Electrochemical Method for the Assay of Organic Peroxides Directly in Acetonitrile

Lipid peroxidation is a major process that determines the quality of various oil samples during their use and storage, in which the primary products are hydroperoxides (HP’<sub>S</sub>). HP’<sub>S</sub> are very stable compounds at ambient conditions and are harmful to human...

Full description

Saved in:
Bibliographic Details
Main Authors: Vanina Ivanova, Mariya Pimpilova, Maria Stoyanova, Nina Dimcheva
Format: Article
Language:English
Published: MDPI AG 2025-01-01
Series:Molecules
Subjects:
Online Access:https://www.mdpi.com/1420-3049/30/2/374
Tags: Add Tag
No Tags, Be the first to tag this record!
_version_ 1832587845999525888
author Vanina Ivanova
Mariya Pimpilova
Maria Stoyanova
Nina Dimcheva
author_facet Vanina Ivanova
Mariya Pimpilova
Maria Stoyanova
Nina Dimcheva
author_sort Vanina Ivanova
collection DOAJ
description Lipid peroxidation is a major process that determines the quality of various oil samples during their use and storage, in which the primary products are hydroperoxides (HP’<sub>S</sub>). HP’<sub>S</sub> are very stable compounds at ambient conditions and are harmful to human health. Therefore, the evaluation of the degree of oil oxidation is an excellent tool for ensuring food safety. The peroxide value (PV) is the main parameter used for quality control in oils. Herein, we propose an alternative electrochemical method to the classical iodometric titration method most widely used for determining the PV. Our approach is based on the electrochemical quantification of hydroperoxides/peroxides in an organic solvent medium (acetonitrile and organic ammonium salt) using a composite electrocatalyst–glassy carbon electrode modified with 2D-nanomaterial graphitic carbon nitride doped with Co<sub>3</sub>O<sub>4</sub>. Calibration was made by the method of standard addition using benzoyl peroxide (BPO) as a model peroxide compound, dissolved in chloroform and added to fresh Rivana-branded anti-cellulite oil, used as a model oil sample. Calibration plots showed a linear response and the very good reproducibility of the analytical result (R<sup>2</sup> ˃ 0.99). Further, in terms of accuracy, the method showed good results, since the BPO quantitative analysis was close to the theoretical response. In addition, the accuracy of the electrochemical method was compared with that of the standard iodometric titration method for determining the PV of vegetable fats (according to a standard method). Finally, using the electrochemical method, the concentration of peroxides was determined in a real sample—an anti-cellulite oil of the trademark Rivana with an expired shelf life.
format Article
id doaj-art-4b30733993794e30a62e03954bc74e0b
institution Kabale University
issn 1420-3049
language English
publishDate 2025-01-01
publisher MDPI AG
record_format Article
series Molecules
spelling doaj-art-4b30733993794e30a62e03954bc74e0b2025-01-24T13:43:49ZengMDPI AGMolecules1420-30492025-01-0130237410.3390/molecules30020374Electrochemical Method for the Assay of Organic Peroxides Directly in AcetonitrileVanina Ivanova0Mariya Pimpilova1Maria Stoyanova2Nina Dimcheva3Department of Physical Chemistry, Plovdiv University “Paisii Hilendarski”, 24, Tzar Assen Str., 4000 Plovdiv, BulgariaLaboratory of Biologically Active Substances, Institute of Organic Chemistry with Centre of Phytochemistry, Bulgarian Academy of Sciences, 139 Ruski Blvd., 4000 Plovdiv, BulgariaDepartment of Physical Chemistry, Plovdiv University “Paisii Hilendarski”, 24, Tzar Assen Str., 4000 Plovdiv, BulgariaDepartment of Physical Chemistry, Plovdiv University “Paisii Hilendarski”, 24, Tzar Assen Str., 4000 Plovdiv, BulgariaLipid peroxidation is a major process that determines the quality of various oil samples during their use and storage, in which the primary products are hydroperoxides (HP’<sub>S</sub>). HP’<sub>S</sub> are very stable compounds at ambient conditions and are harmful to human health. Therefore, the evaluation of the degree of oil oxidation is an excellent tool for ensuring food safety. The peroxide value (PV) is the main parameter used for quality control in oils. Herein, we propose an alternative electrochemical method to the classical iodometric titration method most widely used for determining the PV. Our approach is based on the electrochemical quantification of hydroperoxides/peroxides in an organic solvent medium (acetonitrile and organic ammonium salt) using a composite electrocatalyst–glassy carbon electrode modified with 2D-nanomaterial graphitic carbon nitride doped with Co<sub>3</sub>O<sub>4</sub>. Calibration was made by the method of standard addition using benzoyl peroxide (BPO) as a model peroxide compound, dissolved in chloroform and added to fresh Rivana-branded anti-cellulite oil, used as a model oil sample. Calibration plots showed a linear response and the very good reproducibility of the analytical result (R<sup>2</sup> ˃ 0.99). Further, in terms of accuracy, the method showed good results, since the BPO quantitative analysis was close to the theoretical response. In addition, the accuracy of the electrochemical method was compared with that of the standard iodometric titration method for determining the PV of vegetable fats (according to a standard method). Finally, using the electrochemical method, the concentration of peroxides was determined in a real sample—an anti-cellulite oil of the trademark Rivana with an expired shelf life.https://www.mdpi.com/1420-3049/30/2/374composite catalyst2D nanomaterialnon-aqueous electroanalysisorganic hydroperoxidesperoxide value (PV)
spellingShingle Vanina Ivanova
Mariya Pimpilova
Maria Stoyanova
Nina Dimcheva
Electrochemical Method for the Assay of Organic Peroxides Directly in Acetonitrile
Molecules
composite catalyst
2D nanomaterial
non-aqueous electroanalysis
organic hydroperoxides
peroxide value (PV)
title Electrochemical Method for the Assay of Organic Peroxides Directly in Acetonitrile
title_full Electrochemical Method for the Assay of Organic Peroxides Directly in Acetonitrile
title_fullStr Electrochemical Method for the Assay of Organic Peroxides Directly in Acetonitrile
title_full_unstemmed Electrochemical Method for the Assay of Organic Peroxides Directly in Acetonitrile
title_short Electrochemical Method for the Assay of Organic Peroxides Directly in Acetonitrile
title_sort electrochemical method for the assay of organic peroxides directly in acetonitrile
topic composite catalyst
2D nanomaterial
non-aqueous electroanalysis
organic hydroperoxides
peroxide value (PV)
url https://www.mdpi.com/1420-3049/30/2/374
work_keys_str_mv AT vaninaivanova electrochemicalmethodfortheassayoforganicperoxidesdirectlyinacetonitrile
AT mariyapimpilova electrochemicalmethodfortheassayoforganicperoxidesdirectlyinacetonitrile
AT mariastoyanova electrochemicalmethodfortheassayoforganicperoxidesdirectlyinacetonitrile
AT ninadimcheva electrochemicalmethodfortheassayoforganicperoxidesdirectlyinacetonitrile