Abstract

5-(hydroxymethyl)furan-2-carbaldehyde, better known as hydroxymethylfurfural (HMF), is a well-known freshness parameter of honey: although mostly absent in fresh samples, its concentration tends to increase naturally with aging. However, high quantities of HMF are also found in fresh but adulterated samples or honey subjected to thermal or photochemical stresses. In addition, HMF deserves further consideration due to its potential toxic effects on human health. The processes at the origin of HMF formation in honey and in other foods, containing saccharides and proteins—mainly non-enzymatic browning reactions—can also produce other furanic compounds. Among others, 2-furaldehyde (2F) and 2-furoic acid (2FA) are the most abundant in honey, but also their isomers (i.e., 3-furaldehyde, 3F, and 3-furoic acid, 3FA) have been found in it, although in small quantities. A preliminary characterization of HMF, 2F, 2FA, 3F, and 3FA by cyclic voltammetry (CV) led to hypothesizing the possibility of a comprehensive quantitative determination of all these compounds using a simple and accurate square wave voltammetry (SWV) method. Therefore, a new parameter able to provide indications on quality of honey, named “Furanic Index” (FI), was proposed in this contribution, which is based on the simultaneous reduction of all analytes on an Hg electrode to ca. −1.50 V vs. Saturated Calomel Electrode (SCE). The proposed method, validated, and tested on 10 samples of honeys of different botanical origin and age, is fast and accurate, and, in the case of strawberry tree honey (Arbutus unedo), it highlighted the contribution to the FI of the homogentisic acid (HA), i.e., the chemical marker of the floral origin of this honey, which was quantitatively reduced in the working conditions. Excellent agreement between the SWV and Reverse-Phase High-Performance Liquid Chromatography (RP-HPLC) data was observed in all samples considered.

Highlights

  • High-Performance Liquid Chromatography (RP-HPLC) data was observed in all samples considered

  • Honey is the sweet natural product that honeybees obtain by conversion of the nectar gathered from flowers

  • In order to provide a thorough evaluation of any reactive furanic-based compounds formed in honeys by degradation of this matrix, a rapid and accurate square wave voltammetry (SWV) method has been developed, optimized, and validated to measure the amount of HMF as well as of 2-furaldehyde, 2F, 3-furaldehyde, 3F, 2-furoic acid, 2FA, and 3-furoic acid, 3FA

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Summary

Introduction

Honey is the sweet natural product that honeybees obtain by conversion of the nectar gathered from flowers. In honey, acidic conditions and the predominance of monosaccharides, as fructose and glucose, promote its formation during aging or processing [3,4]. For these reasons, the amount of HMF in honey is considered a freshness parameter: while it is basically absent in fresh and well-preserved honey, its amount naturally increases with aging and in the presence of other factors such as heat, sunlight, and metal ions, which promote the course of the Maillard’s reaction [5,6,7].

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