Novel Strecker degradation products of tyrosine and dihydroxyphenylalanine

Tyrosine was oxidised with either potassium peroxodisulphate or glyoxal. Volatile reaction products were isolated and analysed by GC/FID and GC/MS, derivatised with diazomethane and analysed by the same methods. Eight reaction products were identified. The major products were the expected Strecker aldehyde (4-hydroxyphenylacetaldehyde) and its lower homologue 4-hydroxybenzaldehyde. They were followed by 1-(4-hydroxyphenyl)-3-propionaldehyde, phenylacetaldehyde, benzaldehyde, phenol, 4-hydroxybenzoic, and benzoic acid. Analogously, the oxidation of 3,4-dihydroxyphenylalanine yielded the corresponding Strecker aldehyde (3,4-dihydroxyphenylacetaldehyde), its lower homologue 3,4-dihydroxybenzaldehyde, 3,4-dihydroxybenzoic, 3,4-dihydroxyphenylacetic, and caffeic acid. An identification of these oxidation products of tyrosine and 3,4-dihydroxyphenylalanine assumes homolytic cleavage of the Strecker aldehydes and a recombination of free radicals formed by this cleavage. As minor products, six O- and N-heterocyclic compounds arose in systems containing glyoxal (pyrazine, methyl- and ethylpyrazine, 3-furancarbaldehyde, 5-methyl-2-furancarbaldehyde, 2-pyrrolcarbaldehyde).

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Strecker degradation products of aspartic and glutamic acids and their amides

Czech Journal of Food Sciences ◽

10.17221/6573-cjfs ◽

2013 ◽

Vol 19 (No. 2) ◽

pp. 41-45 ◽

Cited By ~ 4

Author(s):

J. Rössner ◽

J. Velíšek ◽

F. Pudil ◽

J. Davídek

Keyword(s):

Amino Acids ◽

Glutamic Acid ◽

Aspartic Acid ◽

Degradation Products ◽

Dicarboxylic Acids ◽

Reaction Products ◽

Degradation Reactions ◽

Strecker Aldehydes ◽

Volatile Products ◽

Acid Acid

Aspartic and glutamic acids, asparagine and glutamine were oxidised with either potassium peroxodisulphate or glyoxal. Nonvolatile products were derivatised and analysed by GC/FID and GC/MS. Volatile reaction products were isolated and analysed by the same methods. It was found that the degradation reactions of amino acids are complex. Amino acids are principally degraded via the corresponding a-keto acids to Strecker aldehydes (aspartic acid to oxalacetic and 3-oxopropionic acids and glutamic acid to a-ketoglutaric and 4-oxobutyric acids), which are unstable and decomposed by decarboxylation to the corresponding aldehydes. Aspartic acid also eliminates ammonia and yields fumaric acid whereas glutamic acid gives rise to an imine, pyroglutamic acid. A recombination of free radicals leads to dicarboxylic acids (succinic acid from aspartic acid, succinic, glutaric and adipic acids from glutamic acid). The major volatile products (besides the aldehydes) are lower carboxylic acids (acetic acid from aspartic acid and propionic acid acid from glutamic acid) that can at least partly arise by radical reactions. In both quality and quantity terms, a higher amount of degradation products arises by oxidation of amino acids by peroxodisulphate.

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Characterization of dissolved material during the initial phase of softwood kraft pulping

TAPPI Journal ◽

10.32964/tj12.1.37 ◽

2013 ◽

Vol 12 (1) ◽

pp. 37-43 ◽

Cited By ~ 1

Author(s):

HANNU PAKKANEN ◽

TEEMU PALOHEIMO ◽

RAIMO ALÉN

Keyword(s):

Mass Transfer ◽

Molecular Mass ◽

Initial Phase ◽

Degradation Products ◽

Kraft Pulping ◽

Reaction Products ◽

Cooking Temperature ◽

Molecular Masses ◽

Aliphatic Carboxylic Acids

The influence of various cooking parameters, such as effective alkali, cooking temperature, and cooking time on the formation of high molecular mass lignin-derived and low molecular mass carbohydrates-derived (aliphatic carboxylic acids) degradation products, mainly during the initial phase of softwood kraft pulping was studied. In addition, the mass transfer of all of these degradation products was clarified based on their concentrations in the cooking liquor inside and outside of the chips. The results indicated that the degradation of the major hemicellulose component, galactoglucomannan, typically was dependent on temperature, and the maximum degradation amount was about 60%. In addition, about 60 min at 284°F (140°C) was needed for leveling off the concentrations of the characteristic reaction products (3,4-dideoxy-pentonic and glucoisosaccharinic acids) between these cooking liquors. Compared with low molecular mass aliphatic acids, the mass transfer of soluble lignin fragments with much higher molecular masses was clearly slower.

