Authenticity Assessment of γ- and δ-Decalactone fromPrunusFruits by Gas Chromatography Combustion/Pyrolysis Isotope Ratio Mass Spectrometry (GC-C/P-IRMS)

Abstract

Authenticity assessment of gamma-decalactone (1) and delta-decalactone (2) from peach (Prunus persica var. persica), apricot (Prunus armeniaca), and nectarine (Prunus persica var. nectarina) was performed using gas chromatography-isotope ratio mass spectrometry (GC-IRMS) in the combustion (C) and pyrolysis (P) mode. In addition, commercially available synthetic (nature-identical) 1 and 2 as well as biotechnologically produced samples (declared to be "natural") were characterized by their delta(2)H(V)(-)(SMOW) and delta(13)C(V)(-)(PDB) values. For the Prunus fruits under study, rather narrow ranges of delta(13)C(V)(-)(PDB) and delta(2)H(V)(-)(SMOW) data of 1, varying from - 34.6 per thousand to - 38.4 per thousand and -160 per thousand to -206 per thousand, respectively, were obtained. Synthetic references of 1 showed delta(13)C(V)(-)(PDB) and delta(2)H(V)(-)(SMOW) data ranging from -27.4 per thousand to -28.3 per thousand and -151 per thousand to -184 per thousand, respectively. Samples of 1 declared to be "natural" exhibited ranges from -28.1 per thousand to -29.2 per thousand and -192 per thousand to -286 per thousand for delta(13)C(V)(-)(PDB) and delta(2)H(V)(-)(SMOW), respectively. For 2 from peach, apricot, and nectarine, delta(13)C(V)(-)(PDB) values ranging from -34.0 per thousand to -37.9 per thousand were determined; the delta(2)H(V)(-)(SMOW) values ranged from -171 per thousand to -228 per thousand. The delta(13)C(V)(-)(PDB) and delta(2)H(V)(-)(SMOW) data for synthetic 2 were -28.2 per thousand and -171 per thousand, respectively, that is, similar to those of 2 from "natural" origin, ranging from -27.7 per thousand to -30.1 per thousand and -185 per thousand to -230 per thousand for delta(13)C(V)(-)(PDB) and delta(2)H(V)(-)(SMOW), respectively. GC-C/P-IRMS allowed clear-cut analytical differentiation of the synthetic and "ex-plant" origin of 1 and 2, whereas narrow ranges of delta(13)C(V)(-)(PDB) and delta(2)H(V)(-)(SMOW) data were found for samples of synthetic and "natural" origin.

Gas Chromatography‐Combustion‐Isotope Ratio Mass Spectrometry for Traceability and Authenticity in Foods and Beverages

“…Prunus fruits such as peaches, apricots, and nectarines were analyzed by Tamura and others () for the isotopic ratios of γ‐decalactone and δ‐decalactone (δ 13 C ranges of γ‐decalactone and δ‐decalactone for fruits: −34.0‰ to −38.4‰; “natural”: −27.7‰ to −30.1‰; and synthetic: −27.4‰ to −28.3‰ and δ 2 H ranges of both compounds for fruits: −160‰ to −228‰; “natural”: −185‰ to −286‰; and synthetic: −151‰ to −184‰). Berries also have been subjected to isotope analysis, for example, del Mar Caja and others () analyzed raspberry for α‐ionone, β‐ionone, and α‐ionol (δ 13 C ranges of α‐ionone, β‐ionone, and α‐ionol for fruits: −30.3‰ to −36.6‰; “natural”: −9.1‰ to −28.0‰; and synthetic: −24.5‰ to −29.0‰ and δ 2 H ranges of both compounds for fruits: −176‰ to −225‰; “natural”: −43‰ to −257‰; and synthetic: −26‰ to −184‰).…”

Construction of IsoVoc Database for the Authentication of Natural Flavours

“…Much effort has also gone into developing isotopic methods to detect adulteration of natural products with synthetic compounds. Among them, gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS) seems to be the most specific and sophisticated method that can discriminate between natural and synthetic aromas based on the isotopic values of selected volatile organic compounds, VOCs [ 7 , 8 , 9 , 10 , 11 , 12 , 13 , 14 , 15 , 16 , 17 , 18 , 19 , 20 , 21 , 22 , 23 , 24 , 25 ]. The use of GC-C-IRMS is the subject of a review by van Leeuwen et al [ 8 ] and a paper by Strojnik et al [ 26 ] in which the authors emphasise the importance of the relevant analytical conditions to obtain precise isotopic ratios.…”

“…Articles on determining the authenticity of fruit volatile organic compounds based on GC-C-IRMS are summarised in Appendix A ( Table A1 ). These studies cover, for example, raspberry [ 10 , 13 , 18 , 19 , 27 ], peach [ 7 , 11 , 23 , 25 ], strawberry [ 7 , 8 , 20 ], apple [ 16 , 25 , 28 ], nectarine [ 11 , 23 , 25 ], pineapple [ 7 , 9 ], and orange [ 15 , 25 ]. Many aromatic characteristics are shared between different fruits.…”

Turning natural δ-lactones to thermodynamically stable polymers with triggered recyclability

“…δ-dodecalactone, 28 PEG and ω-pentadecalactone, 29 lactide, 30 methylene diphenyl diisocyanate, 10 1,4 butylene oxide, 14 δ-valerolactone 31 and maltohepotaose. 32 δDL occurs naturally in fruits 33 and milk, 34 but can also be produced enzymatically on large scale from fatty acids and essential oils. 35,36 Recently, it was shown that catalytic transfer hydrogenation 37 could be a new and interesting course to synthesize the monomer, which also increases the potential of establishing δDL as a biobased platform monomer.…”