scholarly journals Spin trapping studies of essential oils in lipid systems

Nukleonika ◽  
2015 ◽  
Vol 60 (3) ◽  
pp. 461-468 ◽  
Author(s):  
Katerina Makarova ◽  
Kinga Drązikowska ◽  
Beata Suska ◽  
Katarzyna Zawada ◽  
Iwona Wawer
Keyword(s):  
Essential Oils ◽  
Fenton Reaction ◽  
Spin Trap ◽  
Spin Trapping ◽  
Oh Radicals ◽  
Bath Salts ◽  
Radical Adduct ◽  
Hyperfine Splittings ◽  
Skin Care Products ◽  
Fenton System

Abstract In the present work, we report the results of a spin trapping ESR study of four essential oils widely used for skin care products such as creams and bath salts. The studied essential oils are Rosmarini aetheroleum (rosemary), Menthae piperitae aetheroleum (mint), Lavandulae aetheroleum (lavender), and Thymi aetheroleum (thyme). Fenton reaction in the presence of ethanol was used to generate free radicals. The N-tert-butyl-α-phenylnitrone (PBN) was used as a spin trap. In the Fenton reaction, the rosemary oil had the lowest effect on radical adduct formation as compared to the reference Fenton system. Since essential oils are known to be lipid soluble, we also conducted studies of essential oils in Fenton reaction in the presence of lipids. Two model lipids were used, namely 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) and 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC). The obtained results suggested that in the presence of DOPC lipids, the •OH and PBN/•CHCH3(OH) radicals are formed in both phases, that is, water and lipids, and all the studied essential oils affected the Fenton reaction in a similar way. Whereas, in the DPPC system, the additional type of PBN/X (aN = 16.1 G, aH = 2.9 G) radical adduct was generated. DFT calculations of hyperfine splittings were performed at B3LYP/6-311+G(d,p)/EPR-II level of theory for the set of c-centered PBN adducts in order to identify PBN/X radical.

scholarly journals The spin trapping of pyrimidine nucleotide free radicals in a Fenton system

1989 ◽  
Vol 261 (3) ◽  
pp. 831-839 ◽  
Author(s):  
W D Flitter ◽  
R P Mason
Keyword(s):  
Free Radicals ◽  
Hydroxyl Radical ◽  
Spin Trap ◽  
Gamma Ray ◽  
Thiobarbituric Acid ◽  
Spin Trapping ◽  
Pyrimidine Nucleotide ◽  
Gamma Ray Irradiation ◽  
Radical Attack ◽  
Fenton System

The reaction of the hydroxyl radical, generated by a Fenton system, with pyrimidine deoxyribonucleotides was investigated by using the e.s.r. technique of spin trapping. The spin trap t-nitrosobutane was employed to trap secondary radicals formed by the reaction of the hydroxyl radical with these nucleotides. The results presented here show that hydroxyl-radical attack on thymidine, 2-deoxycytidine 5-monophosphate and 2-deoxyuridine 5-monophosphate produced nucleotide-derived free radicals. The results indicate that .OH radical attack occurs predominantly at the carbon-carbon double bond of the pyrimidine base. The e.s.r. studies showed a good correlation with previous results obtained by authors who used x- or gamma-ray irradiation to generate the hydroxyl radical. A thiobarbituric acid assay was also used to monitor the damage produced to the nucleotides by the Fenton system. These results showed qualitative agreement with the spin-trapping studies.