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Impact of Chitosan-Genipin Films on Volatile Profile of Wine along Storage

Applied Sciences ◽

10.3390/app11146294 ◽

2021 ◽

Vol 11 (14) ◽

pp. 6294

Author(s):

M. Angélica Rocha ◽

Manuel Coimbra ◽

Sílvia Rocha ◽

Cláudia Nunes

Keyword(s):

Volatile Compounds ◽

Carbon Chain ◽

White Wine ◽

Maillard Reaction Products ◽

Red Wines ◽

Reaction Products ◽

Ethyl Hexanoate ◽

Organoleptic Characteristics ◽

Strecker Aldehydes ◽

Key Odorants

Chitosan-genipin films have been proposed for preservation of white wine, maintaining their varietal key odorants and organoleptic characteristics of sulfur dioxide treated wines. Nevertheless, these wines showed aroma notes that slightly distinguish them. It is possible that during the contact of films with wine for at least 2 months, after fermentation and prior to bottling, interactions or chemical reactions are promoted. In this work, wine model solutions with volatile compounds in contact with chitosan-genipin films were performed to evaluate their evolution along time. To complement these analyses, the volatile compounds of white and red wines kept in contact with chitosan-genipin films during 2 and 8 months were also studied. The results obtained allowed us to conclude that the contact of chitosan-genipin films with both white and red wines tend to retain long carbon chain volatile compounds, such as ethyl hexanoate and octan-3-one. It also promoted the formation of Maillard reaction products, such as furfural by dehydration of pentoses and Strecker aldehydes, such as 3-methylbutanal and phenylacetaldehyde, by degradation of amino acids. This study reveals that the use of chitosan-genipin films for wine preservation is also able to promote the formation of compounds that can modulate the wines aroma, maintaining the varietal notes.

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Potential-pH diagrams considering complex oxide solution phases for understanding aqueous corrosion of multi-principal element alloys

npj Materials Degradation ◽

10.1038/s41529-020-00141-6 ◽

2020 ◽

Vol 4 (1) ◽

Author(s):

Kang Wang ◽

Junsoo Han ◽

Angela Yu Gerard ◽

John R. Scully ◽

Bi-Cheng Zhou

Keyword(s):

Solid Solution ◽

Free Energy ◽

Graphical Representation ◽

Equilibrium Composition ◽

Complex Oxide ◽

Oxidation Products ◽

Reaction Products ◽

Aqueous Corrosion ◽

Principal Element ◽

Diagram Method

AbstractThe potential-pH diagram, a graphical representation of the thermodynamically predominant reaction products in aqueous corrosion, is originally proposed for the corrosion of pure metals. The original approach only leads to stoichiometric oxides and hydroxides as the oxidation products. However, numerous experiments show that non-stoichiometric oxide scales are prevalent in the aqueous corrosion of alloys. In the present study, a room temperature potential-pH diagram considering oxide solid solutions, as a generalization of the traditional potential-pH diagram with stoichiometric oxides, is constructed for an FCC single-phase multi-principal element alloy (MPEA) based on the CALculation of PHAse Diagram method. The predominant reaction products, the ions in aqueous solution, and the cation distribution in oxides are predicted. The oxide solid solution is stabilized by the mixing free energy (or mixing entropy) and the stabilizing effect becomes more significant as the temperature increases. Consequently, solid solution oxides are stable in large regions of the potential-pH diagram and the mixing free energy mostly affects the equilibrium composition of the stable oxides, while the shape of stable regions for oxides is mostly determined by the structure of the stable oxides. Agreements are found for Ni2+, Fe2+, and Mn2+ between the atomic emission spectroelectrochemistry measurements and thermodynamic calculations, while deviations exist for Cr3+ and Co2+ possibly due to surface complexation with species such as Cl− and the oxide dissolution. By incorporating the solution models of oxides, the current work presents a general and more accurate way to analyze the reaction products during aqueous corrosion of MPEAs.

