Characterization Of Oxidation Products Research Articles

Characterization of Oxidation Products from HOCl Uptake by Microhydrated Methionine Anions Using Cryogenic Ion Vibrational Spectroscopy

The oxidation of the amino acid methionine (Met) by hypochlorous acid (HOCl) to yield methionine sulfoxide (MetO) has been implicated in both the interfacial chemistry of tropospheric sea spray aerosols and the destruction of pathogens in the immune system. Here, we investigate the reaction of deprotonated methionine water clusters, Met-·(H2O)n, with HOCl and characterize the resulting products using cryogenic ion vibrational spectroscopy and electronic structure calculations. Capture of the MetO- oxidation product in the gas phase requires the presence of water molecules attached to the reactant anion. Analysis of its vibrational band pattern confirms that the sulfide group of Met- has indeed been oxidized. Additionally, the vibrational spectrum of the anion corresponding to the uptake of HOCl by Met-·(H2O)n indicates that it exists as an "exit-channel" complex in which the Cl- product ion is bound to the COOH group following the formation of the S═O motif.

Fenton pre-oxidation of natural organic matter in drinking water treatment through the application of iron nails

ABSTRACT This study investigated for the first time the efficiency of an advanced oxidation process (AOP) zero valent iron/hydrogen peroxide (ZVI/H2O2) employing iron nails for the removal of Natural Organic Matter (NOM) from natural water of Regent’s Park lake, London, UK. The low cost of nails and their easy separation from the water after the treatment make this AOP attractive for water utilities in low- and middle-income countries. The process was investigated as a pre-oxidation step for drinking water treatment. Results showed that UV254 removal in the natural water was lower than that of simulated water containing commercial humic acid (HA), indicating a matrix effect. Statistical analysis confirmed the maximum removal of dissolved organic carbon (DOC) in natural water depends on the initial pH (best at 4.5) and H2O2 dosage (best at 100% excess of stoichiometric dosage). DOC and UV254 removals under this operational condition were 51% and 89%, respectively. Molecular weight (MW) and specific UV absorbance (SUVA254) were significantly reduced to 74% and 78%, respectively. Formation of Chloroform THM in natural water sample after the ZVI/H2O2 process (initial pH 4.5) was below the limit for drinking water, and 48% less than the THM formation in the same water not subjected to pre-oxidation. Characterization of oxidation products on the iron-nail-ZVI surface after the ZVI/H2O2 treatment by SEM, XRD, and XPS identified the formation of magnetite and lepidocrocite. Results suggest that the investigated ZVI/H2O2 process is a promising technology for removing NOM and reducing THM formation during drinking water treatment.

Fatty Acids Methyl Esters (FAME) autoxidation: New insights on insoluble deposit formation process in biofuels

The thermal and oxidation stability of fatty acids methyl esters (FAME) is arousing attention in the transport industry, since they are the main components present in biodiesel products used in the market. Low FAME stability can induce easy fuel degradation and produce oxidation products that can form sticky deposit causing serious malfunctioning and failures of engine and turbines components. We have focused the present work on the study of fuel oxidation process and the characterization of oxidation products in order to identify the main levers to avoid deposit formation. Soy and Rapeseed biodiesels were oxidized using an autoclave Parr reactor and characterized by FTIR, density and viscosity measurements. After oxidation, two different liquid phases were clearly observed. These two phases tend to form complex oil-oil emulsions after remixing as evidenced by optical microscopy. The separation behavior of the different liquid phases remixed after oxidation were studied using Multiple Light Scattering (TurbiscanTM). A comparison was made between the chemical functions of deposit obtained in the liquid phase after demixing (sedimented phase) and the solid deposit obtained on hot metallic surfaces. Results showed a that a complex oil-oil dispersion seems to form during the oxidation process. The phase separation rate of the oil-oil emulsified systems formed from oxidized fuels seems strongly related to the differences of polarity (e.g. oxygenates content) of both sedimented and supernatant phases. The understanding of this sedimentation or “demixing” process leading to deposit can be a key feature to develop strategies to prevent deposit formation in real systems.

Oxidation Stability of Diesel/Biodiesel Fuels Measured by a PetroOxy Device and Characterization of Oxidation Products

In the present work, the oxidation stability of diesel, rapeseed (RME), and soybean (SME) fatty acid methyl esters (FAME) and a blend of diesel with 10% (v/v) RME (B10–RME) was studied. Fuel samples were aged in the PetroOxy test device from 383 to 423 K at 7 bar. Experiments were conducted in oxygen excess, and the global kinetic constants were determined. The global kinetic constants for diesel, B10–RME, and RME at 383 K were 7.92 × 10–6, 2.78 × 10–5, and 8.87 × 10–5 s–1, respectively. The oxidation products formed at different stages of the oxidation were monitored by Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis–differential thermal analysis (TGA–DTA), and gas chromatography/mass spectrometry (GC/MS). The impact of the FAME nature and level of blending on the kinetic rate constant and the oxidation products was investigated. Results show that RME oxidation forms C19 epoxy as the main oxidation product, in addition to a methyl ester FAME derivative and short-chain oxidation...

