) in the troposphere, which were performed aboard the German research aircraft HALO (High Altitude and LOng Range) in different regions and seasons around the globe between 2014 and 2019. The airborne nadir and integrated limb profiles agree excellently among each other. Our airborne observations are further compared to collocated glyoxal measurements of the TROPOspheric Monitoring Instrument (TROPOMI), with good agreement between both data sets for glyoxal observations in (1) pristine terrestrial, (2) pristine marine, (3) mixed polluted, and (4) biomass-burning-affected air masses with high glyoxal concentrations. Exceptions to the overall good agreement are observations of (1) faint and aged biomass burning plumes over the oceans and (2) of low-lying biomass burning or anthropogenic plumes in the terrestrial or marine boundary layer, both of which contain elevated glyoxal that is mostly not captured by TROPOMI. These differences in airborne and satellite-detected glyoxal are most likely caused by the overall small contribution of plumes of a limited extent to the total glyoxal absorption in the atmosphere and the difficulty in remotely detecting weak absorbers located close to low reflective surfaces (e.g. the ocean in the visible wavelength range) or within dense aerosol layers. Observations of glyoxal in aged biomass burning plumes (e.g. observed over the tropical Atlantic off the coast of West Africa in summer 2018, off the coast of Brazil by the end of the dry season 2019, and the East China Sea in spring 2018) could be traced back to related wildfires, such as a plume crossing over the Drake Passage that originated from the Australian bushfires in late 2019. Our observations of glyoxal in such aged biomass burning plumes confirm recent findings of enhanced glyoxal and presumably secondary organic aerosol (SOA) formation in aged wildfire plumes from yet-to-be-identified, longer-lived organic precursor molecules (e.g. aromatics, acetylene, or aliphatic compounds) co-emitted in the fires. Furthermore, elevated glyoxal (median 44 ppt – parts per trillion), as compared to other marine regions (median 10–19 ppt), is observed in the boundary layer over the tropical oceans, which is well in agreement with previous reports. The airborne data sets are further compared to glyoxal simulations performed with the global atmosphere chemistry model EMAC (ECHAM/MESSy Atmospheric Chemistry). When using an EMAC set up that resembles recent EMAC studies focusing on complex chemistry, reasonable agreement is found for pristine air masses (e.g. the unperturbed free and upper troposphere), but a notable glyoxal overestimation of the model exists for regions with high emissions of glyoxal and glyoxal-producing volatile organic compounds (VOCs) from the biosphere (e.g. the Amazon). In all other investigated regions, the model underpredicts glyoxal to varying degrees, in particular when probing mixed emissions from anthropogenic activities (e.g. over continental Europe, the Mediterranean, and East China Sea) and potentially from the sea (e.g. the tropical oceans). Also, the model tends to largely underpredict glyoxal in city plumes and aged biomass burning plumes. The potential causes for these differences are likely to be multifaceted, but they all point to missing glyoxal sources from the degradation of the mixture of potentially longer-chained organic compounds emitted from anthropogenic activities, biomass burning, and from the organic microlayer of the sea surface.
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Coburn, S., I. Ortega, R. Thalman, B. Blomquist, C. W. Fairall, and R. Volkamer. "Measurements of diurnal variations and eddy covariance (EC) fluxes of glyoxal in the tropical marine boundary layer: description of the Fast LED-CE-DOAS instrument." Atmospheric Measurement Techniques 7, no. 10 (October 28, 2014): 3579–95. http://dx.doi.org/10.5194/amt-7-3579-2014.
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Abstract. Here we present first eddy covariance (EC) measurements of fluxes of glyoxal, the smallest α-dicarbonyl product of hydrocarbon oxidation, and a precursor for secondary organic aerosol (SOA). The unique physical and chemical properties of glyoxal – i.e., high solubility in water (effective Henry's law constant, KH = 4.2 × 105 M atm−1) and short atmospheric lifetime (~2 h at solar noon) – make it a unique indicator species for organic carbon oxidation in the marine atmosphere. Previous reports of elevated glyoxal over oceans remain unexplained by atmospheric models. Here we describe a Fast Light-Emitting Diode Cavity-Enhanced Differential Optical Absorption Spectroscopy (Fast LED-CE-DOAS) instrument to measure diurnal variations and EC fluxes of glyoxal and inform about its unknown sources. The fast in situ sensor is described, and first results are presented from a cruise deployment over the eastern tropical Pacific Ocean (20° N to 10° S; 133 to 85° W) as part of the Tropical Ocean tRoposphere Exchange of Reactive halogens and Oxygenated VOCs (TORERO) field experiment (January to March 2012). The Fast LED-CE-DOAS is a multispectral sensor that selectively and simultaneously measures glyoxal (CHOCHO), nitrogen dioxide (NO2), oxygen dimers (O4), and water vapor (H2O) with ~2 Hz time resolution (Nyquist frequency ~1 Hz) and a precision of ~40 pptv Hz−0.5 for glyoxal. The instrument is demonstrated to be a "white-noise" sensor suitable for EC flux measurements. Fluxes of glyoxal are calculated, along with fluxes of NO2, H2O, and O4, which are used to aid the interpretation of the glyoxal fluxes. Further, highly sensitive and inherently calibrated glyoxal measurements are obtained from temporal averaging of data (e.g., detection limit smaller than 2.5 pptv in an hour). The campaign average mixing ratio in the Southern Hemisphere (SH) is found to be 43 ± 9 pptv glyoxal, which is higher than the Northern Hemisphere (NH) average of 32 ± 6 pptv (error reflects variability over multiple days). The diurnal variation of glyoxal in the marine boundary layer (MBL) is measured for the first time, and mixing ratios vary by ~8 pptv (NH) and ~12 pptv (SH) over the course of 24 h. Consistently, maxima are observed at sunrise (NH: 35 ± 5 pptv; SH: 47 ± 7 pptv), and minima at dusk (NH: 27 ± 5 pptv; SH: 35 ± 8 pptv). In both hemispheres, the daytime flux was directed from the atmosphere into the ocean, indicating that the ocean is a net sink for glyoxal during the day. After sunset the ocean was a source for glyoxal to the atmosphere (positive flux) in the SH; this primary ocean source was operative throughout the night. In the NH, the nighttime flux was positive only shortly after sunset and negative during most of the night. Positive EC fluxes of soluble glyoxal over oceans indicate the presence of an ocean surface organic microlayer (SML) and locate a glyoxal source within the SML. The origin of most atmospheric glyoxal, and possibly other oxygenated hydrocarbons over tropical oceans, remains unexplained and warrants further investigation.
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Coburn, S., I. Ortega, R. Thalman, B. Blomquist, C. W. Fairall, and R. Volkamer. "Measurements of diurnal variations and Eddy Covariance (EC) fluxes of glyoxal in the tropical marine boundary layer: description of the Fast LED-CE-DOAS instrument." Atmospheric Measurement Techniques Discussions 7, no. 6 (June 20, 2014): 6245–85. http://dx.doi.org/10.5194/amtd-7-6245-2014.
