The ability of organisms and organic compounds to reduce metal ions and stabilize them into nanoparticles (NPs) forms the basis of green synthesis. To date, synthesis of NPs from various metal ions using a diverse array of plant extracts has been reported. However, a clear understanding of the mechanism of green synthesis of NPs is lacking. Although most studies have neglected to analyze the green-synthesized NPs (GNPs) for the presence of compounds derived from the extract, several studies have demonstrated the conjugation of sugars, secondary metabolites, and proteins in these biogenic NPs. Despite several reports on the bioactivities (antimicrobial, antioxidant, cytotoxic, catalytic, etc.) of GNPs, only a handful of studies have compared these activities with their chemically synthesized counterparts. These comparisons have demonstrated that GNPs possess better bioactivities than NPs synthesized by other methods, which might be attributed to the presence of plant-derived compounds in these NPs. The ability of NPs to bind with organic compounds to form a stable complex has huge potential in the harvesting of precious molecules and for drug discovery, if harnessed meticulously. A thorough understanding of the mechanisms of green synthesis and high-throughput screening of stabilizing/capping agents on the physico-chemical properties of GNPs is warranted to realize the full potential of green nanotechnology.

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Flavonoid conjugates constitute several classes of plant phenolic secondary metabolites including many isomeric compounds differing in the hydroxylation pattern and substitution of their rings with different groups such as alkyls, acyls or sugars. These compounds occur in plant tissues mainly as glycosides and in many cases it is necessary to have reliable and detailed information concerning the structure of these natural products. Our results were obtained using leaf extracts of Arabidopsis thaliana and Lupinus angustifolius in which different glycosides of flavones, flavonols and isoflavones are present. Analysis of collision-induced dissociation (CID)/MS/MS spectra of protonated [M + H](+), sodiated [M + Na](+) or deprotonated [M - H](-) molecules recorded during HPLC runs may bring needed information in this respect. However, registration of mass spectra of [M + Na](+) ions with a good efficiency is possible only after post-column addition of a sodium acetate solution to the LC column eluate. The retention of sodium cation on the saccharidic parts of the molecule is observed after the CID fragmentation. In many cases, the location of this cation on the glycan attached to C-3 hydroxyl group of flavonol led to assignment of its structure. Additionally, the determination of the structure of the aglycone and of the sequence of the glycan part was made possible through the CID data obtained from the [M + H](+) and [M - H](-) ions. CID spectra show a different order of sugar elimination from hydroxyl groups at C-3 and C-7 in flavonol glycosides isolated from A. thaliana leaves and give sufficient information to discriminate flavonoid O-diglycosides from flavonoid di-O-glycosides.

Consumption of plants of the species Brassica oleracea is related to a decreased incidence of certain cancer forms in humans, and this has been linked to the presence of glucosinolates in those vegetables. After ripe seeds, sprouts of some brassicaceous plants contain the highest concentration of these compounds and are therefore a good source of glucosinolates for chemoprotection. In the present experiments, the content and distribution of glucosinolates was determined in ripe seeds and sprouts (seedlings) of five varieties of B. oleracea (white cabbage, red cabbage, Savoy cabbage, broccoli and cauliflower) by high performance liquid chromatography. The type and concentration of individual glucosinolates varied according to variety of B. oleracea, plant parts in which they occurred and the sprouting period of the seed. Concentration of alkyl glucosinolates decreased whereas that of indol-3-ylmethylglucosinolates increased throughout the sprouting period. Roots had the highest glucosinolate concentration in four and seven day old sprouts whereas at both sprouting times, cotyledons had the highest concentration of alkylthio-and alkylsulphinylglucosinolates. #

Profiling of plant secondary metabolites is still a very difficult task. Liquid chromatography (LC) or capillary electrophoresis hyphenated with different kinds of detectors are methods of choice for analysis of polar, thermo labile compounds with high molecular masses. We demonstrate the applicability of LC combined with UV diode array or/and mass spectrometric detectors for the unambiguous identification and quantification of flavonoid conjugates isolated from Arabidopsis thaliana leaves of different genotypes and grown in different environmental conditions. During LC/UV/MS/MS analyses we were able to identify tetra-, tri-, and di-glycosides of kaempferol, quercetin and isorhamnetin. Based on our results we can conclude that due to the co-elution of different chemical compounds in reversed phase HPLC systems the application of UV detectors does not allow to precisely profile all flavonoid conjugates existing in A. thaliana genotypes. Using MS detection it was possible to unambiguously recognize the glycosylation patterns of the aglycones. However, from the mass spectra we could not conclude neither the anomeric form of the C-1 carbon atoms of sugar moieties in glycosidic bonds between sugars or sugar and aglycone nor the position of the second carbon involved in disaccharides. The applicability of collision induced dissociation techniques (CID MS/MS) for structural analyses of the studied group of plant secondary metabolites with two types of analyzers (triple quadrupole or ion trap) was demonstrated.

Abstract:Mass spectrometry is currently one of the most versatile and sensitive instrumental methods applied to structural characterization of plant secondary metabolite mixtures isolated from biological material including flavonoid glycoconjugates. Resolution of the applied mass spectrometers plays an important role in structural studies of mixtures of the target compounds isolated from biological material. High-resolution analyzers allow obtaining information about elemental composition of the analyzed compounds. Application of various mass spectrometric techniques, including different systems of ionization, analysis of both positive and negative ions of flavonoids, fragmentation of the protonated/deprotonated molecules and in some cases addition of metal ions to the studied compounds before ionization and fragmentation, may improve structural characterization of natural products. In our review we present different strategies allowing structural characterization of positional isomers and isobaric compounds existing in class of flavonoid glycoconjugates and their derivatives, which are synthetized in plants and are important components of the human food and drugs as well as animal feed.

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Lupin seed globulin proteins form complexes with flavonoids, predominantly apigenin C-glycosides. Enzymes typical for the gastrointestinal tract were used to hydrolyze lupin seed globulins. Release of native flavonoids as a result of the proteolysis reaction was observed. Different analytical methods such as size exclusion chromatography, HPLC-MS, and fluorescence spectroscopy (steady-state fluorescence, fluorescence anisotropy, fluorescence lifetimes) were used for a detailed characterization of this phenomenon. Flavonoids liberated from lupin globulin proteins as a result of pancreatin-catalyzed digestion were bound by γ-conglutin resistant to this enzyme. Two possible mechanisms of this interaction may be suggested: hydrogen bonding between oligosaccharide chains of glycoproteins and the sugar moieties of the flavonoid glycosides or electrostatic attraction between positively charged γ-conglutin and flavonoids partially ionized at pH 7.5.