Characterization of oxidation products from 1-palmitoyl-2-linoleoyl-sn-glycerophosphatidylcholine in aqueous solutions and their reactions with cysteine, histidine and lysine residues

This report focuses on studies of lipid peroxidation products reactivity towards the side chains of cysteine, histidine, and lysine residues in structurally unordered peptides. Thus we have analyzed linoleic acid peroxidation products (LaPP) obtained by incubating 1-palmitoyl-2-linoleoyl-sn-glycerophosphatidylcholine (PLPC) overnight with or without H2O2 in the presence or absence of CuCl. In total, 55 different LaPP were identified with 26 containing reactive carbonyl groups. The strongest oxidation conditions (H2O2 and Cu(I), i.e. a Fenton-like reagent) yielded 51 LaPP, whereas air oxidation produced only 12 LaPP. Independent of the oxidation conditions, around half of all LaPP were short-chain (oxidative cleavage) and the others long-chain (oxygen addition) PLPC oxidation products. The stronger oxidation conditions increased the number of LaPP, but also oxidized the added peptide Ac-PAAPAAPAPAEXTPV-OH (X=Cys, His or Lys) very quickly, especially under Fenton conditions. Thus, PLPC was oxidized by milder conditions (air or Cu(I)), incubated with the peptide and the peptide modifications were then analyzed by nano-RPC-ESI-Orbitrap-MS. Ten LaPP-derived peptide modifications were identified at lysine, whereas nine products were identified for cysteine and only three for histidine. Three high molecular weight LaPP still esterified to the GPC backbone were detected on Lys-containing peptide. Furthermore, three LaPP-derived mass shifts were obtained at cysteine, which have not previously been reported.

Antioxidant activity of olive phenols: mechanistic investigation and characterization of oxidation products by mass spectrometry

In this work, the antioxidant activity of olive phenols is first characterized by their stoichiometries n(tot)(number of radicals trapped per antioxidant molecule) and their rate constants for the first H-atom abstraction k(1) by the stable radical DPPH. It appears that oleuropein, hydroxytyrosol and caffeic acid have the largest k(1) values, whereas dihydrocaffeic acid, an intestinal metabolite of caffeic acid, is the best antioxidant in terms of n(tot). For phenols with a catechol moiety n(tot) is higher than two, implying an antioxidant effect of their primarily formed oxidation products. A HPLC-MS analysis of the main products formed in the AAPH-induced oxidation of olive phenols reveals the presence of dimers and trimers. With hydroxytyrosol and dihydrocaffeic acid, oligomerization can take place with the addition of water molecules.The antioxidant activity of olive phenols is then evaluated by their ability to inhibit the AAPH-induced peroxidation of linoleic acid in SDS micelles. It is shown that olive phenols and quercetin act as retardants rather than chain breakers like alpha-tocopherol. From a detailed mechanistic investigation, it appears that the inhibition of lipid peroxidation by olive phenols can be satisfactorily interpreted by assuming that they essentially reduce the AAPH-derived initiating radicals. Overall, olive phenols prove to be efficient scavengers of hydrophilic peroxyl radicals with a long lasting antioxidant effect owing to the residual activity of some of their oxidation products.

Characterisation of the oxidation products of pyrite by Thermogravimetric and Evolved Gas analysis

Museum specimens of pyrite are known to undergo oxidation even during storage. Characterisation of the oxidation products is however not always simple due to amorphous character and varying degrees of hydration of the oxidation products. This paper presents an alternative approach to the characterisation of oxidation products by identifying their presence from their characteristic thermal decomposition processes using thermogravimetric and evolved gas analysis. Four pyrite specimens were characterised with varying degrees of oxidation. Iron(II) and iron(III) sulphates were also characterised for comparative purposes. The degradation products were observed to correlate well with the presence of iron(II) sulphate even though there was found to be some discrepancy in the higher temperature decomposition reactions.

A Study of the Oxidation Pathway of Adrenaline by Cyclic Voltammetry: An Undergraduate Analytical Chemistry Laboratory Exercise

An undergraduate laboratory exercise to be used in an undergraduate instrumental methods course is presented for the electrochemical characterization of oxidation products of adrenaline. An objective of this experiment is to use information obtained through cyclic voltammetry and simulation software to develop a qualitative understanding of the oxidation mechanism of adrenaline.

Intradiol Aromatic Ring Cleavage in a Dioxygenase Model System

Abstract Dioxygenase Model, Copper, Catechol The complex (3-n-nonylcatecholato)(1,10-phenanthroline)copper(II) reacts with molecular oxygen to give an isomeric mixture of 2-n-nonylmuconic acid and several secondary oxidation products. The catecholato ligand is oxidatively cleaved in an intradiol fashion reminescent of the reactions catalyzed by intradiol aromatic dioxygenases. The 1,10-phenanthroline ligand can be quantitatively recovered and is not oxidized. In addition to characterization of oxidation products, the kinetics of oxygen consumption have been analyzed. The rate law for oxygen uptake is -d[O2]/dt = k[O2] [copper]2 .