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Abstract. Here we present first Eddy Covariance (EC) measurements of fluxes of glyoxal, the smallest α-dicarbonyl product of hydrocarbon oxidation, and a precursor for secondary organic aerosol (SOA). The unique physical and chemical properties of glyoxal, i.e., high solubility in water (Henry's Law constant, KH = 4.2 × 105 M atm−1) and short atmospheric lifetime (~2 h at solar noon) make it a unique indicator species for organic carbon oxidation in the marine atmosphere. Previous reports of elevated glyoxal over oceans remain unexplained by atmospheric models. Here we describe a Fast Light Emitting Diode Cavity Enhanced Differential Optical Absorption Spectroscopy (Fast LED-CE-DOAS) instrument to measure diurnal variations and EC fluxes of glyoxal, and inform about its unknown sources. The fast in situ sensor is described, and first results are presented from a cruise deployment over the Eastern tropical Pacific Ocean (20° N to 10° S; 133° W to 85° W) as part of the Tropical Ocean Troposphere Exchange of Reactive Halogens and OVOC (TORERO) field experiment (January to March 2012). The Fast LED-CE-DOAS is a multispectral sensor that selectively and simultaneously measures glyoxal (CHOCHO), nitrogen dioxide (NO2), oxygen dimers (O4) and water vapor (H2O) with ~2 Hz time resolution, and a precision of ~40 pptv Hz−0.5 for glyoxal. The instrument is demonstrated to be a "white-noise" sensor suitable for EC flux measurements; further, highly sensitive and inherently calibrated glyoxal measurements are obtained from temporal averaging of data (~2 pptv detection limit over 1 h). The campaign averaged mixing ratio in the Southern Hemisphere (SH) is found to be 43 ± 9 pptv glyoxal, and is higher than in the Northern Hemisphere (NH: 32 ± 6 pptv; error reflects variability over multiple days). The diurnal variation of glyoxal in the MBL is measured for the first time, and mixing ratios vary by ~8 ppt (NH) and ~12 pptv (SH) over the course of 24 h. Consistently, maxima are observed at sunrise (NH: 35 ± 5 pptv; SH: 47 ± 7 pptv) and minima at dusk (NH: 27 ± 5 pptv; SH: 35 ± 8 pptv). Ours are the first EC flux measurements of glyoxal. In both hemispheres, the daytime flux was directed from the atmosphere into the ocean, indicating that the ocean is a net sink for glyoxal during the day. After sunset the ocean was a source for glyoxal to the atmosphere (positive flux) in the SH; this primary ocean source was operative throughout the night. In the NH, the nighttime flux was positive only shortly after sunset, and negative during most of the night. Positive EC fluxes of soluble glyoxal over oceans indicate the presence of an ocean surface organic microlayer (SML), and locate a glyoxal source within the SML. The origin of atmospheric glyoxal, and possibly other oxygenated hydrocarbons over tropical oceans warrants further investigation.
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Wang, Yapeng, Jinhua Tao, Liangxiao Cheng, Chao Yu, Zifeng Wang, and Liangfu Chen. "A Retrieval of Glyoxal from OMI over China: Investigation of the Effects of Tropospheric NO2." Remote Sensing 11, no. 2 (January 11, 2019): 137. http://dx.doi.org/10.3390/rs11020137.
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East China is the ‘hotspot’ of glyoxal (CHOCHO), especially over the Pearl River Delta (PRD) region, where glyoxal is yielded from the oxidation of aromatics. To better understand the glyoxal spatial-temporal characteristics over China and evaluate the effectiveness of atmospheric prevention efforts on the reduction of volatile organic compound (VOC) emissions, we present an algorithm for glyoxal retrieval using the Ozone Monitoring instrument (OMI) over China. The algorithm is based on the differential optical absorption spectroscopy (DOAS) and accounts for the interference of the tropospheric nitrogen dioxide (NO2) spatial-temporal distribution on glyoxal retrieval. We conduct a sensitively test based on a synthetic spectrum to optimize the fitting parameters set. It shows that the fitting interval of 430–458 nm and a 4th order polynomial are optimal for glyoxal retrieval when using the daily mean value of the earthshine spectrum in the Pacific region as a reference. In addition, tropospheric NO2 pre-fitted during glyoxal retrieval is first proposed and tested, which shows a ±10% variation compared with the reference scene. The interference of NO2 on glyoxal was further investigated based on the OMI observations, and the spatial distribution showed that changes in the NO2 concentration can affect the glyoxal result depending on the NO2 spatial distribution. A method to prefix NO2 during glyoxal retrieval is proposed in this study and is referred to as OMI-CAS. We perform an intercomparison of the glyoxal from the OMI-CAS with the seasonal datasets provided by different institutions for North China (NC), South China (SC), the Yangtze River Delta (YRD) and the ChuanYu (CY) region in southwestern China in the year 2005. The results show that our algorithm can obtain the glyoxal spatial and temporal variations in different regions over China. OMI-CAS has the best correlations with other datasets in summer, with the correlations between OMI-CAS and OMI-Harvard, OMI-CAS and OMI-IUP, and OMI-CAS and Sciamachy-IUP being 0.63, 0.67 and 0.67, respectively. Autumn results followed, with the correlations of 0.58, 0.36 and 0.48, respectively, over China. However, the correlations are less or even negative for spring and winter. From the regional perspective, SC has the best correlation compared with other regions, with R reaching 0.80 for OMI-CAS and OMI-IUP in summer. The discrepancies between different glyoxal datasets can be attributed to the fitting parameters and larger glyoxal retrieval uncertainties. Finally, useful recommendations are given based on the results comparison according to region and season.
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Shamsi, Anas, Khan M. Abdullah, Hina Usmani, Areeba Shahab, Hamza Hasan, and Imrana Naseem. "Glyoxal Induced Transition of Transferrin to Aggregates: Spectroscopic, Microscopic and Molecular Docking Insight." Current Pharmaceutical Biotechnology 20, no. 12 (October 18, 2019): 1028–36. http://dx.doi.org/10.2174/1389201020666190731122806.
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Background & Objective: The present study was aimed at characterizing the conformational alterations induced in human transferrin, the iron regulatory protein by glyoxal. Since protein aggregation is at the core of many disorders, thus interest in this domain has increased significantly during the past years. Methods: In our present study, the effect of glyoxal was monitored on human transferrin using multispectroscopic and multi-microscopic studies. Results: Intrinsic fluorescence spectroscopy suggested changes in native conformation of human transferrin evident by decreased fluorescence and blue shift in the presence of glyoxal. Further, extrinsic fluorescence was retorted and the results showed the formation of aggregates; apparent by increased Congo red (CR) absorbance, Thioflavin T (ThT) and ANS fluorescence and TEM of human transferrin in the presence of glyoxal. Molecular docking was also employed to see which residues are at core of human transferrin and glyoxal interaction. Reactive oxygen species (ROS) generation assays revealed enhanced ROS levels by human transferrin after treatment with glyoxal. Conclusion: Thus, our study proposes that glyoxal induces the formation of aggregates in human transferrin. These aggregates further generate ROS which are key players in the complications associated with diabetes mellitus, giving our study clinical perspective.
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Branco, Roberta V., Melissa L. E. Gutarra, Jose M. Guisan, Denise M. G. Freire, Rodrigo V. Almeida, and Jose M. Palomo. "Improving the Thermostability and Optimal Temperature of a Lipase from the Hyperthermophilic ArchaeonPyrococcus furiosusby Covalent Immobilization." BioMed Research International 2015 (2015): 1–8. http://dx.doi.org/10.1155/2015/250532.
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A recombinant thermostable lipase (Pf2001Δ60) from the hyperthermophilic ArchaeonPyrococcus furiosus(PFUL) was immobilized by hydrophobic interaction on octyl-agarose (octyl PFUL) and by covalent bond on aldehyde activated-agarose in the presence of DTT at pH = 7.0 (one-point covalent attachment) (glyoxyl-DTT PFUL) and on glyoxyl-agarose at pH 10.2 (multipoint covalent attachment) (glyoxyl PFUL). The enzyme’s properties, such as optimal temperature and pH, thermostability, and selectivity, were improved by covalent immobilization. The highest enzyme stability at 70°C for 48 h incubation was achieved for glyoxyl PFUL (around 82% of residual activity), whereas glyoxyl-DTT PFUL maintained around 69% activity, followed by octyl PFUL (27% remaining activity). Immobilization on glyoxyl-agarose improved the optimal temperature to 90°C, while the optimal temperature of octyl PFUL was 70°C. Also, very significant changes in activity with different substrates were found. In general, the covalent bond derivatives were more active than octyl PFUL. TheEvalue also depended substantially on the derivative and the conditions used. It was observed that the reaction of glyoxyl-DTT PFUL using methyl mandelate as a substrate at pH 7 presented the best results for enantioselectivityE=22and enantiomeric excess (ee (%) = 91).
