Hemp Chemotype Definition by Cannabinoids Characterization Using LC-ESI(+)-LTQ-FTICR MS and Infrared Multiphoton Dissociation

The development and application of advanced analytical methods for a comprehensive analysis of Cannabis sativa L. extracts plays a pivotal role in order to have a reliable evaluation of their chemotype definition to guarantee the efficacy and safety in pharmaceutical use. This paper deals with the qualitative and quantitative determination of cannabidiol (CBD), tetrahydrocannabinol (THC), cannabinol (CBN), tetrahydrocannabivarin (THCV), cannabidivarin (CBDV), and cannabigerol (CBG) based on a liquid chromategraphy-mass spectrometry (LC-MS) method using electrospray ionization in positive mode (ESI+), coupled with a hybrid quadrupole linear ion trap (LTQ) and Fourier transform ion cyclotron resonance mass spectrometer (FTICR-MS). For the first time, structural information of phytocannabinoids is available upon precursor ions’ isolation within the FTICR trapping cell and subsequent fragmentation induced by infrared multiphoton dissociation (IRMPD). Such fragmentation and accurate mass measurement of product ions, alongside collision-induced dissociation (CID) within LTQ, was advantageous to propose a reliable fragmentation pattern for each compound. Then, the proposed LC-ESI(+)-LTQ-FTICR MS method was successfully applied to the hemp chemotype definition of three registered Italian accessions of hemp C. sativa plants (Carmagnola C.S., Carmagnola, and Eletta Campana), thus resulting in the Eletta Campana accession being the best one for cannabis product manufacturing.

Multi-proxy assessment of surface sediments using APPI-P FTICR-MS reveals a complex biogeochemical record along a salinity gradient in the Pearl River estuary and coastal South China Sea

The Pearl River drains the second largest watershed in China, funnelling large amounts of freshwater and organic matter into the northern part of the South China Sea through an estuary characterized by pronounced biogeochemical gradients. In this study we analyzed organic extracts of surface sediments collected along land-sea transect that captures a transition from freshwater environment at the site of the Pearl River discharge, to marine settings at the most distal sampling point in the coastal South China Sea. Samples were analyzed using Fourier transform ion cyclotron mass spectrometry (FTICR-MS), to assess the molecular composition of the organic species present in the sediment and understand the sources and diagenesis of deposited organic matter. Results show a complex mixture of molecular markers, many of which can be used as proxies to distinguish between the freshwater and saline settings. For example, geochemical signal at the freshwater site is notably characterized by species belonging to hydrocarbon and sulphur-containing compound classes – these are likely markers of terrestrial, natural and/or anthropogenic organic matter inputs. On the other hand, samples from the coastal marine site bear a unique signature of putative tetrapyrrole species, molecular indicators of phytoplankton phaeopigments. Notably, some unusual and or novel species, such as sterenes and alkanones were putatively identified. These and other biomarkers species that can be detect using our single injection method provide convenient multiple proxies necessary for interpreting dynamic changes from land to the ocean, which have even been complicated by anthropogenic activities.

A novel route for identifying starch diagenetic products in the archaeological record

This work introduces a novel analytical chemistry method potentially applicable to the study of archaeological starch residues. The investigation involved the laboratory synthesis of model Maillard reaction mixtures and their analysis through Fourier-Transform Ion Cyclotron Resonance Mass Spectrometry (FTICR-MS). Thus, starch from sixteen plant species were matured while reacting it with the amino acid glycine. The FTICR-MS analysis revealed > 5,300 molecular compounds, with numerous unique heteroatom rich compound classes, ranging from 20 (Zea mays) to 50 (Sorghum bicolor). These classes were investigated as repositories of chemical structure retaining source and process-specific character, linked back to botanical provenance. We discussed the Maillard reaction products thus generated, a possible pathway for the preservation of degraded starch, while also assessing diagenetic recalcitrance and adsorption potential to mineral surfaces. In some cases, hydrothermal experimentation on starches without glycine reveals that the chemical complexity of the starch itself is sufficient to produce some Maillard reaction products. The article concludes that FTICR-MS offers a new analytical window to characterize starchy residue and its diagenetic products, and is able to recognize taxonomic signals with the potential to persist in fossil contexts.

Determination and Metabolite Profiling of Mixtures of Triterpenoid Saponins from Seeds of Chilean Quinoa (Chenopodium quinoa) Germplasm

The seed pericarp of Chenopodium quinoa Willd. (quinoa) contains a mixture of triterpenoid saponins conferring undesired organoleptic properties. In this study, we evaluated saponin content and their corresponding sapogenins in 114 different quinoa accessions. Relative saponin content ranged from 0.22 to 15.04 mg/g of seed dry weight among the genotypes studied and the genotype effect was significant (p < 0.001). About 75% of the genotypes could be classified as low-saponin content lines which is promising in view of ongoing plant breeding efforts. In addition to the quantitative determination of saponins, metabolic profiling was performed by LC-FTICR-MS and LC-MS/MS. We obtained highly accurate mass estimation from ion spectra allowing the identification of twelve saponins of the oleanane type. These differ in their aglycons and in the number and type of glycoside units. Interestingly, we identified a saponin compound that, to our knowledge, had not been reported previously. Our study highlights that there is considerable variability concerning saponin content in quinoa, which contributes to the valorization of genetic resources towards the identification of genotypes that could be utilized in current and future quinoa breeding programs.

