Enhanced removal of chiral emerging contaminants by an electroactive biofilter.

50% of pharmaceuticals and 25% of herbicides used worldwide are chiral. Each enantiomer has a unique toxicity and biodegradation profile, affecting differently to organisms. Chirality plays a key role in the behavior of these emerging contaminants (ECs) in terms of their pharmacological or herbicidal activity, but this peculiarity is often overlooked in environmental research.

Quantification of relevant metabolites in apoptotic bodies from HK-2 cells by targeted metabolomics based on liquid chromatography-tandem mass spectrometry.

Background: Apoptotic bodies play an important role in the cellular communication as a consequence of the great variety of biomolecules they harbor. There is evidence that 1st generation apoptotic bodies from HK-2 cells induced by cisplatin or UV light trigger apoptosis in naïve HK-2 cells whereas 2nd generation apoptotic bodies activate cell proliferation showing an opposite effect. Thus, the development of new analytical strategies to quantify the changes in the involved metabolites is imperative to shed light on the biological mechanisms which trigger apoptosis and cell proliferation.

Chiral Analysis of Pesticides and Emerging Contaminants by Capillary Electrophoresis-Application to Toxicity Evaluation.

Chiral analysis is a very relevant topic in environmental chemistry. This is due to the different properties of the stereoisomers of chiral compounds. In the case of agrochemicals, the desired activity, degradation rate, or toxicity, among other characteristics, may differ between stereoisomers, and the same is true for emerging contaminants, such as pharmaceuticals and cosmetics.

miRNA and DNA analysis by negative ion electron transfer dissociation and infrared multiple-photon dissociation mass spectrometry.

Background: The use of simple and hybrid fragmentation techniques for the identification of molecules in tandem mass spectrometry provides different and complementary information on the structure of molecules. Nevertheless, these techniques have not been as widely explored for oligonucleotides as for peptides or proteins. The analysis of microRNAs (miRNAs) warrants special attention, given their regulatory role and their relationship with several diseases.

Unlocking peach juice byproduct potential in food waste biorefineries: Phenolic compounds profile, antioxidant capacity and fermentable sugars.

This work assesses an integrated pathway for the revalorization of peach byproduct (PB) within a biorefinery. PB was subjected to an oven-drying (OD) treatment for its evaluation as a storage treatment. It was compared to freeze-drying and untreated material in terms of antioxidant capacity (AOC), phenolic compounds (PC) profile and fermentable sugar production.

Rapid indirect separation of glutamine enantiomers by micellar electrokinetic chromatography. Analysis of dietary supplements.

Glutamine is the most abundant free proteinogenic α-amino acid. It is naturally produced in the organism and acts as a precursor for the synthesis of different biologically important molecules (such as proteins or nucleotides). However, under stressful conditions, the organism is unable to produce it in enough amounts to function properly.

Rapid enantiomeric separation of indacaterol by electrokinetic chromatography.

The first chiral methodology enabling the separation of indacaterol enantiomers was developed in this work by cyclodextrin-electrokinetic chromatography. Indacaterol (IND) is a chiral drug marketed as a pure enantiomer. Then, the separation and quantification of each enantiomer is of great importance for the quality control of pharmaceutical formulations.

Enantioseparation and ecotoxicity evaluation of ibrutinib by Electrokinetic Chromatography using single and dual systems.

In this work, two chiral methods enabling the separation of ibrutinib enantiomers were developed by Electrokinetic Chromatography. A cyclodextrin (CD) or a mixture of the CD and a chiral ionic liquid (CIL) was used as chiral selector. Using the single CD system, seven neutral and six anionic CDs were tested in a formate buffer at pH 3.

Simultaneous microextraction of pesticides from wastewater using optimized μSPEed and μQuEChERS techniques for food contamination analysis.

Food contamination with pesticides poses significant risks to consumer safety and undermines confidence in food supply chains. Detecting pesticides in food samples is a challenging task that requires efficient extraction techniques. This study aims to compare and validate two microextraction techniques, μSPEed and μQuEChERS-dSPE, for the simultaneous extraction of eight pesticides (paraquat, thiabendazole, asulam, picloram, ametryn, atrazine, linuron, and cymoxanil) from wastewater samples.

Enantiomeric analysis of drugs in water samples by using liquid-liquid microextraction and nano-liquid chromatography.