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Chen, Ying, Wei Qin, Zehua Li, Zhihao Guo, Yuan Liu, Tong Lan, and Chu Wang. "Site-specific chemoproteomic profiling of targets of glyoxal." Future Medicinal Chemistry 11, no. 23 (December 2019): 2979–87. http://dx.doi.org/10.4155/fmc-2019-0221.
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Aim: Advanced glycation end products (AGE) are the biomarkers of aging and diabetes which are formed via reactions between glycating agents and biomacromolecules. However, no proteomic study has been reported to systematically investigate the protein substrates of AGEs. Results: In this paper, we used an aniline-based probe to capture the glyoxal-imine intermediate which is the transition sate of glyoxal-derived AGEs. Combined with the tandem orthogonal proteolysis activity-based protein profiling strategy, we successfully identified 962 lysines modified by glyoxal. Conclusion: Enzymes in glycolysis are heavily modified by glyoxal and our biochemical experiments showed that glyoxal can significantly inhibit the activity of GAPDH and glycolysis. These data indicated that AGEs modifications may contribute to pathological processes through impairing the glycolytic process.
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Averina, Elena, Johannes Konnerth, and Hendrikus W. G. van Herwijnen. "Protein Adhesives: Investigation of Factors Affecting Wet Strength of Alkaline Treated Proteins Crosslinked with Glyoxal." Polymers 14, no. 20 (October 15, 2022): 4351. http://dx.doi.org/10.3390/polym14204351.
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Proteins obtained as side-products from starch production (potato and corn proteins) were investigated for wood adhesives application. To improve the wet strength of protein-based adhesives, glyoxal was added as a crosslinking agent. The effect of glyoxal on the wet strength of protein-based adhesives was investigated at different pH, protein: glyoxal ratios and solid content. The alkaline pretreatment of proteins was carried out by two different methods which reduced the molecular weight of proteins to different extents. The effect of molecular weight reduction on the wet strength of protein-glyoxal adhesives was also observed. It was found that pH level affects wet strength more significantly compared to solid content and protein-to-crosslinker ratio. Potato and corn proteins crosslinked with glyoxal showed maximal wet strength results in an acidic pH range
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Walker, Hannah, Daniel Stone, Trevor Ingham, Sina Hackenberg, Danny Cryer, Shalini Punjabi, Katie Read, et al. "Observations and modelling of glyoxal in the tropical Atlantic marine boundary layer." Atmospheric Chemistry and Physics 22, no. 8 (April 27, 2022): 5535–57. http://dx.doi.org/10.5194/acp-22-5535-2022.
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Abstract. In situ field measurements of glyoxal at the surface in the tropical marine boundary layer have been made with a temporal resolution of a few minutes during two 4-week campaigns in June–July and August–September 2014 at the Cape Verde Atmospheric Observatory (CVAO; 16∘52′ N, 24∘52′ W). Using laser-induced phosphorescence spectroscopy with an instrumental detection limit of ∼1 pptv (1 h averaging), volume mixing ratios up to ∼10 pptv were observed, with 24 h averaged mixing ratios of 4.9 and 6.3 pptv observed during the first and second campaigns, respectively. Some diel behaviour was observed, but this was not marked. A box model using the detailed Master Chemical Mechanism (version 3.2) and constrained with detailed observations of a suite of species co-measured at the observatory was used to calculate glyoxal mixing ratios. There is a general model underestimation of the glyoxal observations during both campaigns, with mean midday (11:00–13:00) observed-to-modelled ratios for glyoxal of 3.2 and 4.2 for the two campaigns, respectively, and higher ratios at night. A rate of production analysis shows the dominant sources of glyoxal in this environment to be the reactions of OH with glycolaldehyde and acetylene, with a significant contribution from the reaction of OH with the peroxide HC(O)CH2OOH, which itself derives from OH oxidation of acetaldehyde. Increased mixing ratios of acetaldehyde, which is unconstrained and potentially underestimated in the base model, can significantly improve the agreement between the observed and modelled glyoxal during the day. Mean midday observed-to-modelled glyoxal ratios decreased to 1.3 and 1.8 for campaigns 1 and 2, respectively, on constraint to a fixed acetaldehyde mixing ratio of 200 pptv, which is consistent with recent airborne measurements near CVAO. However, a significant model under-prediction remains at night. The model showed limited sensitivity to changes in deposition rates of model intermediates and the uptake of glyoxal onto aerosol compared with sensitivity to uncertainties in chemical precursors. The midday (11:00–13:00) mean modelled glyoxal mixing ratio decreased by factors of 0.87 and 0.90 on doubling the deposition rates of model intermediates and aerosol uptake of glyoxal, respectively, and increased by factors of 1.10 and 1.06 on halving the deposition rates of model intermediates and aerosol uptake of glyoxal, respectively. Although measured levels of monoterpenes at the site (total of ∼1 pptv) do not significantly influence the model calculated levels of glyoxal, transport of air from a source region with high monoterpene emissions to the site has the potential to give elevated mixing ratios of glyoxal from monoterpene oxidation products, but the values are highly sensitive to the deposition rates of these oxidised intermediates. A source of glyoxal derived from production in the ocean surface organic microlayer cannot be ruled out on the basis of this work and may be significant at night.
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Banerjee, Sauradipta. "Effect of Glyoxal Modification on a Critical Arginine Residue (Arg-31α) of Hemoglobin: Physiological Implications of Advanced Glycated end Product an in vitro Study." Protein & Peptide Letters 27, no. 8 (September 24, 2020): 770–81. http://dx.doi.org/10.2174/0929866526666191125101122.
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Background: Non-enzymatic protein glycation is involved in structure and stability changes that impair protein functionality, resulting in several human diseases, such as diabetes and amyloidotic neuropathies (Alzheimer’s disease, Parkinson’s disease and Andrade’s syndrome). Glyoxal, an endogenous reactive oxoaldehyde, increases in diabetes and reacts with several proteins to form advanced glycation end products through Maillard-like reaction. Objective: Human hemoglobin, the most abundant protein in blood cells is subjected to nonenzymatic modification by reactive oxoaldehydes in diabetic condition. In the present study, the effect of a low concentration of glyoxal (5 μM) on hemoglobin (10 μM) has been investigated following a period of 30 days incubation in vitro. Methods: Different techniques, mostly biophysical and spectroscopic (e.g. circular dichroism, differential scanning calorimetric study, dynamic light scattering, mass spectrometry, etc.) were used to study glyoxal-induced changes of hemoglobin. Results: Glyoxal-treated hemoglobin exhibits decreased absorbance around 280 nm, decreased fluorescence and reduced surface hydrophobicity compared to normal hemoglobin. Glyoxal treatment enhances the stability of hemoglobin and lowers its susceptibility to thermal aggregation compared to control hemoglobin as seen by different studies. Finally, peptide mass fingerprinting study showed glyoxal to modify an arginine residue of α-chain of hemoglobin (Arg-31α) to hydroimidazolone. Conclusion: Increased level of glyoxal in diabetes mellitus as well as its high reactivity may cause modifications of the heme protein. Thus, considering the significance of glyoxal-induced protein modification under physiological conditions, the observation appears clinically relevant in terms of understanding hydroimidazolone-mediated protein modification under in vivo conditions.
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Galloway, M. M., P. S. Chhabra, A. W. H. Chan, J. D. Surratt, R. C. Flagan, J. H. Seinfeld, and F. N. Keutsch. "Glyoxal uptake on ammonium sulphate seed aerosol: reaction products and reversibility of uptake under dark and irradiated conditions." Atmospheric Chemistry and Physics 9, no. 10 (May 25, 2009): 3331–45. http://dx.doi.org/10.5194/acp-9-3331-2009.