Degradation of p-hydroxyphenylacetic acid by photoassisted Fenton reaction

2001 ◽  
Vol 44 (5) ◽  
pp. 31-38 ◽  
Author(s):  
J.L. Acero ◽  
F.J. Benítez ◽  
F.J. Real ◽  
A.I. Leal
Keyword(s):  
Fenton Reaction ◽  
Advanced Oxidation Processes ◽  
Radical Reaction ◽  
Industrial Plant ◽  
Oh Radicals ◽  
Oxidation Processes ◽  
Fenton’S Reaction ◽  
Optimum Ph ◽  
Hydroxyphenylacetic Acid ◽  
Fenton System

The chemical decomposition of p-hydroxyphenylacetic acid, a phenolic pollutant present in agro-industrial plant effluents, has been investigated by means of the Fenton's reaction and the photoassisted Fenton's reaction, the so-called photo-Fenton system. The degradation levels achieved have been compared to those obtained by applying other Advanced Oxidation Processes, such as the combination UV/H2O2. The optimum pH to carry out the decomposition of this organic compound by either Fenton or photo-Fenton systems was found to be pH = 3. The presence of buffers such as phosphate impedes these processes due to the formation of ferric complexes. A reaction mechanism, which allows calculating the contribution of the radical reaction to the global process, has been proposed. According to this mechanism, the dominant way of degradation of p-hydroxyphenylacetic acid is through its reaction with the OH radicals originated in the photolysis of H2O2 and, especially, in the Fenton's reaction.

scholarly journals Site-specific spin trapping of tyrosine radicals in the oxidation of metmyoglobin by hydrogen peroxide

1998 ◽  
Vol 330 (3) ◽  
pp. 1293-1299 ◽  
Author(s):  
R. Michael GUNTHER ◽  
Richard A. TSCHIRRET-GUTH ◽  
H. Ewa WITKOWSKA ◽  
C. Yang FANN ◽  
P. David BARR ◽  
...  
Keyword(s):  
Hydrogen Peroxide ◽  
Spin Trap ◽  
Sperm Whale ◽  
Spin Trapping ◽  
Tryptophan Residue ◽  
Radical Adduct ◽  
Unpaired Electron Density ◽  
Trapping Agent ◽  
Tyrosine Radical ◽  
Radical Yield

The reaction between metmyoglobin and hydrogen peroxide produces both a ferryl-oxo heme and a globin-centred radical(s) from the two oxidizing equivalents of the hydrogen peroxide. Evidence has been presented for localization of the globin-centred radical on one tryptophan residue and tyrosines 103 and 151. When the spin-trapping agent 5,5-dimethyl-1-pyrroline N-oxide (DMPO) is included in the reaction mixture, a radical adduct has been detected, but the residue at which that adduct is formed has not been determined. Replacement of either tryptophans 7 and 14 or tyrosines 146 and 151 with phenylalanine has no effect on the formation of DMPO adduct in the reaction with hydrogen peroxide. When tyrosine 103 is replaced with phenylalanine, however, only DMPOX, a product of the oxidation of the spin-trap, is detected. Tyrosine-103 is, therefore, the site of radical adduct formation with DMPO. The spin trap 2-methyl-2-nitrosopropane (MNP), however, forms radical adducts with any recombinant sperm whale metmyoglobin that contains either tyrosine 103 or 151. Detailed spectral analysis of the DMPO and MNP radical adducts of isotopically substituted tyrosine radical yield complete structural determinations. The multiple sites of trapping support a model in which the unpaired electron density is spread over a number of residues in the population of metmyoglobin molecules, at least some of which are in equilibrium with each other.

scholarly journals Formation of peroxide- and globin-derived radicals from the reaction of methaemoglobin and metmyoglobin with t-butyl hydroperoxide: an ESR spin-trapping investigation

1997 ◽  
Vol 322 (2) ◽  
pp. 633-639 ◽  
Author(s):  
Jolanda Van der ZEE
Keyword(s):  
Spin Trap ◽  
Hydrogen Abstraction ◽  
Spin Trapping ◽  
Tyrosyl Radical ◽  
Alkoxyl Radical ◽  
Butyl Hydroperoxide ◽  
Heterolytic Cleavage ◽  
Esr Spin Trapping ◽  
Radical Adduct ◽  
Protein Radicals

