Analysis of 18 Free Amino Acids in Honeybee and Bumblebee Honey from Eastern and Northern Europe and Central Asia Using HPLC-ESI-TQ-MS/MS Approach Bypassing Derivatization Step

Abstract

The profile of amino acids and mono- and disaccharides in conventional polyfloral honey originated from Latvia and Tajikistan and less found in nature bumblebee honey from Russia was investigated. The analysis of free amino acids (FAAs) accomplished by multiple reaction monitoring (MRM) using triple quadrupole mass selective detection (HPLC-ESI-TQ-MS/MS) revealed the presence of 17 FAAs. The concentration of FAAs varied in the range of 0.02–44.41 mg 100 g−1 FW. Proline was the main representative of FAAs, contributing to the total amount of FAAs from 41.7% to 80.52%. The highest concentration of proline was found in bumblebee and buckwheat honey, corresponding to 44.41 and 41.02 mg 100 g−1, respectively. The concentration of essential amino acids (AAs), i.e., leucine, and isoleucine was found to be the highest in buckwheat honey contributing up to 12.5% to the total amount of FAAs. While, the concentration of branched-chain AAs fluctuated within the range of 1.08–31.13 mg 100 g−1 FW, with buckwheat honey having the highest content and polyfloral honey the lowest, respectively. The results of this study confirmed the abundance of FAAs both in honeybee and bumblebee honey. However, the concentration of individual FAAs, such as proline, aspartic acid, leucine, and isoleucine in bumblebee honey was many folds higher than observed in honeybee polyfloral honey.

Translational Research on Bee Pollen as a Source of Nutrients: A Scoping Review from Bench to Real World

“…Among behavioral similarities, some floral volatiles were shown to attract both insects [ 55 ]. A comparative study of honeybee and bumblebee honeys from different geographical and botanical origins reported a similar qualitative composition of free AAs between the two types of honeys, although the quantitative composition was different [ 56 ]. Another comparative study reported recently that honeybees and bumblebees both avoid foraging nutritionally poor (e.g., having low protein and high lipid content) and highly toxic pollen, compared to other insects [ 57 ].…”

A comprehensive characterization of phenolics, amino acids and other minor bioactives of selected honeys and identification of botanical origin markers

“…A significant decrease in proline concentration in honey was reported when honeybee was fed with sucrose rather than pollens (Nisbet et al, 2018). The prevalence and the pollen origin make proline an important criterion for detecting honey adulteration (Dimins et al, 2022). Buckwheat honey contained the highest total free amino acid content, and total branched-chain amino acids (BCAA), including leucine, isoleucine and valine.…”

“…Except for the predominant proline which originates from the hypopharyngeal glands in the worker honeybee (Davies, 1978), some other free amino acids were identified as botanical markers. For examples, leucine, isoleucine, and tyrosine are major amino acids in buckwheat honey (Dimins et al, 2022), and asparagine is enriched in ilex honey (Paramás et al, 2006). A non-proteinogenic amino acid, γ-aminobutyric acid, was unique to chestnut-tree honey (Paramás et al, 2006).…”

Insight into the Recent Application of Chemometrics in Quality Analysis and Characterization of Bee Honey during Processing and Storage

“…The composition of amino acids in honey is dependent on the pollen species from where the nectar originates, therefore, it can serve as an index for botanical differentiation [56,254]. Proline, originated from the salivary secretion of bees acting on honey collection and maturation, has been found in higher amounts than the other amino acids in honeys, as the major contributor with 50-85% of the total amino acids [208,255,256], while in some studies, phenylalanine has been reported to be the predominant one [253,257]. In general, honeydew contains higher amounts of amino acids than floral honeys [203], and can be differentiated from raw floral honey by amino acids composition in all amino acids except for phenylalanine, tyrosine, and proline [255].…”