Plant-derived natural products have long been considered a valuable source of lead compounds for drug development. Natural extracts are usually composed of hundreds to thousands of metabolites, whereby the bioactivity of natural extracts can be represented by synergism between several metabolites. However, isolating every single compound from a natural extract is not always possible due to the complex chemistry and presence of most secondary metabolites at very low levels. Metabolomics has emerged in recent years as an indispensable tool for the analysis of thousands of metabolites from crude natural extracts, leading to a paradigm shift in natural products drug research. Analytical methods such as mass spectrometry (MS) and nuclear magnetic resonance (NMR) are used to comprehensively annotate the constituents of plant natural products for screening, drug discovery as well as for quality control purposes such as those required for phytomedicine. In this review, the current advancements in plant sample preparation, sample measurements, and data analysis are presented alongside a few case studies of the successful applications of these processes in plant natural product drug discovery.

Hydrogen sulfide (H2S) is currently considered among the endogenously produced gaseous molecules that exert various signaling effects in mammalian species. It is the third physiological gasotransmitter discovered so far after NO and CO. H2S was originally ranked among the toxic gases at elevated levels to humans. Currently, it is well-known that, in the cardiovascular system, H2S exerts several cardioprotective effects including vasodilation, antioxidant regulation, inhibition of inflammation, and activation of anti-apoptosis. With an increasing interest in monitoring H2S, the development of analysis methods should now follow. This review stages special emphasis on the several analytical technologies used for its determination including spectroscopic, chromatographic, and electrochemical methods. Advantages and limitations with regards to the application of each technique are highlighted with special emphasis on its employment for H2S in vivo measurement i.e., biofluids, tissues. Fluorescence methods applied for H2S measurement offer an attractive non-invasive and promising approach in addition to its selectivity, however they cannot be considered as H2S-specific probes. On the other hand, colorimetric assays are among the most common methods used for in vitro H2S detection, albeit their employment in vivo H2S measurement has not yet been possible . Separation techniques such as gas or liquid chromatography offer higher selectivity compared to direct spectrophotometric or fluorescence methods especially for suitable for endpoint H2S measurements i.e. plasma or tissue samples. Despite all the developed analytical procedures used for H2S determination, the need for highly selective, much work should be devoted to resolve all the pitfalls of the current methods.

In their environment, plants interact with a multitude of living organisms and have to cope with a large variety of aggressions of biotic or abiotic origin. What has been known for several decades is that the extraordinary variety of chemical compounds the plants are capable of synthesizing may be estimated in the range of hundreds of thousands, but only a fraction has been fully characterized to be implicated in defense responses. Despite the vast importance of these metabolites for plants and also for human health, our knowledge about their biosynthetic pathways and functions is still fragmentary. Recent progress has been made particularly for the phenylpropanoids and oxylipids metabolism, which is more emphasized in this review. With an increasing interest in monitoring plant metabolic reprogramming, the development of advanced analysis methods should now follow. This review capitalizes on the advanced technologies used in metabolome mapping in planta, including different metabolomics approaches, imaging, flux analysis, and interpretation using bioinformatics tools. Advantages and limitations with regards to the application of each technique towards monitoring which metabolite class or type are highlighted, with special emphasis on the necessary future developments to better mirror such intricate metabolic interactions in planta.

Herbs of the Umbelliferae family are popular spices valued worldwide for their many nutritional and health benefits. Herein, five chief umbelliferous fruits viz., cumin, fennel, anise, coriander and caraway were assessed for its secondary metabolites diversity along with compositional changes incurring upon roasting as analyzed via ultra-high performance liquid chromatography coupled to photodiode array and electrospray ionization mass detectors UHPLC-qToF/MS. A total of 186 metabolites were annotated, according to metabolomics society guidelines, belonging mainly to flavonoids, fatty acids and phenolic acids. Multivariate models viz., PCA, HCA and OPLS-DA were further employed to assess fruits' heterogeneity in an untargeted manner and determine mechanistic changes in bioactive makeup post roasting viz., glycosidic cleavage, lipid degradation and Maillard reaction. Finally, the fruits' antioxidant activity showed decline upon roasting and in correlation with its total phenolic content. This study presents the first complete map of umbelliferous fruit metabolome, compositional differences and its roasting effect.