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Abstract. Chamber studies of glyoxal uptake onto ammonium sulphate aerosol were performed under dark and irradiated conditions to gain further insight into processes controlling glyoxal uptake onto ambient aerosol. Organic fragments from glyoxal dimers and trimers were observed within the aerosol under dark and irradiated conditions. Glyoxal monomers and oligomers were the dominant organic compounds formed under the conditions of this study; glyoxal oligomer formation and overall organic growth were found to be reversible under dark conditions. Analysis of high-resolution time-of-flight aerosol mass spectra provides evidence for irreversible formation of carbon-nitrogen (C-N) compounds in the aerosol. We have identified 1H-imidazole-2-carboxaldehyde as one C-N product. To the authors' knowledge, this is the first time C-N compounds resulting from condensed phase reactions with ammonium sulphate seed have been detected in aerosol. Organosulphates were not detected under dark conditions. However, active photochemistry was found to occur within aerosol during irradiated experiments. Carboxylic acids and organic esters were identified within the aerosol. An organosulphate, which had been previously assigned as glyoxal sulphate in ambient samples and chamber studies of isoprene oxidation, was observed only in the irradiated experiments. Comparison with a laboratory synthesized standard and chemical considerations strongly suggest that this organosulphate is glycolic acid sulphate, an isomer of the previously proposed glyoxal sulphate. Our study shows that reversibility of glyoxal uptake should be taken into account in SOA models and also demonstrates the need for further investigation of C-N compound formation and photochemical processes, in particular organosulphate formation.
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Ren, Dakai, and Kaichang Li. "Development of wet strength additives from wheat gluten." Holzforschung 59, no. 6 (November 1, 2005): 598–603. http://dx.doi.org/10.1515/hf.2005.097.
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Abstract Glyoxal-polyacrylamide (GPA) resin is widely used as a wet strength additive for various paper and paperboard products. However, GPA resin is derived from petrochemicals and contributes to contaminants in the recycling of papers. Wheat gluten is one of the most abundant proteins in nature. This research investigated how to convert gliadin, a key component of wheat gluten, to an effective temporary wet-strength additive. Gliadin was first modified with glycidyltrimethylammonium chloride (GTA) to generate positively charged GTA-gliadin. Further reaction of GTA-gliadin with glyoxal yielded GTA-gliadin-glyoxal resins. Conditions for these two reactions were investigated to maximize the dry and wet strengths of GTA-gliadin-glyoxal-treated paper. At a dosage of 1 wt.%, GTA-gliadin-glyoxal resin was comparable to GPA resin in terms of enhancing the dry and wet strengths of treated paper.
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Galloway, M. M., P. S. Chhabra, A. W. H. Chan, J. D. Surratt, R. C. Flagan, J. H. Seinfeld, and F. N. Keutsch. "Glyoxal uptake on ammonium sulphate seed aerosol: reaction products and reversibility of uptake under dark and irradiated conditions." Atmospheric Chemistry and Physics Discussions 8, no. 6 (December 12, 2008): 20799–838. http://dx.doi.org/10.5194/acpd-8-20799-2008.
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Abstract. Chamber studies of glyoxal uptake onto neutral ammonium sulphate aerosol were performed under dark and irradiated conditions to gain further insight into processes controlling glyoxal uptake onto ambient aerosol. Organic fragments from glyoxal dimers and trimers were observed within the aerosol under dark and irradiated conditions; glyoxal oligomer formation and overall organic growth were found to be reversible under dark conditions. Analysis of high-resolution time-of-flight aerosol mass spectra provides evidence for irreversible formation of carbon-nitrogen (C-N) compounds in the aerosol. These compounds are likely to be imidazoles formed by reaction of glyoxal with the ammonium sulphate seed. To the authors' knowledge, this is the first time C-N compounds resulting from condensed phase reactions with ammonium sulphate seed have been detected in aerosol. Organosulphates were not detected under dark conditions. However, active oxidative photochemistry, similar to that found in cloud processing, was found to occur within aerosol during irradiated experiments. Organosulphates, carboxylic acids, and organic esters were identified within the aerosol. Our study suggests that both C-N compound formation and photochemical processes should be considered in models of secondary organic aerosol formation via glyoxal.
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Lerot, C., T. Stavrakou, I. De Smedt, J. F. Müller, and M. Van Roozendael. "Glyoxal vertical columns from GOME-2 backscattered light measurements and comparisons with a global model." Atmospheric Chemistry and Physics Discussions 10, no. 9 (September 6, 2010): 21147–88. http://dx.doi.org/10.5194/acpd-10-21147-2010.
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Abstract. Glyoxal vertical column densities have been retrieved from nadir backscattered radiances measured from 2007 to 2009 by the spaceborne GOME-2/METOP-A sensor. The retrieval algorithm is based on the DOAS technique and optimized settings have been used to determine glyoxal slant columns. The liquid water absorption is accounted for using a two-step DOAS approach, leading to a drastic improvement of the fit quality over remote clear water oceans. Air mass factors are calculated by means of look-up tables of weighting functions pre-calculated with the LIDORT v3.3 radiative transfer model and using a priori glyoxal vertical distributions provided by the IMAGESv2 chemical transport model. The total error estimate comprises random and systematic errors associated to the DOAS fit, the air mass factor calculation and the cloud correction. The highest glyoxal vertical column densities are mainly observed in continental tropical regions, while the mid-latitude columns strongly depend on the season with maximum values during warm months. An anthropogenic signature is also observed in highly populated regions of Asia. Comparisons with glyoxal columns simulated with IMAGESv2 in different regions of the world generally point to a missing glyoxal source, most probably of biogenic origin.
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Lerot, C., T. Stavrakou, I. De Smedt, J. F. Müller, and M. Van Roozendael. "Glyoxal vertical columns from GOME-2 backscattered light measurements and comparisons with a global model." Atmospheric Chemistry and Physics 10, no. 24 (December 17, 2010): 12059–72. http://dx.doi.org/10.5194/acp-10-12059-2010.
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Abstract. Glyoxal vertical column densities have been retrieved from nadir backscattered radiances measured from 2007 to 2009 by the spaceborne GOME-2/METOP-A sensor. The retrieval algorithm is based on the DOAS technique and optimized settings have been used to determine glyoxal slant columns. The liquid water absorption is accounted for using a two-step DOAS approach, leading to a drastic improvement of the fit quality over remote clear water oceans. Air mass factors are calculated by means of look-up tables of weighting functions pre-calculated with the LIDORT v3.3 radiative transfer model and using a priori glyoxal vertical distributions provided by the IMAGESv2 chemical transport model. The total error estimate comprises random and systematic errors associated to the DOAS fit, the air mass factor calculation and the cloud correction. The highest glyoxal vertical column densities are mainly observed in continental tropical regions, while the mid-latitude columns strongly depend on the season with maximum values during warm months. An anthropogenic signature is also observed in highly populated regions of Asia. Comparisons with glyoxal columns simulated with IMAGESv2 in different regions of the world generally point to a missing glyoxal source, most probably of biogenic origin.
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Lacko, Michal, Felix Piel, Andreas Mauracher, and Patrik Španěl. "Chemical ionization of glyoxal and formaldehyde with H3O+ ions using SIFT-MS under variable system humidity." Physical Chemistry Chemical Physics 22, no. 18 (2020): 10170–78. http://dx.doi.org/10.1039/d0cp00297f.
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Ismayilova, S. Z. "THE CHELATING POLYIMINE BASED ON P-PHENYLENEDIAMINE AND GLYOXAL." Chemical Problems 18, no. 4 (2020): 445–50. http://dx.doi.org/10.32737/2221-8688-2020-4-445-450.
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Condensation of p-phenylenediamine and glyoxal at a molar ratio of 1: 1 made it possible to synthesize a new polyimine with chelating ability. The complexation of this polyimine with transition metals was studied and the composition and structure of the complexes obtained were explored by means of IR, electron spectroscopy, EPR, derivatography, and elemental analysis.
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Xi, Xuedong, Antonio Pizzi, Hong Lei, Guanben Du, Xiaojian Zhou, and Yuying Lin. "Characterization and Preparation of Furanic-Glyoxal Foams." Polymers 12, no. 3 (March 20, 2020): 692. http://dx.doi.org/10.3390/polym12030692.