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DFT study of the effect of solvent on the H-atom transfer involved in the scavenging of the free radicals ●HO2 and ●O2 − by caffeic acid phenethyl ester and some of its derivatives

Journal of Molecular Modeling ◽

10.1007/s00894-014-2509-9 ◽

2014 ◽

Vol 20 (11) ◽

Cited By ~ 14

Author(s):

Olivier Holtomo ◽

Mama Nsangou ◽

Jean Jules Fifen ◽

Ousmanou Motapon

Keyword(s):

Free Radicals ◽

Caffeic Acid ◽

Caffeic Acid Phenethyl Ester ◽

Dft Study ◽

Atom Transfer ◽

Effect Of Solvent

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Occurrence and distribution of ladderane oxidation products in different oceanic regimes

Biogeosciences ◽

10.5194/bg-9-2407-2012 ◽

2012 ◽

Vol 9 (7) ◽

pp. 2407-2418 ◽

Cited By ~ 17

Author(s):

D. Rush ◽

E. C. Hopmans ◽

S. G. Wakeham ◽

S. Schouten ◽

J. S. Sinninghe Damsté

Keyword(s):

Fatty Acids ◽

Water Column ◽

Arabian Sea ◽

Degradation Products ◽

Oxidation Products ◽

Short Chain ◽

Sediment Surface ◽

Ammonium Oxidation ◽

Anammox Activity ◽

Sediment Matrix

Abstract. Ladderane fatty acids are commonly used as biomarkers for bacteria involved in anaerobic ammonium oxidation (anammox). These lipids have been experimentally shown to undergo aerobic microbial degradation to form short chain ladderane fatty acids. However, nothing is known of the production or the distribution of these oxic biodegradation products in the natural environment. In this study, we analysed marine water column particulate matter and sediment from three different oceanic regimes for the presence of ladderane oxidation products (C14 ladderane fatty acids) and of original ladderane fatty acids (C18 and C20 ladderane fatty acids). We found that ladderane oxidation products, i.e. C14 ladderane fatty acids, are already produced within the water column of the Arabian Sea oxygen minimum zone (OMZ) and thus only low amounts of oxygen (< 3 μM) are needed for the β-oxidation of original ladderane fatty acids to proceed. However, no short chain ladderane fatty acids were detected in the Cariaco Basin water column, where oxygen concentrations were below detection limit, suggesting that the β-oxidation pathway is inhibited by the absence of molecular oxygen, or that the microbes performing the degradation are not proliferating under these conditions. Comparison of distributions of ladderane fatty acids indicates that short chain ladderane fatty acids are mostly produced in the water column and at the sediment surface, before being preserved deeper in the sediments. Short chain ladderane fatty acids were abundant in Arabian Sea and Peru Margin sediments (ODP Leg 201), often in higher concentrations than the original ladderane fatty acids. In a sediment core taken from within the Arabian Sea OMZ, short chain ladderanes made up more than 90% of the total ladderanes at depths greater than 5 cm below sea floor. We also found short chain ladderanes in higher concentrations in hydrolysed sediment residues compared to those freely occurring in lipid extracts, suggesting that they had become bound to the sediment matrix. Furthermore, these matrix-bound short chain ladderanes were found at greater sediment depths than short chain ladderanes in the lipid extract, suggesting that binding to the sediment matrix aids the preservation of these lipids. Though sedimentary degradation of short chain ladderane fatty acids did occur, it appeared to be at a slower rate than that of the original ladderane fatty acids, and short chain ladderane fatty acids were found in sediments from the Late Pleistocene (~ 100 kyr). Together these results suggest that the oxic degradation products of ladderane fatty acids may be suitable biomarkers for past anammox activity in OMZs.

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Thermodynamic simulation of oxidation process of the Moss-Mo3Si hypoeutectic alloy, doped with scandium or neodymium

Butlerov Communications ◽

10.37952/roi-jbc-01/19-57-2-90 ◽

2019 ◽

Vol 57 (2) ◽

pp. 90-100

Author(s):

Alexey V. Larionov ◽

◽

Ludmila Y. Udoeva ◽

Vladimir M. Chumarev ◽

◽

...

