Crude peroxidase from onion solid waste as a tool for organic synthesis. Part I: Cyclization of 2′,3,4,4′,6′-pentahydroxy-chalcone into aureusidin

The potential of a crude peroxidase (POD) from onion solid waste as a biocatalyst for the synthesis of a naturally occurring aurone is described. The crude enzyme preparation effectively promotes the cyclization of 2′,3,4,4′,6′-pentahydroxy-chalcone (which is not a natural substrate of onion POD) into aureusidin.     

Clean recovery of antioxidant flavonoids from onions: Optimising solvent free microwave extraction method

A solvent free microwave hydrodiffusion and gravity extraction (MHG) of flavonol content from onion (Allium cepa L.) was studied. Effectiveness of this innovative method in extraction of onion total phenolic content, total quercetin (TQ), quercetin aglycon (QA), quercetin-3,4′-diglucoside (QDG), quercetin-4′-monoglucoside (Q4G), quercetin-3-monoglucoside (Q3G), kaempferol (KMF) and myricetin (MRT) have been evaluated and compared with conventional solvent extraction. Microwave extraction offers important advantages like shorter extraction time (23 min), cleaner feature (no solvent or water used) and extraction of valuable onion crude juice retaining fresh organoleptic properties with higher phenolic content (58.29 mg GAE/g DW) at optimized power (500 W). Microwave extraction resulted significant yield (81.5%) with 41.9% of flavonol contents, with better retain of remaining flavonoids (55.9%) in residues of onions. QDG (239.7 mg/100 g DW) and Q4G (82.55 mg/100 g DW) have been reported the main flavonol in this study. Minor quantities of QA (traces), Q3G (4.22 mg/100 g DW) and KMF (3.99 mg/100 g DW) were also detected in microwave onion extracts.     

Chromatographic methods for determination of S-substituted cysteine derivatives—A comparative study

A novel HPLC method for determination of a wide variety of S-substituted cysteine derivatives in Allium species has been developed and validated. This method allows simultaneous separation and quantification of S-alk(en)ylcysteine S-oxides, γ-glutamyl-S-alk(en)ylcysteines and γ-glutamyl-S-alk(en)ylcysteine S-oxides in a single run. The procedure is based on extraction of these amino acids and dipeptides by methanol, their derivatization by dansyl chloride and subsequent separation by reversed phase HPLC. The main advantages of the new method are simplicity, excellent stability of derivatives, high sensitivity, specificity and the ability to simultaneously analyze the whole range of S-substituted cysteine derivatives. This method was critically compared with other chromatographic procedures used for quantification of S-substituted cysteine derivatives, namely with two other HPLC methods (derivatization by o-phthaldialdehyde/tert-butylthiol and fluorenylmethyl chloroformate), and with determination by gas chromatography or capillary electrophoresis. Major advantages and drawbacks of these analytical procedures are discussed. Employing these various chromatographic methods, the content and relative proportions of individual S-substituted cysteine derivatives were determined in four most frequently consumed alliaceous vegetables (garlic, onion, shallot, and leek).     

A simple; efficient and environmentally friendly method for the extraction of pesticides from onion by matrix solid-phase dispersion with liquid chromatography-tandem mass spectrometric detection

An evaluation of the extraction of pesticides from onion by matrix solid-phase dispersion (MSPD) with the determination by liquid chromatography tandem mass spectrometry using electrospray as the ionization source (LC-ESI-MS/MS) was carried out. The performance of different sorbents, including reused C18 bonded silica, was evaluated. Different parameters affecting the extraction efficiency were evaluated, such as the type and amount of sorbent, the time of interaction after the fortification step, the time of sample dispersion and the elution solvent. The matrix effect regarding the recovery of the pesticides by MSPD was also investigated. The best results were obtained using 0.5 g of sample, 1.0 g reused C18, interaction time of 1 h, dispersion time of 5 min, and acetonitrile as the elution solvent. The method was validated by the fortification of the onion sample, free of pesticides, at different concentration levels (0.01, 0.1 and 1.0 mg kg⁻¹). Average recoveries ranged from 78.3 to 120.4% and relative standard deviation below 20% was obtained. Detection and quantification limits ranged from 0.003 to 0.03 mg kg⁻¹ and from 0.01 to 0.1 mg kg⁻¹, respectively.     