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Synthetic foams have become an essential industrial product for a great variety of applications. Furfuryl alcohol, as a biomass chemical, was reacted with glyoxal at room temperature to prepare furanic-glyoxal rigid foams, and p-toluenesulfonic acid was used as a catalyst to initiate the reaction. Foams with different molar ratios (furfuryl alcohol/glyoxal) were prepared in this work, and uniform cells foams have been obtained. Their compression resistance, 24-h water absorption, density, and other basic properties were tested. Scanning electron microscopy (SEM) was used to observe the cellular morphology of the foams prepared, thermogravimetric analysis (TGA) helped to understand their thermal and combustion properties, and FTIR and Matrix Assisted Laser Desorption Ionisation Time of Flight (MALDI ToF) mass spectroscopy to explain the structure of the resulting foams to clarify the reactions occurring during foaming. The results show that the compression resistance of furanic-glyoxal foams declined as the furfuryl alcohol/glyoxal ratio decreases also. SEM observations revealed that foams with open-cell were obtained when furfuryl alcohol was added in greater amounts, and more closed cell structures were formed as the proportion of glyoxal increased. TGA results showed that the initial ignition temperature of furanic-glyoxal foams is ~200 °C higher than that of wood, and the smaller comprehensive combustion index S (about 0.15 × 10−7 (%2 K−3 min−2)) indicates that the foam burns slowly and has poor flammability, that is, it is not easy to burn.
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Lerot, Christophe, François Hendrick, Michel Van Roozendael, Leonardo M. A. Alvarado, Andreas Richter, Isabelle De Smedt, Nicolas Theys, et al. "Glyoxal tropospheric column retrievals from TROPOMI – multi-satellite intercomparison and ground-based validation." Atmospheric Measurement Techniques 14, no. 12 (December 10, 2021): 7775–807. http://dx.doi.org/10.5194/amt-14-7775-2021.
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Abstract. We present the first global glyoxal (CHOCHO) tropospheric column product derived from the TROPOspheric Monitoring Instrument (TROPOMI) on board the Sentinel-5 Precursor satellite. Atmospheric glyoxal results from the oxidation of other non-methane volatile organic compounds (NMVOCs) and from direct emissions caused by combustion processes. Therefore, this product is a useful indicator of VOC emissions. It is generated with an improved version of the BIRA-IASB scientific retrieval algorithm relying on the differential optical absorption spectroscopy (DOAS) approach. Among the algorithmic updates, the DOAS fit now includes corrections to mitigate the impact of spectral misfits caused by scene brightness inhomogeneity and strong NO2 absorption. The product comes along with a full error characterization, which allows for providing random and systematic error estimates for every observation. Systematic errors are typically in the range of 1 ×1014–3 ×1014 molec. cm−2 (∼30 %–70 % in emission regimes) and originate mostly from a priori data uncertainties and spectral interferences with other absorbing species. The latter may be at the origin, at least partly, of an enhanced glyoxal signal over equatorial oceans, and further investigation is needed to mitigate them. Random errors are large (>6×1014 molec. cm−2) but can be reduced by averaging observations in space and/or time. Benefiting from a high signal-to-noise ratio and a large number of small-size observations, TROPOMI provides glyoxal tropospheric column fields with an unprecedented level of detail. Using the same retrieval algorithmic baseline, glyoxal column data sets are also generated from the Ozone Monitoring Instrument (OMI) on Aura and from the Global Ozone Monitoring Experiment-2 (GOME-2) on board Metop-A and Metop-B. Those four data sets are intercompared over large-scale regions worldwide and show a high level of consistency. The satellite glyoxal columns are also compared to glyoxal columns retrieved from ground-based Multi-AXis DOAS (MAX-DOAS) instruments at nine stations in Asia and Europe. In general, the satellite and MAX-DOAS instruments provide consistent glyoxal columns both in terms of absolute values and variability. Correlation coefficients between TROPOMI and MAX-DOAS glyoxal columns range between 0.61 and 0.87. The correlation is only poorer at one mid-latitude station, where satellite data appear to be biased low during wintertime. The mean absolute glyoxal columns from satellite and MAX-DOAS generally agree well for low/moderate columns with differences of less than 1×1014 molec. cm−2. A larger bias is identified at two sites where the MAX-DOAS columns are very large. Despite this systematic bias, the consistency of the satellite and MAX-DOAS glyoxal seasonal variability is high.
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Knote, C., A. Hodzic, J. L. Jimenez, R. Volkamer, J. J. Orlando, S. Baidar, J. Brioude, et al. "Simulation of semi-explicit mechanisms of SOA formation from glyoxal in aerosol in a 3-D model." Atmospheric Chemistry and Physics 14, no. 12 (June 24, 2014): 6213–39. http://dx.doi.org/10.5194/acp-14-6213-2014.
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Abstract. New pathways to form secondary organic aerosol (SOA) have been postulated recently. Glyoxal, the smallest dicarbonyl, is one of the proposed precursors. It has both anthropogenic and biogenic sources, and readily partitions into the aqueous phase of cloud droplets and deliquesced particles where it undergoes both reversible and irreversible chemistry. In this work we extend the regional scale chemistry transport model WRF-Chem to include detailed gas-phase chemistry of glyoxal formation as well as a state-of-the-science module describing its partitioning and reactions in the aerosol aqueous-phase. A comparison of several proposed mechanisms is performed to quantify the relative importance of different formation pathways and their regional variability. The CARES/CalNex campaigns over California in summer 2010 are used as case studies to evaluate the model against observations. A month-long simulation over the continental United States (US) enables us to extend our results to the continental scale. In all simulations over California, the Los Angeles (LA) basin was found to be the hot spot for SOA formation from glyoxal, which contributes between 1% and 15% of the model SOA depending on the mechanism used. Our results indicate that a mechanism based only on a reactive (surface limited) uptake coefficient leads to higher SOA yields from glyoxal compared to a more detailed description that considers aerosol phase state and chemical composition. In the more detailed simulations, surface uptake is found to give the highest SOA mass yields compared to a volume process and reversible formation. We find that the yields of the latter are limited by the availability of glyoxal in aerosol water, which is in turn controlled by an increase in the Henry's law constant depending on salt concentrations ("salting-in"). A time dependence in this increase prevents substantial partitioning of glyoxal into aerosol water at high salt concentrations. If this limitation is removed, volume pathways contribute > 20% of glyoxal-SOA mass, and the total mass formed (5.8% of total SOA in the LA basin) is about a third of the simple uptake coefficient formulation without consideration of aerosol phase state and composition. Results from the continental US simulation reveal the much larger potential to form glyoxal-SOA over the eastern continental US. Interestingly, the low concentrations of glyoxal-SOA over the western continental US are not due to the lack of a potential to form glyoxal-SOA here. Rather these small glyoxal-SOA concentrations reflect dry conditions and high salt concentrations, and the potential to form SOA mass here will strongly depend on the water associated with particles.
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Kudyakov, Alexander I., and Alexey B. Steshenko. "Study of Hardened Cement Paste with Crystalline Glyoxal." Key Engineering Materials 683 (February 2016): 113–17. http://dx.doi.org/10.4028/www.scientific.net/kem.683.113.
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The results of studies of modified hardened cement paste with glyoxal-containing additive are given in this article. The goal was to study the patterns of influence of crystalline glyoxal on compressive strength of hardened cement paste. Introduction of crystalline glyoxal in the amount of 0.01-0.05% by weight of cement in the cement paste enables the increase in the compressive strength of hardened cement paste in 28 days by 7-8%. The studies have established that the introduction of crystalline glyoxal in the amount of 0.1-1% by weight of cement is inefficient; there is a decrease of the strength values in comparison with control samples. The results of microstructure investigation (of control samples and samples of the modified hardened cement paste) have shown that the introduction of crystalline glyoxal in the amount of 0.01-0.05% by weight of cement provides the structure of hardened cement paste that does not contain sedimentative pores and increases the quantity of hydroaluminate.