Using MALDI-FTICR-MS Imaging to Track Low-Molecular-Weight Aromatic Derivatives of Fungal Decayed Wood

Low-molecular-weight (LMW) aromatics are crucial in meditating fungal processes for plant biomass decomposition. Some LMW compounds are employed as electron donors for oxidative degradation in brown rot (BR), an efficient wood-degrading strategy in fungi that selectively degrades carbohydrates but leaves modified lignins. Previous understandings of LMW aromatics were primarily based on “bulk extraction”, an approach that cannot fully reflect their real-time functions during BR. Here, we applied an optimized molecular imaging method that combines matrix-assisted laser desorption ionization (MALDI) with Fourier-transform ion cyclotron resonance mass spectrometry (FTICR-MS) to directly measure the temporal profiles of BR aromatics as Rhodonia placenta decayed a wood wafer. We found that some phenolics were pre-existing in wood, while some (e.g., catechin-methyl ether and dihydroxy-dimethoxyflavan) were generated immediately after fungal activity. These pinpointed aromatics might be recruited to drive early BR oxidative mechanisms by generating Fenton reagents, Fe2+ and H2O2. As BR progressed, ligninolytic products were accumulated and then modified into various aromatic derivatives, confirming that R. placenta depolymerizes lignin. Together, this work confirms aromatic patterns that have been implicated in BR fungi, and it demonstrates the use of MALDI-FTICR-MS imaging as a new approach to monitor the temporal changes of LMW aromatics during wood degradation.

On the Trail of the German Purity Law: Distinguishing the Metabolic Signatures of Wheat, Corn and Rice in Beer

Here, we report a non-targeted analytical approach to investigate the influence of different starch sources on the metabolic signature in the final beer product. An extensive sample set of commercial beers brewed with barley, wheat, corn and/or rice were analyzed by both direct infusion Fourier transform ion cyclotron mass spectrometry (DI-FTICR MS, 400 samples) and UPLC-ToF-MS (100 samples). By its unrivaled mass resolution and accuracy, DI-FTICR-MS was able to uncover the compositional space of both polar and non-polar metabolites that can be traced back to the use of different starch sources. Reversed phase UPLC-ToF-MS was used to access information about molecular structures (MS2-fragmentation spectra) and isomeric separation, with a focus on less polar compounds. Both analytical approaches were able to achieve a clear statistical differentiation (OPLS-DA) of beer samples and reveal metabolic profiles according to the starch source. A mass difference network analysis, applied to the exact marker masses resolved by FTICR, showed a network of potential secondary metabolites specific to wheat, corn and rice. By MS2-similarity networks, database and literature search, we were able to identify metabolites and compound classes significant for the use of the different starch sources. Those were also found in the corresponding brewing raw materials, confirming the potential of our approach for quality control and monitoring. Our results also include the identification of the aspartic acid-conjugate of N-β-D-glucopyranosyl-indole-3-acetic acid as a potential marker for the use of rice in the brewing industry regarding quality control and food inspection purposes.

New Insights into the Seasonal Variation of DOM Quality of a Humic-Rich Drinking-Water Reservoir—Coupling 2D-Fluorescence and FTICR MS Measurements

Long-term changes in dissolved organic matter (DOM) quality, especially in humic-rich raw waters, may lead to intensive adaptions in drinking-water processing. However, seasonal DOM quality changes in standing waters are poorly understood. To fill this gap, the DOM quality of a German drinking water reservoir was investigated on a monthly basis by Fourier-transform ion cyclotron resonance mass spectrometry (FTICR MS) measurements and 2D fluorescence for 18 months. FTICR MS results showed seasonal changes of molecular formula (MF) intensities, indicating photochemical transformation of DOM as a significant process for DOM quality variation. For an assessment of the two humic-like components, identified by parallel factor analysis (PARAFAC) of excitation–emission matrices (EEM), their loadings were Spearman’s rank-correlated with the intensities of the FTICR MS-derived MF. One of the two PARAFAC components correlated to oxygen-rich and relatively unsaturated MF identified as easily photo-degradable, also known as coagulants in flocculation processes. The other PARAFAC component showed opposite seasonal fluctuations and correlated with more saturated MF identified as photo-products with some of them being potential precursors of disinfection byproducts. Our study indicated the importance of elucidating both the chemical background and seasonal behavior of DOM if raw water-quality control is implemented by bulk optical parameters.