The reaction of human methaemoglobin and horse metmyoglobin with t-butyl hydroperoxide (t-BuOOH) was investigated with the ESR spin-trapping technique. With the spin trap 5,5-dimethyl-1-pyrroline N-oxide (DMPO) the formation of peroxyl, alkoxyl and methyl radicals derived from t-BuOOH could be detected. The relative contributions of these radicals were determined at various DMPO concentrations by computer simulation. From these data it could be concluded that the alkoxyl radical was the initial radical produced, which indicates that the hydroperoxide is cleaved homolytically. Further investigations, with the nitroso spin trap 2-methyl-2-nitrosopropane (MNP), showed the formation of globin-centred radicals. Non-specific proteolysis of the MNP adducts revealed isotropic three-line spectra, which means that the radical adducts were centred on a tertiary carbon with no bonds to a hydrogen or nitrogen. Comparison with MNP adducts of several amino acids indicated that in methaemoglobin the radical adduct was most probably located on a valine residue. With metmyoglobin the same adduct was obtained, whereas an additional adduct could be assigned to a tyrosyl radical. These protein radicals most probably resulted from hydrogen abstraction by the metal–oxo species, formed by heterolytic cleavage of the hydroperoxide. These results therefore show that homolytic cleavage of the hydroperoxide leads to the formation of peroxide-derived radicals, whereas concurrent heterolytic cleavage results in protein-derived radicals.

Investigation of the reaction pathway of OH radicals produced by Fenton oxidation in the conditions of wastewater treatment

2001 ◽  
Vol 44 (5) ◽  
pp. 15-15 ◽  
Author(s):  
J. Yoon ◽  
Y. Lee ◽  
S. Kim
Keyword(s):  
Landfill Leachate ◽  
Fenton Reaction ◽  
Reaction Pathway ◽  
Oxidation Products ◽  
Ferrous Ion ◽  
Oh Radicals ◽  
Effective Manner ◽  
Short Period ◽  
High Concentrations ◽  
Fenton System

Fenton reaction has been often used to treat industrial wastewater or landfill leachate. However, most mechanistic research into the Fenton reaction has been confined to low concentration conditions (usually the concentration of iron is less than 1 mM). These conditions are removed from the circumstances of real application. This is especially true in the treatment of landfill leachate in Korea. Therefore, we investigated the characteristics of the Fenton system using high concentrations of iron (mostly [Fe2+] = 1∼10 mM, [H2O2] = 5 mM, [Organic (t-BuOH or methanol)] = 0 or 30 mM) and interpreted the results from the known reaction mechanisms of the Fenton system. As a result, the use of high ferrous ion [≥1 mM) is believed to be appropriate for producing large quantities of OH• within a short period of time, causing fast consumption of hydrogen peroxide. However, OH• scavenging by the ferrous ion, the changes of oxidation products due to the oxygen depleted conditions, and the precipitation effect of ferric ion must be considered for the successful application of Fenton reaction. On the other hand, in low ferrous ion (<1 mM), it is important to utilize the redox cycles of iron in an effective manner.

Photoredox Reactions of Iodo Iron(III) Complexes Containing Tetradentate Ligands

2001 ◽  
Vol 66 (1) ◽  
pp. 109-118 ◽  
Author(s):  
Jozef Šima ◽  
Dáša Lauková ◽  
Vlasta Brezová
Keyword(s):  
Schiff Bases ◽  
Spin Trapping ◽  
Molar Ratio ◽  
Oh Radicals ◽  
Solvated Electrons ◽  
Open Chain ◽  
Tetradentate Ligands ◽  
Visible Irradiation ◽  
Epr Spin Trapping ◽  
Spin Trapping Technique