The nano-LC technique is increasingly used for both fast studies on enantiomeric analysis and test beds of novel stationary phases due to the small volumes involved and the short conditioning and analysis times. In this study, the enantioseparation of 10 drugs from different families was carried out by nano-LC, utilizing silica with immobilized amylose tris(3-chloro-5-methylphenylcarbamate) column. The effect on chiral separation caused by the addition of different salts to the mobile phase was evaluated.

Exploring the Metabolic Differences between Cisplatin- and UV Light-Induced Apoptotic Bodies in HK-2 Cells by an Untargeted Metabolomics Approach.

Among the extracellular vesicles, apoptotic bodies (ABs) are only formed during the apoptosis and perform a relevant role in the pathogenesis of different diseases. Recently, it has been demonstrated that ABs from human renal proximal tubular HK-2 cells, either induced by cisplatin or by UV light, can lead to further apoptotic death in naïve HK-2 cells. Thus, the aim of this work was to carry out a non-targeted metabolomic approach to study if the apoptotic stimulus (cisplatin or UV light) affects in a different way the metabolites involved in the propagation of apoptosis.

Quantitative multiple fragment monitoring with enhanced in-source fragmentation/annotation mass spectrometry.

Analytical techniques with high sensitivity and selectivity are essential to the quantitative analysis of clinical samples. Liquid chromatography coupled to tandem mass spectrometry is the gold standard in clinical chemistry. However, tandem mass spectrometers come at high capital expenditure and maintenance costs.

Immobilization of Alcalase on Silica Supports Modified with Carbosilane and PAMAM Dendrimers.

Enzyme immobilization is a powerful strategy for enzyme stabilization and recyclability. Materials covered with multipoint molecules are very attractive for this goal, since the number of active moieties to attach the enzyme increases with respect to monofunctional linkers. This work evaluates different dendrimers supported on silica to immobilize a protease enzyme, Alcalase.

Multifunctional and Collaborative Protection of Proteins, Peptides, Phenolic Compounds, and Other Molecules against Oxidation in Apricot Seeds Extracts.

Antioxidant activity studies usually focus on a single type of molecule and do not consider possible collaborations among different molecules. The purpose of this work was to obtain multicomponent extracts exerting protection against oxidation from apricot seeds and to study the individual role of these components in the whole protection. Pressurized liquid extraction was employed to obtain extracts, and a response surface methodology enabled exploration of the effect of extraction conditions on the composition and prevalence of the antioxidant mechanism.

Comparative study of factors affecting the recovery of proteins from malt rootlets using pressurized liquids and ultrasounds.

Malt rootlets (MR) are a waste from brewing with high protein content. This work proposes to study the impact of extracting parameters on the recovery of proteins and the characteristics of extracts from MR using ultrasound-assisted extraction (UAE) and pressurized liquid extraction (PLE). A Box-Behnken experimental design was employed to study the effect of extracting parameters on the protein yield, while characterization comprised the study of antioxidant properties, the identification of extracted proteins using high-resolution tandem mass spectrometry, and the evaluation of the co-extraction of phenolic compounds.

Untargeted HPLC-MS-based metabolomics approach to reveal cocoa powder adulterations.

Cocoa powder is a highly consumed product all over the world which could be substituted by cheaper raw materials resulting in food fraud. In this work, a non-targeted metabolomics approach based on the use of reversed-phase liquid chromatography coupled to high-resolution mass spectrometry was developed to carry out the characterization of cocoa powder samples adulterated, at two different levels, with carob flour, soy flour, and chicory. The sample preparation protocol and the chromatographic parameters were optimized to extract and detect the highest number of molecular features.

Applications of Capillary Electrophoresis-Mass Spectrometry to Chiral Analysis.

Capillary electrophoresis (CE) is a technique that has already proven its importance in the separation of enantiomers. The combination of CE with mass spectrometry (MS) detection further boosts the possibilities of CE in terms of achieving higher sensitivity with the possibility of an unambiguous assignment of analytes of interest. This chapter details four different examples using CE in the electrokinetic chromatography (EKC) mode coupled to MS with application to four different fields of analysis (pharmaceutical, biomedical, food, and agrochemical).

Composition of Nonextractable Polyphenols from Sweet Cherry Pomace Determined by DART-Orbitrap-HRMS and Their and Potential Antioxidant, Antiaging, and Neuroprotective Activities.

Sweet cherry pomace is an important source of phenolic compounds with beneficial health properties. As after the extraction of phenolic compounds, a phenolic fraction called nonextractable polyphenols (NEPs) remains usually retained in the extraction residue, alkaline and acid hydrolyses and enzymatic-assisted extraction (EAE) were carried out in this work to recover NEPs from the residue of conventional extraction from sweet cherry pomace. and evaluation of the antioxidant, antihypertensive, antiaging, and neuroprotective capacities employing was achieved for the first time.