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Rodigast, M., A. Mutzel, J. Schindelka, and H. Herrmann. "A new source of methyl glyoxal in the aqueous phase." Atmospheric Chemistry and Physics Discussions 15, no. 21 (November 12, 2015): 31891–924. http://dx.doi.org/10.5194/acpd-15-31891-2015.
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Abstract. Carbonyl compounds are ubiquitous in atmospheric multiphase system participating in gas, particle, and aqueous-phase chemistry. One important compound is methyl ethyl ketone (MEK), as it is detected in significant amounts in the gas phase as well as in cloud water, ice, and rain. Consequently, it can be expected that MEK influences the liquid phase chemistry. Therefore, the oxidation of MEK and the formation of corresponding oxidation products were investigated in the aqueous phase. Several oxidation products were identified from the oxidation with OH radicals, including 2,3-butanedione, hydroxyacetone, and methyl glyoxal. The molar yields were 29.5 % for 2,3-butanedione, 3.0 % for hydroxyacetone, and 9.5 % for methyl glyoxal. Since methyl glyoxal is often related to the formation of organics in the aqueous phase, MEK should be considered for the formation of aqueous secondary organic aerosol (aqSOA). Based on the experimentally obtained data, a reaction mechanism for the formation of methyl glyoxal has been developed and evaluated with a model study. Besides known rate constants, the model contains measured photolysis rate constants for MEK (kp = 5 × 10−5 s−1), 2,3-butanedione (kp = 9 × 10−6 s−1), methyl glyoxal (kp = 3 × 10−5 s−1), and hydroxyacetone (kp = 2 × 10−5 s−1). From the model predictions, a branching ratio of 60/40 for primary/secondary H-atom abstraction at the MEK skeleton was found. This branching ratio reproduces the experiment results very well, especially the methyl glyoxal formation, which showed excellent agreement. Overall, this study demonstrates MEK as a methyl glyoxal precursor compound for the first time.
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Lim, Y. B., Y. Tan, and B. J. Turpin. "Chemical insights, explicit chemistry, and yields of secondary organic aerosol from OH radical oxidation of methylglyoxal and glyoxal in the aqueous phase." Atmospheric Chemistry and Physics 13, no. 17 (September 3, 2013): 8651–67. http://dx.doi.org/10.5194/acp-13-8651-2013.
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Abstract. Atmospherically abundant, volatile water-soluble organic compounds formed through gas-phase chemistry (e.g., glyoxal (C2), methylglyoxal (C3), and acetic acid) have great potential to form secondary organic aerosol (SOA) via aqueous chemistry in clouds, fogs, and wet aerosols. This paper (1) provides chemical insights into aqueous-phase OH-radical-initiated reactions leading to SOA formation from methylglyoxal and (2) uses this and a previously published glyoxal mechanism (Lim et al., 2010) to provide SOA yields for use in chemical transport models. Detailed reaction mechanisms including peroxy radical chemistry and a full kinetic model for aqueous photochemistry of acetic acid and methylglyoxal are developed and validated by comparing simulations with the experimental results from previous studies (Tan et al., 2010, 2012). This new methylglyoxal model is then combined with the previous glyoxal model (Lim et al., 2010), and is used to simulate the profiles of products and to estimate SOA yields. At cloud-relevant concentrations (~ 10−6 − ~ 10−3 M; Munger et al., 1995) of glyoxal and methylglyoxal, the major photooxidation products are oxalic acid and pyruvic acid, and simulated SOA yields (by mass) are ~ 120% for glyoxal and ~ 80% for methylglyoxal. During droplet evaporation oligomerization of unreacted methylglyoxal/glyoxal that did not undergo aqueous photooxidation could enhance yields. In wet aerosols, where total dissolved organics are present at much higher concentrations (~ 10 M), the major oxidation products are oligomers formed via organic radical–radical reactions, and simulated SOA yields (by mass) are ~ 90% for both glyoxal and methylglyoxal. Non-radical reactions (e.g., with ammonium) could enhance yields.
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Galloway, M. M., A. J. Huisman, L. D. Yee, A. W. H. Chan, C. L. Loza, J. H. Seinfeld, and F. N. Keutsch. "Yields of oxidized volatile organic compounds during the OH radical initiated oxidation of isoprene, methyl vinyl ketone, and methacrolein under high-NO<sub>x</sub> conditions." Atmospheric Chemistry and Physics 11, no. 21 (November 2, 2011): 10779–90. http://dx.doi.org/10.5194/acp-11-10779-2011.
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Abstract. We present first-generation and total production yields of glyoxal, methylglyoxal, glycolaldehyde, and hydroxyacetone from the oxidation of isoprene, methyl vinyl ketone (MVK), and methacrolein (MACR) with OH under high NOx conditions. Several of these first-generation yields are not included in commonly used chemical mechanisms, such as the Leeds Master Chemical Mechanism (MCM) v. 3.2. The first-generation yield of glyoxal from isoprene was determined to be 2.1 (±0.6)%. Inclusion of first-generation production of glyoxal, glycolaldehyde and hydroxyacetone from isoprene greatly improves performance of an MCM based model during the initial part of the experiments. In order to further improve performance of the MCM based model, higher generation glyoxal production was reduced by lowering the first-generation yield of glyoxal from C5 hydroxycarbonyls. The results suggest that glyoxal production from reaction of OH with isoprene under high NOx conditions can be approximated by inclusion of a first-generation production term together with secondary production only via glycolaldehyde. Analogously, methylglyoxal production can be approximated by a first-generation production term from isoprene, and secondary production via MVK, MACR and hydroxyacetone. The first-generation yields reported here correspond to less than 5% of the total oxidized yield from isoprene and thus only have a small effect on the fate of isoprene. However, due to the abundance of isoprene, the combination of first-generation yields and reduced higher generation production of glyoxal from C5 hydroxycarbonyls is important for models that include the production of the small organic molecules from isoprene.
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Solís-Calero, C., J. Ortega-Castro, A. Hernández-Laguna, J. Frau, and F. Muñoz. "A DFT study of the carboxymethyl-phosphatidylethanolamine formation from glyoxal and phosphatidylethanolamine surface. Comparison with the formation of N(ε)-(carboxymethyl)lysine from glyoxal and l-lysine." Physical Chemistry Chemical Physics 17, no. 12 (2015): 8210–22. http://dx.doi.org/10.1039/c4cp05360e.
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Shi, Qiuju, Weina Zhang, Yuemeng Ji, Jiaxin Wang, Dandan Qin, Jiangyao Chen, Yanpeng Gao, Guiying Li, and Taicheng An. "Enhanced uptake of glyoxal at the acidic nanoparticle interface: implications for secondary organic aerosol formation." Environmental Science: Nano 7, no. 4 (2020): 1126–35. http://dx.doi.org/10.1039/d0en00016g.
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Lawson, S. J., P. W. Selleck, I. E. Galbally, M. D. Keywood, M. J. Harvey, C. Lerot, D. Helmig, and Z. Ristovski. "Seasonal in situ observations of glyoxal and methylglyoxal over the temperate oceans of the Southern Hemisphere." Atmospheric Chemistry and Physics Discussions 14, no. 15 (August 25, 2014): 21659–708. http://dx.doi.org/10.5194/acpd-14-21659-2014.
