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The electrochemical properties of nine chlorogenic acids (CGAs) isomers: three caffeoylquinic acids, CQAs (5-CQA, 4-CQA, 3-CQA), three dicaffeoylquinic acids, diCQAs (3, 3, 4, and three feruloylquinic acids, FQAs (5-FQA, 4-FQA, 3-FQA) were studied by differential pulse voltammetry (DPV) method. The study has shown that electrochemical properties of CQAs and diCQAs are strongly dependent on their chemical structure and electronic properties, particularly on presence of electron-donating -OH and -CH=CHgroups, and a strong electron-withdrawing effect of ester (-COOR) group presented in their structures. The electrochemical properties of FQAs were additionally influenced by the presence of methoxy group (-OCH 3 ) attached on the aromatic ring. DPV measurements show that electrochemical oxidation of CQAs and diCQAs at a GCE is reversible, pH dependent, two-electron-two-proton process occured on catechol moiety in the structure of these molecules. Electrochemical oxidation of FQAs proceeded by an EC mechanism. In the first, electrochemical oxidation step, a phenoxy radical was formed by irreversible one-electron-one-proton process. In the second, chemical step, phenoxy radical undergoes hydrolysis generated a new more electroactive compound with methoxy-catechol moiety in the structure. This compound was reversible oxidised to methoxy-ortho-quionone structure by two-electron-two-proton process. The electrochemical properties of 5-CQA (main CGAs in coffee) were investigated more in detail. It was observed that anodic oxidation peak current of 5-CQA show its maximum in PBS solution of pH 7 and linear relationship within the concentration range of 5-50 mol L -1 , with LOD of 1.2·10 -6 mol L -1 . DPVs of coffee show that electrochemical properties of coffee extracts were very similar to that of investigated CGAs. Therefore, DPV was used for characterization of CGAs in coffees. It was shown that DPV is a very sensitive and selective method for determination of total CGAs content in coffee.

The electrochemical behaviour of three structurally related flavonols, quercetin, morin, and rutin was studied by cyclic, differential pulse, and square-wave voltammetry methods. The study reveals that their electrochemical behaviour strongly depends on their chemical structure and electronic properties, particularly on the presence of electron-donating -OH groups, i.e. their numbers and position on rings A, B, and C in the structure of these flavonols. The important factors of the electrochemical oxidation behaviour of flavonols are as follows. (i) The presence of two electron-donating -OH groups on the B ring in the ortho-position. (ii). The 2,3-double bond in conjugation with a 4-oxo group on the C ring. (iii) The electron donating 3-OH group on the C ring, and (iv) the electron-donating 5-OH and 7-OH groups on A ring. Quercetin satisfies all of the requirements mentioned above and therefore has the best electron-donating properties of all investigated flavonols. The first oxidation peak of quercetin (peak A1) corresponds to the reversible oxidation of 3',4'-OH groups (catechol moiety) at the B ring to the ortho-quinone structure by two-electron-two-proton (2e --2H + ) process. This electrochemically active and unstable ortho-quinone species then undergoes chemical rearrangements or addition reactions, indicates an electrochemical-chemical (EC) reaction mechanism. At higher anodic potential the -OH group at position 3 of ring C was oxidized (peak A2), by the reversible one-electron-oneproton reaction. In this study, it was for the first time observed that the second reduction peak of quercetin (peak C2) corresponds to the 3-OH group on ring C. The hydroxyl groups at position 5 and 7 at ring A have significantly smaller electron-donating effect than -OH groups at ring B, and therefore were oxidized at higher anodic potentials (peak A3). This oxidation is an irreversible process. Morin with meta-2',4'-dihydroxyl groups (resorcinol moiety) shows the higher value of oxidation potential of peak A1 than quercetin, indicating that oxidation of 2',4'-OH groups on ring B of morin to quinone structure is more difficult in comparison to that of quercetin. This fact clearly shows the importance of the presence of two hydroxyl groups in the ortho-diphenolic arrangement on the ring B of flavonols. The first oxidation process of morin is an one-electron-one-proton reversible reaction, which proceeds in an EC mechanism. The oxidation peak of morin A3 should be associated with the oxidation of 5,7-dihydroxyl moiety of ring A, which oxidation occurs at very high oxidation potentials. This oxidation is an irreversible process because no reduction peak was observed. The absence of oxidation peak A2

Indexing p. 1  Editorial Bord p. 1  Guide for Authors p. 3  Manuscript preparation p. 5

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The accurate and precise characterization of eight chlorogenic acids (CGAs) isomers, caffeoylquinic acids (5-CQA, 4-CQA, 3-CQA), dicaffeoylquinic acids (3,5-diCQA, 4,5-diCQA, 3,4-diCQA), and feruloylquinic acids (5-FQA, 4-FQA), was carried out using different brands of coffee. High-performance liquid chromatography (HPLC), differential pulse (DPV) and square-wave voltammetry (SWV) were applied for the investigation. HPLC proved to be an accurate and precise method for separation, identification and quantification of CGAs isomers in coffee extracts. DPV and SWV have shown that electrochemical behaviour of coffee extracts was very similar to that of CGAs isomers and DPV and SWV can be used for the correct characterization of CGAs in coffee. All three techniques have shown a very high correlation of CGAs content in all investigated coffee samples. Therefore, HPLC, DPV and SWV methods can be used in combination as very selective, sensitive and precise methods for characterization of CGAs isomers in coffee extracts.

Although neglected as an industrial raw material, rose hip has been important for both nutritional and medical purposes for centuries. The main goal of this study was to propose a rapid and inexpensive non-thermal technique such as high voltage electrical discharge (HVED) to preserve valuable rose hip bioactive compounds, towards the development of high-quality products, including low-calorie products. The objective of this work was to evaluate the effects of HVED on the physicochemical properties and the microbiological safety of rose hip nectar formulations and, for comparison, on a pasteurised sample. Physicochemical analysis proved that rose hip pulp and the prepared nectars were valuable sources of polyphenols and ascorbic acid with high antioxidant activity. The HVED technique had minimal effects on the quality characteristics of the nectars under the different process conditions (50, 100 Hz; 10, 15, 20 min). In addition, the pasteurised nectar showed the greatest loss of ascorbic acid (54%) and phenolic compounds (40%). The microbiological quality of nectars was examined immediately after preparation/treatment and after 6 and 12 days of storage at 4 °C. In addition to the pasteurised sample, HVED-treated rose hip nectar prepared from microwave-blanched puree with extended shelf life had satisfactory microbiological safety after storage.