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.
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.
Abiotic and biotic stresses are the main reasons of substantial crop yield losses worldwide. Research devoted to reveal mechanisms of plant reactions during their interactions with the environment are conducted on the level of genome, transcriptome, proteome, and metabolome. Data obtained during these studies would permit to define biochemical and physiological mechanisms of plant resistance or susceptibility to affecting factors/stresses. Metabolomics based on mass spectrometric techniques is an important part of research conducted in the direction of breeding new varieties of crop plants tolerant to the affecting stresses and possessing good agronomical features. Studies of this kind are carried out on model, crop and resurrection plants. Metabolites profiling yields large sets of data and due to this fact numerous advanced statistical and bioinformatic methods permitting to obtain qualitative and quantitative evaluation of the results have been developed. Moreover, advanced integration of metabolomics data with these obtained on other omics levels: genome, transcriptome and proteome should be carried out. Such a holistic approach would bring us closer to understanding biochemical and physiological processes of the cell and whole plant interacting with the environment and further apply these observations in successful breeding of stress tolerant or resistant crop plants.
Summary: Determining the role of plant secondary metabolites in stress conditions is problematic due to the diversity of their structures and the complexity of their interdependence with different biological pathways. Correlation of metabolomic data with the genetic background provides essential information about the features of metabolites. LC‐MS analysis of leaf metabolites from 100 barley recombinant inbred lines (RILs) revealed that 98 traits among 135 detected phenolic and terpenoid compounds significantly changed their level as a result of drought stress. Metabolites with similar patterns of change were grouped in modules, revealing differences among RILs and parental varieties at early and late stages of drought. The most significant changes in stress were observed for ferulic and sinapic acid derivatives as well as acylated glycosides of flavones. The tendency to accumulate methylated compounds was a major phenomenon in this set of samples. In addition, the polyamine derivatives hordatines as well as terpenoid blumenol C derivatives were observed to be drought related. The correlation of drought‐related compounds with molecular marker polymorphisms resulted in the definition of metabolomic quantitative trait loci in the genomic regions of single‐nucleotide polymorphism 3101‐111 and simple sequence repeat Bmag0692 with multiple linkages to metabolites. The associations pointed to genes related to the defence response and response to cold, heat and oxidative stress, but not to genes related to biosynthesis of the compounds. We postulate that the significant metabolites have a role as antioxidants, regulators of gene expression and modulators of protein function in barley during drought.
Twenty-nine flavonoid glycosides were identified in the aqueous extract (PC) of Petroselinum crispum var. crispum leaves and apiin, the major compound, was isolated thereof. Apigenin was obtained (90% purity) by the hydrolysis of apiin. A high content of phenolics (12.49 ± 1.70 mg GAE per g of parsley extract – Folin–Ciocalteu method) and total flavonoids (15.05 ± 2.20 mg of quercetin equivalents per g of parsley extract – aluminum chloride method) was quantified in P. crispum, as well as high antioxidant activity ((EC50 – 15.50 mg mL−1, DPPH method) and (189.8 mM Fe(II) per mg of dry plant aqueous extract – FRAP method)). In vivo analysis with Saccharomyces cerevisiae cells showed low toxicity of the aqueous extract of parsley, however, it revealed a high dose-dependent antioxidant potential, mainly in the lipoperoxidation assay. In addition, flavonoid apiin also showed antioxidant action on yeast cells under oxidative stress in the cell viability assay (0.1 mM) and lipid peroxidation (0.01 and 0.1 mM), while apigenin was slightly antioxidant. Therefore, it is likely that the antioxidant activity of apiin is related to the total antioxidant capacity of parsley.
Silver nanoparticles are widely used in industry, medicine, biotechnology and agriculture. As a consequence, these nanoparticles are reaching the environment as waste products, which might have a negative impact on the environment, especially on plants. This includes the elicitation of various biochemical processes in plants. In this article, we report on the changes in secondary metabolic profile of Arabidopsis thaliana seedlings subjected to silver nanoparticle treatment in vitro. Briefly, various sizes (10 nm, 40 nm and 100 nm in diameter) and concentrations (0.5-5.0 ppm) of silver nanoparticles were tested. Ultraperformance liquid chromatography coupled with ultraviolet and fluorescence detectors as well as hyphenated to a high-resolution mass spectrometer (UPLC-PDA-FLR, UPLC-HESI-HRMS) and HPLC - ion trap mass spectrometer (HPLC-ESI-MS/MS), were applied to identify and quantify secondary metabolites. To understand whether silver ions could induce changes in the secondary metabolite profile, seedlings treated with silver nitrate in concentrations equivalent to these of nanoparticles were also analysed. The results showed significant differences in the accumulation of phenolic and indole compounds between treatments. Silver nanoparticles and silver ions induced the biosynthesis of camalexin, hydroxycamalexin O-hexoside and hydroxycamalexin malonyl-hexoside. These compounds are important phytoalexins for Brassicaceae family (especially for Camelinae clad) and are also synthetized in response to biotic and abiotic stresses. Statistically significant changes have been also observed for five phenolic compounds and 5'Glucosyl-dihydroneoascorbigen in different treatment conditions.