Unveiling the Pool of Metallophores in Native Environments and Correlation with Their Potential Producers.

For many organisms, metallophores are essential biogenic ligands that ensure metal scavenging and acquisition from their environment. Their identification is challenging in highly organic matter rich environments like peatlands due to low solubilization and metal scarcity and high matrix complexity. In contrast to common approaches based on sample modification by spiking of metal isotope tags, we have developed a two-dimensional (2D) Solid-phase extraction-Liquid chromatography-mass spectrometry (SPE-LC-MS) approach for the highly sensitive (LOD 40 fmol per g of soil), high-resolution direct detection and identification of metallophores in both their noncomplexed (apo) and metal-complexed forms in native environments. The characterization of peat collected in the Bernadouze (France) peatland resulted in the identification of 53 metallophores by a database mass-based search, 36 among which are bacterial. Furthermore, the detection of the characteristic (natural) metal isotope patterns in MS resulted in the detection of both Fe and Cu potential complexes. A taxonomic-based inference method was implemented based on literature and public database (antiSMASH database version 3.0) searches, enabling to associate over 40% of the identified bacterial metallophores with potential producers. In some cases, low completeness with the MIBiG reference BCG might be indicative of alternative producers in the ecosystem. Thus, coupling of metallophore detection and producers' inference could pave a new way to investigate poorly documented environment searching for new metallophores and their producers yet unknown.

Multivariate Statistical Analysis for Mutual Dependence Assessment of Selected Polyphenols, Organic Acids and Metals in Cool-Climate Wines.

Polyphenols, organic acids and metal ions are an important group of compounds that affect the human health and quality of food and beverage products, including wines. It is known that a specific correlation between these groups exist. While wines coming from the New World and the Old World countries are extensively studied, wines coming from cool-climate countries are rarely discussed in the literature. One of the goals of this study was to determine the elemental composition of the wine samples, which later on, together as polyphenols and organic acids content, was used as input data for chemometric analysis. The multivariate statistical approach was applied in order to find specific correlations between the selected group of compounds in the cool-climate wines and the features that distinguish the most and differ between red and white wines and rosé wines. Moreover, special attention was paid to resveratrol and its correlation with selected wine constituents.

Profiling of polar ionogenic metabolites in Polish wines by capillary electrophoresis-mass spectrometry.

The composition of wine is determined by a complex interaction between environmental factors, genetic factors (i.e., grape varieties), and winemaking practices (including technology and storage). Metabolomics using NMR spectroscopy, GC-MS, and/or LC-MS has shown to be a useful approach for assessing the origin, authenticity, and quality of various wines. Nonetheless, the use of additional analytical techniques with complementary separation mechanisms may aid in the deeper understanding of wine's metabolic processes. In this study, we demonstrate that CE-MS is a very suitable approach for the efficient profiling of polar ionogenic metabolites in wines. Without using any sample preparation or derivatization, wine was analyzed using a 10-min CE-MS workflow with interday RSD values for 31 polar and charged metabolites below 3.8% and 23% for migration times and peak areas, respectively. The utility of this workflow for the global profiling of polar ionogenic metabolites in wine was evaluated by analyzing different cool-climate Polish wine samples.

Green, simple analytical method for biogenic amines determination in fruit juice samples using salting-out assisted liquid-liquid microextraction andgas chromatography-mass spectrometry.

Salting-out assisted liquid-liquid microextraction (SALLME) was integrated withthederivatization procedure to establish a one-step sample pre-treatment approach for rapid analysis of14 biogenic amines (BAs) in fruit juices. The methodology consists of salting-out ofanalytes,derivatization with ethyl chloroformate (ECF), extraction with ethyl acetate (EtAc), andtheanalysis of the derivatized BAs using gas chromatography-mass spectrometry (GC-MS). Optimization oftheSALLME parameters, including the amount of sample, NaOH, and ECF was carried out through a Box-Behnken response surface design. The developed method exhibits satisfactory limits ofdetection (from 1.5 to 8.1 µg/L) andquantification (from 5.0 to 26.7 µg/L), and average recoveries between 84% and 108%. The developed procedure was used for BAs determination injuices ofdifferent berries withthe highest determined concentrations found for cadaverine, putrescine, tryptamine, andtyramine. Both GAPI and AGREE tools were used to assess the green character of the SALLME-GC-MS procedure.

Multicriteria Decision Analysis and Grouping of Analytical Procedures for Phthalates Determination in Disposable Baby Diapers.

This study presents the application of one of the tools from the multicriteria decision analysis set (MCDA), the Technique for Order Preference by Similarity to Ideal Solution (TOPSIS). Selected green analytical chemistry metrics were used to rank analytical procedures for the phthalate determination in disposable baby diapers. Nine analytical procedures were assessed in order to find one that has the lowest environmental impact and the best analytical figures of merit. Nine different criteria, where weighting was based on the experts' evaluation, were used in the procedures' assessment. With the use of TOPSIS, an easy and straightforward technique, selection of the most appropriate procedure was made.

Organic Acids and Polyphenols Determination in Polish Wines by Ultrasound-Assisted Solvent Extraction of Porous Membrane-Packed Liquid Samples.

In the near future, Poland is going to have more and more favorable conditions for viticulture. Organic acids and polyphenols are among the most commonly analyzed compounds due to their beneficial properties for human health and their importance in the winemaking process. In this work, a new technique involving ultrasound-assisted solvent extraction of porous membrane-packed liquid samples (UASE-PMLS) was for the first time described and applied for real samples. The methodology based on UASE-PMLS for organic acids and polyphenols in wine samples was optimized and validated. Using the new technique coupled to GC-MS, organic acids and polyphenols were evaluated in Polish wine samples. Extraction solvent, extraction temperature, derivatization time and sample pH were optimized. Chemometric tools were used for data treatment. Good linearity was obtained for the concentration ranges evaluated with r values between 0.9852 and 0.9993. All parameters of method validation (intra- and inter-day precision and matrix effect) were over 80% with coefficient of variation (CV) up to 17%. Recovery was between (92.0 ± 8.5)% and (113 ± 16)%. Finally, green assessment was evaluated using Analytical Eco-Scale and Green Analytical Procedure Index (GAPI). The UASE-PMLS is characterized by many advantages, e.g., the extraction process is fast and easy coupled to GC-MS. Regarding other extraction techniques, the amount of used solvent is minimum, and no waste is generated. Therefore, it is an environmentally friendly technique.