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Abstract. Dicarbonyls glyoxal and methylglyoxal have been measured with 2,4-dinitrophenylhydrazine (2,4-DNPH) cartridges and high performance liquid chromatography (HPLC), optimised for dicarbonyl detection, in clean marine air over the temperate Southern Hemisphere (SH) oceans. Measurements of a range of dicarbonyl precursors (volatile organic compounds, VOCs) were made in parallel. These are the first in situ measurements of glyoxal and methylglyoxal over the remote temperate oceans. Six 24 h samples were collected in late summer (February–March) over the Chatham Rise in the South West Pacific Ocean during the Surface Ocean Aerosol Production (SOAP) voyage in 2012, while 34 24 h samples were collected at Cape Grim Baseline Air Pollution Station in late winter (August–September) 2011. Average glyoxal mixing ratios in clean marine air were 7 ppt at Cape Grim, and 24 ppt over Chatham Rise. Average methylglyoxal mixing ratios in clean marine air were 28 ppt at Cape Grim and 12 ppt over Chatham Rise. The mixing ratios of glyoxal at Cape Grim are the lowest observed over the remote oceans, while mixing ratios over Chatham Rise are in good agreement with other temperate and tropical observations, including concurrent MAX-DOAS observations. Methylglyoxal mixing ratios at both sites are comparable to the only other marine methylglyoxal observations available over the tropical Northern Hemisphere (NH) ocean. Ratios of glyoxal : methylglyoxal > 1 over Chatham Rise but < 1 at Cape Grim, suggesting different formation and/or loss processes or rates dominate at each site. Dicarbonyl precursor VOCs, including isoprene and monoterpenes, are used to calculate an upper estimate yield of glyoxal and methylglyoxal in the remote marine boundary layer and explain at most 1–3 ppt of dicarbonyls observed, corresponding to 11 and 17% of the observed glyoxal and 28 and 10% of the methylglyoxal at Chatham Rise and Cape Grim, respectively, highlighting a significant but as yet unknown production mechanism. Glyoxal surface observations from both sites were converted to vertical columns and compared to average vertical column densities (VCDs) from GOME-2 satellite retrievals. Both satellite columns and in situ observations are higher in summer than winter, however satellite vertical column densities exceeded the surface observations by more than 1.5 × 1014 molecules cm−2 at both sites. This discrepancy may be due to the incorrect assumption that all glyoxal observed by satellite is within the boundary layer, or may be due to challenges retrieving low VCDs of glyoxal over the oceans due to interferences by liquid water absorption, or use of an inappropriate normalisation reference value in the retrieval algorithm. This study provides much needed data to verify the presence of these short lived gases over the remote ocean and provide further evidence of an as yet unidentified source of both glyoxal and also methylglyoxal over the remote oceans.
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Lange, Jessica N., Kyle D. Wood, John Knight, Dean G. Assimos, and Ross P. Holmes. "Glyoxal Formation and Its Role in Endogenous Oxalate Synthesis." Advances in Urology 2012 (2012): 1–5. http://dx.doi.org/10.1155/2012/819202.
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Calcium oxalate kidney stones are a common condition affecting many people in the United States. The concentration of oxalate in urine is a major risk factor for stone formation. There is evidence that glyoxal metabolism may be an important contributor to urinary oxalate excretion. Endogenous sources of glyoxal include the catabolism of carbohydrates, proteins, and fats. Here, we review all the known sources of glyoxal as well as its relationship to oxalate synthesis and crystal formation.
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Yan, Yutao, Youming Dong, Jianzhang Li, Shifeng Zhang, Changlei Xia, Sheldon Q. Shi, and Liping Cai. "Enhancement of mechanical and thermal properties of Poplar through the treatment of glyoxal-urea/nano-SiO2." RSC Advances 5, no. 67 (2015): 54148–55. http://dx.doi.org/10.1039/c5ra07294h.
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An environmental-friendly glyoxal-urea (GU) resin is synthesized from urea and glyoxal, and combined with nano-SiO2 to treat Poplar wood and endow it superior mechanical and thermal properties.
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Lawson, S. J., P. W. Selleck, I. E. Galbally, M. D. Keywood, M. J. Harvey, C. Lerot, D. Helmig, and Z. Ristovski. "Seasonal in situ observations of glyoxal and methylglyoxal over the temperate oceans of the Southern Hemisphere." Atmospheric Chemistry and Physics 15, no. 1 (January 12, 2015): 223–40. http://dx.doi.org/10.5194/acp-15-223-2015.
Full textAbstract:
Abstract. The dicarbonyls glyoxal and methylglyoxal have been measured with 2,4-dinitrophenylhydrazine (2,4-DNPH) cartridges and high-performance liquid chromatography (HPLC), optimised for dicarbonyl detection, in clean marine air over the temperate Southern Hemisphere (SH) oceans. Measurements of a range of dicarbonyl precursors (volatile organic compounds, VOCs) were made in parallel. These are the first in situ measurements of glyoxal and methylglyoxal over the remote temperate oceans. Six 24 h samples were collected in summer (February–March) over the Chatham Rise in the south-west Pacific Ocean during the Surface Ocean Aerosol Production (SOAP) voyage in 2012, while 34 24 h samples were collected at Cape Grim Baseline Air Pollution Station in the late winter (August–September) of 2011. Average glyoxal mixing ratios in clean marine air were 7 ppt at Cape Grim and 23 ppt over Chatham Rise. Average methylglyoxal mixing ratios in clean marine air were 28 ppt at Cape Grim and 10 ppt over Chatham Rise. The mixing ratios of glyoxal at Cape Grim are the lowest observed over the remote oceans, while mixing ratios over Chatham Rise are in good agreement with other temperate and tropical observations, including concurrent Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) observations. Methylglyoxal mixing ratios at both sites are comparable to the only other marine methylglyoxal observations available over the tropical Northern Hemisphere (NH) ocean. Ratios of glyoxal : methylglyoxal > 1 over Chatham Rise but < 1 at Cape Grim suggest that a different formation and/or loss processes or rates dominate at each site. Dicarbonyl precursor VOCs, including isoprene and monoterpenes, are used to calculate an upper-estimate yield of glyoxal and methylglyoxal in the remote marine boundary layer and explain at most 1–3 ppt of dicarbonyls observed, corresponding to 10% and 17% of the observed glyoxal and 29 and 10% of the methylglyoxal at Chatham Rise and Cape Grim, respectively, highlighting a significant but as yet unknown production mechanism. Surface-level glyoxal observations from both sites were converted to vertical columns and compared to average vertical column densities (VCDs) from GOME-2 satellite retrievals. Both satellite columns and in situ observations are higher in summer than winter; however, satellite vertical column densities exceeded the surface observations by more than 1.5 × 1014 molecules cm−2 at both sites. This discrepancy may be due to the incorrect assumption that all glyoxal observed by satellite is within the boundary layer, or it may be due to challenges retrieving low VCDs of glyoxal over the oceans due to interferences by liquid water absorption or the use of an inappropriate normalisation reference value in the retrieval algorithm. This study provides much-needed data to verify the presence of these short-lived gases over the remote ocean and provide further evidence of an as yet unidentified source of both glyoxal and also methylglyoxal over the remote oceans.
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Chan Miller, C., G. Gonzalez Abad, H. Wang, X. Liu, T. Kurosu, D. J. Jacob, and K. Chance. "Glyoxal retrieval from the Ozone Monitoring Instrument." Atmospheric Measurement Techniques 7, no. 11 (November 25, 2014): 3891–907. http://dx.doi.org/10.5194/amt-7-3891-2014.
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Abstract. We present an algorithm for the retrieval of glyoxal from backscattered solar radiation, and apply it to spectra measured by the Ozone Monitoring Instrument (OMI). The algorithm is based on direct spectrum fitting, and adopts a two-step fitting routine to account for liquid water absorption. Previous studies have shown that glyoxal retrieval algorithms are highly sensitive to the position of the spectral fit window. This dependence was systematically tested on real and simulated OMI spectra. We find that a combination of errors resulting from uncertainties in reference cross sections and spectral features associated with the Ring effect are consistent with the fit-window dependence observed in real spectra. This implies an optimal fitting window of 435–461 nm, consistent with previous satellite glyoxal retrievals. The results from the retrieval of simulated spectra also support previous findings that have suggested that glyoxal is sensitive to NO2 cross-section temperature. The retrieval window limits of the liquid water retrieval are also tested. A retrieval window 385–470 nm reduces interference with strong spectral features associated with sand. We show that cross-track dependent offsets (stripes) present in OMI can be corrected using offsets derived from retrieved slant columns over the Sahara, and apply the correction to OMI data. Average glyoxal columns are on average lower than those of previous studies likely owing to the choice of reference sector for offset correction. OMI VCDs (vertical column densities)are lower compared to other satellites over the tropics and Asia during the monsoon season, suggesting that the new retrieval is less sensitive to water vapour abundance. Consequently we do not see significant glyoxal enhancements over tropical oceans. OMI-derived glyoxal-to-formaldehyde ratios over biogenic and anthropogenic source regions are consistent with surface observations.
