Variation in the Main Health-Promoting Compounds and Antioxidant Capacity of Three Leafy Vegetables in Southwest China.

Malabar spinach (Basella alba), amaranth (Amaranthus tricolor), and sweet potato (Ipomoea batatas) are leafy vegetables found in Southwest China. The variation of chlorophyll, carotenoids, ascorbic acid, total flavonoids, phenolic compounds, and antioxidant capacity was studied in the leaves and stems of the three vegetables. The content of main health-promoting compounds and the antioxidant capacity in the leaves were higher than that in the stems, indicating that the leaves of the three vegetables possess greater nutritional value. The trend of total flavonoids in all three vegetables was similar to the trend of antioxidant capacity, suggesting that the total flavonoids may be the major antioxidants wihin these vegetables. Eight individual phenolic compounds were detected in three different vegetables. The most abundant levels of individual phenolic compounds in the leaves and stems of malabar spinach, amaranth, and sweet potato were 6'-O-feruloyl-d-sucrose (9.04 and 2.03 mg g-1 DW), hydroxyferulic acid (10.14 and 0.73 mg g-1 DW), and isorhamnetin-7-O-glucoside (34.93 and 6.76 mg g-1 DW), respectively. Sweet potato exhibited a higher total and individual phenolic compound content compared to malabar spinach and amaranth. Overall, the results demonstrate that the three leafy vegetables possess high nutritional value, and could be used not only for consumption but also in various other fields, including medicine and chemistry.

Structural Studies on Diverse Betacyanin Classes in Matured Pigment-Rich Fruits of Basella alba L. and Basella alba L. var. 'Rubra' (Malabar Spinach).

Identification of betacyanins in Basella alba L. and Basella alba L. var. 'Rubra' fruits was performed by low- and high-resolution mass spectrometry (LRMS and HRMS) as well as 1H, 13C and two-dimensional NMR which revealed hitherto completely not known betacyanin classes in the plant kingdom. Especially, the presence of unique nitrogenous acyl moieties in the structures of the pigments was ascertained by the HRMS Orbitrap detection. Except for detected polar betacyanin glycosylated derivatives, presence of a series of previously not reported pigments such as malonylated betanidin 6-O-ß-glusosides with their acyl migration isomers along with the evidence of the 3''-hydroxy-butyrylated betacyanins is reported. The first complete NMR data were obtained for novel and principal acylated gomphrenins with hydroxycinnamic acids: 6'-O-E-caffeoyl-gomphrenin (malabarin), 6'-O-E-sinapoyl-gomphrenin (gandolin), 6'-O-E-4-coumaroyl-gomphrenin (globosin) and 6'-O-E-feruloyl-gomphrenin (basellin).

Conjugation of Oxidized Betanidin and Gomphrenin Pigments from Basella alba L. Fruits with Glutathione.

Formation of glutathionic conjugates with quinonoid forms generated through oxidation of betanidin and gomphrenin obtained from fruits of Basella alba L. was studied by high-performance liquid chromatography coupled with triple quadrupole tandem mass spectrometry (HPLC-DAD-ESI-MS/MS) and ion-trap time-of-flight high-resolution mass spectrometry (LCMS-IT-TOF). The conjugates were studied for the aim of trapping the formed quinonoids by glutathione which would indicate a presence of specific quinonoid structures in reaction products of the pigments with 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) cation radicals. The structure of betanidin conjugate, which was formed with high efficiency, was established by NMR analysis. In the case of gomphrenin conjugate, its structure was tentatively indicated as analogous to betanidin conjugate by MS n fragmentation paths. In contrast, no detectable glutathionic conjugate of betanin quinonoid (quinone methide) was present in similar betanin reaction mixtures. As a result of additional experiments performed during oxidation of gomphrenin by ABTS cation radicals in the absence of glutathione, except for decarboxylated and dehydrogenated gomphrenin derivatives, generation of betanidin and its derivatives was observed which indicated that the subsequent dopachromic intermediate rearrangement affected hydrolysis of the glucosidic bond. This is in contrast to betanin which is not deglucosylated in the same conditions during the oxidation. The obtained results shed some light on the oxidation pathways of various glycosylated betacyanins with gomphrenin being presumably the most potent antioxidant ascertained in this group of pigments.

Thermal Degradation of Major Gomphrenin Pigments in the Fruit Juice of Basella alba L. (Malabar Spinach).

Generation of decarboxylated and dehydrogenated gomphrenins during heating of Basella alba L. fruit juice containing high levels of betacyanin pigments was monitored by LC-DAD-ESI-MS/MS. The presence of principal decarboxylation products, 2-, 17-, and 2,17-decarboxy-gomphrenins, their diastereomers, as well as minor levels of their dehydrogenated derivatives are reported. In addition, determination of molecular masses of decarboxylated gomphrenins by high-resolution mass spectrometry (LCMS-IT-TOF) was performed. Enzymatic deglucosylation of decarboxylated and dehydrogenated gomphrenins resulted in the generation of betanidin diagnostic derivatives for further identification processes. In addition, experiments were conducted to prove that the position of glucosylation of the chromophoric part of betacyanins (betanidin part) has decisive influence on different chromatographic properties of their decarboxylated derivatives.

In vivo tracing of organochloride and organophosphorus pesticides in different organs of hydroponically grown malabar spinach (Basella alba L.).

An in vivo uptake and elimination tracing study based on solid phase microextraction (SPME) was conducted to investigate the accumulation, persistence and distribution of organochloride pesticides (OCPs) and organophosphorus pesticides (OPPs) in malabar spinach (Basella alba L.) plants. Uptake and elimination of the pesticides were traced in leaves, stems and roots of living malabar spinach plants. Root concentration factor (RCF), distribution concentration factor (DCF) and transpiration stream concentration factor (TSCF) were calculated based on the in vivo tracing data. The tracing data showed that the OCPs were much more accumulative and persistent than the OPPs in roots, while they were similarly accumulative and persistent in leaves and stems. RCF values of the OPPs or OCPs were likely to increase with the increase in LogKow values except fenthion. Obtained DCF values indicated that OPPs and OCPs were more accumulative in the organs containing more lipids. TSCF values showed that the translocation of OPPs and OCPs from roots to foliage was firstly dependent on the hydrophobicity of the compounds, but also significantly affected by the water solubility. This is the first study of generating RCF, DCF and TSCF data in living plants by in vivo sampling method, which provides a foundation to promote the application of in vivo SPME and improve understanding of contaminant behaviors in living plants.