Visualization technique for uncertainty budgets: Onion charts

A concise graphical depiction, the “onion” chart, is described for presenting uncertainty budgets for any measurand, y, having a set of component variances, . The onion chart consists of a concentric series of rings. Each ring is constructed from the set of fractional contributions, . The outer ring includes all and depicts the combined standard uncertainty, u _c (y), where u _c ²(y) ≡ ∑u _i ²(y). Moving inward, each successive ring deletes the largest remaining . A “reduced” is calculated for that ring from the remaining set of , with the fractional contributions calculated using the “reduced” . This format facilitates rapid visual comparison of the importance of each component, with minor components becoming visible as the larger components are successively deleted. An example is presented using data from pH metrology, including the physical interpretation of the resulting diagram.     

The Organosulfur Chemistry of the Genus Allium – Implications for the Organic Chemistry of Sulfur

A Cook's tour is presented of the organosulfur chemistry of the genus Allium, as represented, inter alia, by garlic (Allium sativum L.) and onion (Allium cepa L.). We report on the biosynthesis of the S-alk(en)yl-L -cysteine S-oxides (aroma and flavor precursors) in intact plants and on how upon cutting or crushing the plants these precursors are cleaved by allinase enzymes, giving sulfenic acids—highly reactive organosulfur intermediates. In garlic, 2-propenesulfenic acid gives allicin, a thiosulfinate with antibiotic properties, while in onion 1-propenesulfenic acid rearranges to the sulfine (Z)-propanethial S-oxide, the lachrymatory factor (LF) of onion. Highlights of onion chemistry include the assignment of stereochemistry to the LF and determination of the mechanism of its dimerization; the isolation, characterization, and synthesis of thiosulfinates which most closely duplicate the taste and aroma of the freshly cut bulb, and additional unusual compounds such as zwiebelanes (dithiabicyclo[2.1.1]hexanes), a bis-sulfine (a 1,4-butanedithial S,S′-dioxide), antithrombotic and antiasthmatic cepaenes (α-sulfinyl disulfides), and vic-disulfoxides. Especially noteworthy in the chemistry of garlic are the discovery of ajoene, a potent antithrombotic agent from garlic, and the elucidation of the unique sequence of reactions that occur when diallyl disulfide, which is present in steam-distilled garlic oil, is heated. Reaction mechanisms under discussion include [3, 3]- and [2, 3]-sigma-tropic rearrangements involving sulfur (e.g. sulfoxide-accelerated thio- and dithio-Claisen rearrangements) and cycloadditions involving thiocarbonyl systems. In view of the culinary importance of alliaceous plants as well as the unique history of their use in folk medicine, this survey concludes with a discussion of the physiological activity of the components of these plants: cancer prevention, antimicrobial activity, insect and animal attractive/repulsive activity, olfactory–gustatory–lachrymatory properties, effect on lipid metabolism, platelet aggregation inhibitory activity and properties associated with ajoene. And naturally, comments about onion and garlic induced bad breath and heartburn may not be overlooked.     

Crude peroxidase from onion solid waste as a tool for organic synthesis. Part II: oxidative dimerization-cyclization of methyl p-coumarate, methyl caffeate and methyl ferulate

The ability of a crude onion peroxidase preparation to act as a biocatalyst for the oxidative dimerization-cyclization of methyl p-coumarate, methyl caffeate and methyl ferulate is presented. The products of the reaction have been fully characterized and were found to possess potent antioxidant activity in a ferric reducing antioxidant power (FRAP) assay.