Keyword(s):

Oxidation Process ◽

Thermodynamic Simulation ◽

Oxidation Products ◽

Hypoeutectic Alloy ◽

Protective Film ◽

Chemical Transformations ◽

Reaction Products ◽

Moist Air ◽

Condensed Product ◽

Hsc Chemistry

In order to study the effect of yttrium additives on the oxidation of molybdenum silicide alloys, thermodynamic modeling of the interaction in Mo-Mo3Si-Sc5Si3 и Mo-Mo3Si-NdSi systems with dry and moist air was performed in the temperature range 25-2000 °C. The calculations were performed using the HSC Chemistry 6.12 software, into the database of which the calculated missing thermochemical characteristics silicates, molybdates of scandium and neodymium were entered. Based on the obtained dependences of the composition of phases on temperature and charge of the oxidant (air or vapor-air mixture), the sequence of phase formation was determined and the compositions of oxidation products were estimated. It is shown that, under equilibrium conditions, the oxidation process with dry and moist air proceeds almost equally, since the interaction of the components of the alloy with oxygen is thermodynamically preferable than with water vapor. According to the obtained thermodynamic models, the oxidation process of the Mo-5Si-3(Sc, Nd) (wt.%) alloys involves a sequence of the following chemical transformations: at the beginning Mo and Sc (Nd) silicides oxidize forming Sc2O3 ( Nd2O3), SiO2 and elemental Mo, then molybdenum is oxidized to MoO2 and Sc2O3 or Nd2O3 interacts with SiO2 with the formation of appropriate silicates Sc2Si2O7 или Nd2Si2O7. As a result of the complete oxidation of the alloy, MoO3 and Sc2(MoO4)3 or Nd2Mo4O15 are added to the condensed product, and molybdenum oxide (MoO3)n vapor appears in the gas phase. In addition, the formation of Nd2Mo2O7 and Nd2 (MoO4)3 is possible. During the oxidation of the Mo-5Si-3Nd alloy at T> 1700 oC, Nd(OH)3 can be formed in the condensed reaction products. According to the results of complete thermodynamic analysis, the formation of silicates and molybdates of scandium and neodymium can promote to the formation of a protective film on the surface of the alloys, which limits the diffusion of oxygen in them, and as a result, the oxidation resistance of alloys should increase.

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Ultrasonic irradiation of chemical compounds in aqueous solutions

10.12681/eadd/3981 ◽

1992 ◽

Author(s):

Αναστασία Κοτρωναρου

Keyword(s):

Aqueous Solutions ◽

Ultrasonic Irradiation ◽

Energy Utilization ◽

Oxidation Products ◽

Utilization Efficiency ◽

Interfacial Region ◽

Reaction Products ◽

Operation Conditions ◽

Cavitation Bubbles ◽

Ph Range

The ultrasonic irradiation of para-nitrophenol, S(-II), and parathion is studied in aqueous solutions at 20 kHz and ~ 75 W-cnT2. Para-nitrophenol was degraded primarily by denitration and secondarily by ΌΗ radical attack to yield N 02, NO3, benzoquinone, hydroquinone, 4-nitrocatechol, formate and oxalate. These reaction products and the kinetic observations are consistent with a model involving high-temperature reactions of p-nitrophenol in the interfa.cia.1 region of cavitation bubbles. The average effective temperature of the interfacial region surrounding the cavitation bubbles was estimated to be T ~ 800 K. Ultrasonic irradiation of S(-II) is studied in aqueous solutions over the pH range 7 - 12. The reaction of HS“ with OH is the principal pathway for theoxidation of S(-II) at pH > 10; the oxidation products are SO2“, SO2", and S20 Upon prolonged sonication, SO2" is the only observed product. At pH < 8.5, thermal decomposition of H2S within or near collapsing cavitation bubbles becomes the important pathway and elemental sulfur is found as an additional product of the sonolysis of S(-II). The sonolytic oxidation of H2S at pH > 10 was successfully modeled with an aqueous-phase free-radical chemistry mechanism and assumingcontinuous and uniform ΌΗ input into solution from the imploding cavitation bubbles. Parathion degradation occurred primarily by enhanced hydrolysis and secondarily by direct ΌΗ radical attack.The effect of various physical and chemical parameters on sonolytic yields is examined. The observed effects are in qualitative agreement with the sonolysis mechanisms proposed for the chemicals of interest and the existing hydrodynamic theories of acoustic cavitation. The formation of iodine upon ultrasonic irradiation of potassium iodide solutions and the sonolysis of S(-II) are used as probes to compare the sonochemical efficiency of different experimental set-ups. This work elucidates the mechanisms of the ultrasonic decomposition of typical organic and inorganic pollutants. It is shown that ultrasound has the potential to become a viable alternative for the destruction of chemical contaminants in water and wastewater. The current limitation of sonolysis is its low energy utilization efficiency, but there is room for improvement by optimizing reactor design and physical/chemical operation conditions. This work offers some recommendations and insight in that respect.

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