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Miller, C. C., G. G. Abad, H. Wang, X. Liu, T. Kurosu, D. J. Jacob, and K. Chance. "Glyoxal retrieval from the Ozone Monitoring Instrument." Atmospheric Measurement Techniques Discussions 7, no. 6 (June 18, 2014): 6065–112. http://dx.doi.org/10.5194/amtd-7-6065-2014.
Full textAbstract:
Abstract. We present an algorithm for the retrieval of glyoxal from backscattered solar radiation, and apply it to spectra measured by the Ozone Monitoring Instrument (OMI). The algorithm is based on direct spectrum fitting, and adopts a two-step fitting routine to account for liquid water absorption. Previous studies have shown that glyoxal retrieval algorithms are highly sensitive to the position of the spectral fit window. This dependence was systematically tested on real and simulated OMI spectra. We find that a combination of errors resulting from uncertainties in reference cross sections and spectral features associated with the Ring effect are consistent with the fit-window dependence observed in real spectra. This implies an optimal fitting window of 435–461 nm, consistent with previous satellite glyoxal retrievals. The results from the retrieval of simulated spectra also support previous findings that have suggested that glyoxal is sensitive to NO2 cross section temperature. The retrieval window limits of the liquid water retrieval are also tested. A retrieval window 385–470 nm reduces interference with strong spectral features associated with sand. We show that cross track dependent offsets (stripes) present in OMI can be corrected using offsets derived from retrieved slant columns over the Sahara, and apply the correction to OMI data. Average glyoxal columns are on average lower than those of previous studies likely owing to the choice of reference sector for offset correction. OMI VCDs are lower compared to other satellites over the tropics and Asia during the monsoon season, suggesting that the new retrieval is less sensitive to water vapor abundance. Consequently we do not see significant glyoxal enhancements over tropical oceans. OMI derived glyoxal-to-formaldehyde ratios over biogenic and anthropogenic source regions are consistent with surface observations.
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Channathodiyil, Prasanna, and Jonathan Houseley. "Glyoxal fixation facilitates transcriptome analysis after antigen staining and cell sorting by flow cytometry." PLOS ONE 16, no. 1 (January 22, 2021): e0240769. http://dx.doi.org/10.1371/journal.pone.0240769.
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A simple method for extraction of high quality RNA from cells that have been fixed, stained and sorted by flow cytometry would allow routine transcriptome analysis of highly purified cell populations and single cells. However, formaldehyde fixation impairs RNA extraction and inhibits RNA amplification. Here we show that good quality RNA can be readily extracted from stained and sorted mammalian cells if formaldehyde is replaced by glyoxal—a well-characterised fixative that is widely compatible with immunofluorescent staining methods. Although both formaldehyde and glyoxal efficiently form protein-protein crosslinks, glyoxal does not crosslink RNA to proteins nor form stable RNA adducts, ensuring that RNA remains accessible and amenable to enzymatic manipulation after glyoxal fixation. We find that RNA integrity is maintained through glyoxal fixation, permeabilisation with methanol or saponin, indirect immunofluorescent staining and flow sorting. RNA can then be extracted by standard methods and processed into RNA-seq libraries using commercial kits; mRNA abundances measured by poly(A)+ RNA-seq correlate well between freshly harvested cells and fixed, stained and sorted cells. We validate the applicability of this approach to flow cytometry by staining MCF-7 cells for the intracellular G2/M-specific antigen cyclin B1 (CCNB1), and show strong enrichment for G2/M-phase cells based on transcriptomic data. Switching to glyoxal fixation with RNA-compatible staining methods requires only minor adjustments of most existing staining and sorting protocols, and should facilitate routine transcriptomic analysis of sorted cells.
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Lim, Y. B., Y. Tan, and B. J. Turpin. "Chemical insights, explicit chemistry and yields of secondary organic aerosol from methylglyoxal and glyoxal." Atmospheric Chemistry and Physics Discussions 13, no. 2 (February 19, 2013): 4687–725. http://dx.doi.org/10.5194/acpd-13-4687-2013.
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Abstract. Atmospherically abundant, volatile water soluble organic compounds formed through gas phase chemistry (e.g., glyoxal (C2), methylglyoxal (C3) and acetic acid) have great potential to form secondary organic aerosol (SOA) via aqueous chemistry in clouds, fogs and wet aerosols. This paper (1) provides chemical insights into aqueous-phase OH radical-initiated reactions leading to SOA formation from methylglyoxal and (2) uses this and a previously published glyoxal mechanism (Lim et al., 2010) to provide SOA yields for use in chemical transport models. Detailed reaction mechanisms including peroxy radical chemistry and a full kinetic model for aqueous photochemistry of acetic acid and methylglyoxal are developed and validated by comparing simulations with the experimental results from previous studies (Tan et al., 2010, 2012). This new methylglyoxal model is then combined with the previous glyoxal model (Lim et al., 2010), and is used to simulate the profiles of products and to estimate SOA yields. At cloud relevant concentrations (∼ 10−6–∼ 10−3 M; Munger et al., 1995) of glyoxal and methylglyoxal, the major photooxidation products are oxalic acid and pyruvic acid, and simulated SOA yields (by mass) are ∼ 120% for glyoxal and ∼ 80% for methylglyoxal. Oligomerization of unreacted aldehydes during droplet evaporation could enhance yields. In wet aerosols, where total dissolved organics are present at much higher concentrations (∼ 10 M), the major products are oligomers formed via organic radical-radical reactions, and simulated SOA yields (by mass) are ∼ 90% for both glyoxal and methylglyoxal.
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Galloway, M. M., A. J. Huisman, L. D. Yee, A. W. H. Chan, C. L. Loza, J. H. Seinfeld, and F. N. Keutsch. "Yields of oxidized volatile organic compounds during the OH radical initiated oxidation of isoprene, methyl vinyl ketone, and methacrolein under high–NO<sub>x</sub> conditions." Atmospheric Chemistry and Physics Discussions 11, no. 4 (April 6, 2011): 10693–720. http://dx.doi.org/10.5194/acpd-11-10693-2011.
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Abstract. We present first-generation and total production yields of glyoxal, methylglyoxal, glycolaldehyde, and hydroxyacetone from the oxidation of isoprene, methyl vinyl ketone (MVK), and methacrolein (MACR) with OH under high NOx conditions. Several of these first-generation yields are not included in commonly used chemical mechanisms, such as the Leeds Master Chemical Mechanism (MCM) v. 3.1. Inclusion of first-generation production of glyoxal, glycolaldehyde and hydroxyacetone from isoprene and methylglyoxal from MACR greatly improves performance of an MCM based model during the initial part of the experiments. In order to further improve performance of the MCM based model, higher generation glyoxal production was reduced by lowering the first-generation yield of glyoxal from C5 carbonyls. The results suggest that glyoxal production from reaction of OH with isoprene under high NOx conditions can be approximated by inclusion of a first-generation production term together with secondary production only via glycolaldehyde. Analogously, methylglyoxal production can be approximated by a first-generation production term from isoprene, and secondary production via MVK, MACR and hydroxyacetone. The first-generation yields reported here correspond to less than 5% of the total oxidized yield from isoprene and thus only have a small effect on the fate of isoprene. However, due to the abundance of isoprene, the combination of first-generation yields and reduced higher generation production of glyoxal from C5 carbonyls is important for models which include the production of the small organic molecules from isoprene.