First eco-toxicological evidence of ivabradine effect on the marine bacterium Vibrio fischeri: A chiral view.

Ivabradine (S-ivabradine) is a contemporary antihypertensive drug designed and commercialized for cardiovascular diseases treatment over the world. In this work the enantiomer-specific stability and acute toxicity of ivabradine to the marine bacterium Vibrio fischeri as well as the potential mechanism of action were investigated for the first time. With this aim, real concentrations of ivabradine enantiomers under abiotic and biotic conditions were determined by Capillary Electrophoresis (CE) with cyclodextrins (CDs) as chiral selectors.

Stereoselective separation of dimethenamid by cyclodextrin electrokinetic chromatography using deep eutectic solvents.

An Electrokinetic Chromatography (EKC) method was developed in this work enabling for the first time the separation of the four stereoisomers of the acetamide herbicide dimethenamid. A screening of different anionic cyclodextrins (CDs) revealed that the use of a single CD system did not allow the separation of the four dimethenamid stereoisomers while dual systems improved the chiral separation. The combination of 15 mM (2-carboxyethyl)-β-CD (CE-β-CD) with 10 mM methyl-γ-CD (M-γ-CD) originated the partial separation of dimethenamid stereoisomers.

Synthesis and characterization of carnitine-based ionic liquids and their evaluation as additives in cyclodextrin-electrokinetic chromatography for the chiral separation of thiol amino acids.

In this study, new chiral ionic liquids based on the non-protein amino acid L-carnitine as cationic chiral counterpart and several anions (bis(trifluoromethane)sulfonimide (NTf), L-lactate or Cl) as counterions were synthesized. Moreover, three different salts based on L-carnitine were also synthesized and the other three were commercially acquired and used for comparison. The synthesized ionic liquids and salts were characterized by nuclear magnetic resonance, fourier transform infrared spectroscopy, high-performance liquid chromatography-mass spectrometry, and elemental analysis.

In vitro assessment of the bioavailability of bioactive non-extractable polyphenols obtained by pressurized liquid extraction combined with enzymatic-assisted extraction from sweet cherry (Prunus avium L.) pomace.

In vitro digestion and absorption simulation processes of non-extractable polyphenols (NEPs) obtained by pressurized liquid extraction combined with enzymatic-assisted extraction with Promod enzyme (PLE-EAE) from the residue of conventional extraction of sweet cherry pomace were studied. In general, total phenolic and proanthocyanidin contents decreased in each phase of the digestion. However, the antioxidant capacity increased when the digestion process progressed.

Glycosyl imprinted mesoporous microspheres for the determination of glycopeptide antibiotics using ultra-high performance liquid chromatography coupled with tandem mass spectrometry.

Glycopeptide antibiotics are critical weapons against serious Gram-positive resistant bacteria, and therefore the development of analytical methods for their determination is essential. In this work, with the aim of extending the scope of molecularly imprinted mesoporous materials to the recognition of large molecules such as proteins and peptides, we selected the glycosyl moiety of glycopeptide antibiotics as a template and synthesised a boronic acid functional monomer by click chemistry reaction to prepare glycosyl imprinted mesoporous microspheres. On the basis of boronate affinity, the template and the functional monomer formed a self-assembly structure that was incorporated into the silica framework during polymerisation.

Rapid fingerprinting of extractable and non-extractable polyphenols from tropical fruit peels using direct analysis in real time coupled to orbitrap mass spectrometry.

A simple and rapid direct analysis in real-time coupled to high-resolution mass spectrometry (DART-HRMS) methodology was developed to generate the extractable and non-extractable polyphenols (NEPs) fingerprint for four different passion fruits, G. mangostana, and A. squamosa peels as case-study to investigate the influence of alkaline hydrolysis and enzymatic-assisted extraction (EAE) on the recovery of NEPs.

Pressurized Liquid Extraction Combined with Enzymatic-Assisted Extraction to Obtain Bioactive Non-Extractable Polyphenols from Sweet Cherry ( L.) Pomace.

Sweet cherry generates large amounts of by-products within which pomace can be a source of bioactive phenolic compounds. Commonly, phenolic compounds have been obtained by conventional extraction methodologies. However, a significant fraction, called non-extractable polyphenols (NEPs), stays held in the conventional extraction residues.