Photoredox reactions occurring in irradiated methanolic solutions of trans-[FeIII(R,R'-salen)(CH3OH)I], where R,R'-salen2- are N,N'-ethylenebis(R,R'-salicylideneiminato), tetradentate open-chain N2O2-Schiff bases with R,R' = H, 5-Cl, 5-Br, 3,5-di-Br, 3,5-di-(CH3), 3-OCH3, 5-OCH3, have been investigated and their mechanism proposed. The complexes are redox-stable in the dark. Ultraviolet and/or visible irradiation of methanolic solution of the complexes induces photoreduction of Fe(III) to Fe(II). Depending on the composition of the irradiated solutions, •CH2OH radicals or solvated electrons were identified by the EPR spin trapping technique. The final product of the photooxidation coupled with the photoreduction of Fe(III) is formaldehyde and the molar ratio of Fe(II) and CH2O is close to 2 : 1. The efficiency of the photoredox process is strongly wavelength-dependent and influenced by the peripheral groups R,R' of the tetradentate ligands.

scholarly journals Enhancement of Iron-Based Photo-Driven Processes by the Presence of Catechol Moieties

Catalysts ◽  
2021 ◽  
Vol 11 (3) ◽  
pp. 372
Author(s):  
Javier Moreno-Andrés ◽  
Iván Vallés ◽  
Paula García-Negueroles ◽  
Lucas Santos-Juanes ◽  
Antonio Arques
Keyword(s):  
Fenton Reaction ◽  
Advanced Oxidation Processes ◽  
Salt Water ◽  
Degradation Process ◽  
Contaminants Of Emerging Concern ◽  
Low Salt ◽  
Aquaculture Industry ◽  
Iron Based ◽  
Ph Range ◽  
Fenton System

Photo-induced Advanced Oxidation Processes (AOPs) using H2O2 or S2O82− as radical precursors were assessed for the abatement of six different contaminants of emerging concern (CECs). In order to increase the efficiency of these AOPs at a wider pH range, the catechol organic functional compound was studied as a potential assistant in photo-driven iron-based processes. Different salinity regimes were also studied (in terms of Cl− concentration), namely low salt water (1 g·L−1) or a salt–water (30 g·L−1) matrix. Results obtained revealed that the presence of catechol could efficiently assist the photo-Fenton system and partly promote the photo-induced S2O82− system, which was highly dependent on salinity. Regarding the behavior of individual CECs, the photo-Fenton reaction was able to enhance the degradation of all six CECs, meanwhile the S2O82−-based process showed a moderate enhancement for acetaminophen, amoxicillin or clofibric acid. Finally, a response-surface methodology was employed to determine the effect of pH and catechol concentration on the different photo-driven processes. Catechol was removed during the degradation process. According to the results obtained, the presence of catechol in organic macromolecules can bring some advantages in water treatment for either freshwater (wastewater) or seawater (maritime or aquaculture industry).

Photocatalytic Degradation of 4-Chlorophenol by •OH Radicals Generated by Thiophene Oligomers Incorporated in ZSM-5 Zeolite Channels

2003 ◽  
Vol 68 (11) ◽  
pp. 2219-2230 ◽  
Author(s):  
Gabriel Čík ◽  
Milada Hubinová ◽  
František Šeršeň ◽  
Jozef Krištín ◽  
Monika Antošová
Keyword(s):  
Reactive Oxygen Species ◽  
Visible Light ◽  
Photocatalytic Degradation ◽  
Maleic Acid ◽  
Aqueous Suspension ◽  
Reactive Oxygen ◽  
Spin Trapping ◽  
Oh Radicals ◽  
Oxygen Species ◽  
Trapping Method

Degradation of 4-chlorophenol by reactive oxygen species was studied, the latter being generated by photo-assisted reactions of thiophene oligomers, synthesized in channels of the Na-ZSM-5 zeolite. The photoreaction was carried out in an aqueous suspension of photocatalyst, irradiated with visible light (λ > 400 nm). The spin-trapping method was used to detect the generated •OH radicals. The main products of the photodecomposition of 4-chlorophenol were found to be phenol, hydroquinone and maleic acid.

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