Supramolecular solvents: a gateway to all-in-one extractions in chemical exposomics.

The characterization of the human chemical exposome through daily estimated intakes or biomonitoring has become paramount to understand the causal pathways leading to common diseases. The paradigm shift that has taken place in looking at health has moved research from the classical biomedical model based on "one exposure, one disease" to a more comprehensive approach based on multiple chemicals and low dose effects. For this purpose, untargeted and/or suspect analysis of chemicals based on liquid chromatography and high-resolution mass spectrometry (LC-HRMS) has been proposed as the most relevant strategy for sequencing the exposome.

Tailoring supramolecular solvents with phosphoryl groups for highly efficient extraction of chlorophenols in natural waters.

Background: Chlorophenols are routinely determined in aquatic systems to check compliance with the restrictive international legislations set for protection of human and aquatic life. Their control requires affordable analytical methods, particularly in labs at low- and medium-income countries. Liquid chromatography-UV detection is a convenient technique for this purpose, but the availability of suitable sample processing remains pending.

Comprehensive characterization of organic compounds in indoor dust after generic sample preparation with SUPRAS and analysis by LC-HRMS/MS.

In this study supramolecular solvents (SUPRAS) are employed for the first time to perform a wide screening of organic compounds in indoor dust samples. The potential of SUPRAS to efficiently extract a wide polarity range of compounds, and to simplify and improve the green properties of sample treatment in this area are discussed. SUPRAS made up of inverse aggregates of hexanol in tetrahydrofuran:water mixtures, which have been previously and successfully applied to the target determination of a variety of organic contaminants in different environmental matrices, were employed.

Supramolecular solvents for making comprehensive liquid-liquid microextraction in multiclass screening methods for drugs of abuse in urine based on liquid chromatography-high resolution mass spectrometry.

Multiclass screening methods involving hundreds of structurally unrelated compounds are becoming essential in many control labs and research areas. Accurate mass screening of a theoretically unlimited number of chemicals can be undertaken using liquid chromatography coupled to high resolution mass spectrometry (LCHRMS), but the lack of comprehensive sample treatments hinders this unlimited potential. In this research, the capability of supramolecular solvents (SUPRAS) for making comprehensive liquid-liquid microextraction (LLME) in multiclass screening methods based on LCHRMS was firstly explored.

Supramolecular solvent extraction and ambient mass spectrometry for the determination of organic contaminants in food packaging material.

A rapid method based on a fast sample treatment with supramolecular solvents (SUPRASs) and ambient mass spectrometry (AMS) analysis was developed for the screening and quantification of organic contaminants in food packaging materials (FCMs). The suitability of SUPRASs made up of medium chain alcohols in ethanol:water mixtures was investigated, given their low toxicity, proven capacity for multi-residue analysis (since they provide a wide variety of interactions and multiple binding sites) and restricted access properties for simultaneous sample extraction and clean-up. Two families of emerging organic pollutants, bisphenols and organophosphate flame retardants, were targeted as representative compounds.

Ribbon-shaped supramolecular solvents: Synthesis, characterization and potential for making greener the microextraction of water organic pollutants.

Liquid-liquid microextraction (LLME) techniques have experienced a tremendous growth over the last years but still face major challenges related to the use of more efficient and environmentally friendly solvents. Supramolecular solvents (SUPRASs) have proved outstanding efficiency in LLME, but many of the experimental conditions required for SUPRAS formation and/or application cannot be considered green or experimentally convenient. This paper was intended to make greener both SUPRAS formation and their application to the LLME of low-concentration organic pollutants in environmental waters.

Characterization of a new sustainable supramolecular solvent and application to the determination of oxy-PAHs in meat, seafood and fish tissues.

In this study we develop a green treatment method based on supramolecular solvents (SUPRASs) made up of reverse aggregates of short/medium chain length alcohols (C-C) in mixtures of water and a sustainable organic solvent (methyl-tetrahydrofuran). SUPRASs ingredients have low toxicity and can be obtained from renewable sources. The new SUPRASs were characterized and its suitability for determination of oxygenated polycyclic aromatic hydrocarbons (oxy-PAHs) in food was tested.

Green nanostructured liquids for the analysis of urine in drug-facilitated sexual assault cases.

In this work, we optimize and validate a simple, time-saving, and environmentally friendly sample preparation method based on supramolecular solvents (SUPRAS), green nanostructured liquids, for the extraction of selected drug-facilitated sexual assault (DFSA) substances from human urine. The methodology was fast and simple (stirring, centrifugation, and dilution). Cubosomic SUPRAS were formed by the addition of 1,2-hexanediol (200 μL) to 1.

Drugs of abuse in tap water from eight European countries: Determination by use of supramolecular solvents and tentative evaluation of risks to human health.

Recent research findings have confirmed the presence of illicit drugs in tap water from some European Union (UE) member states. Contaminants in tap water come directly from drinking water sources such as rivers or lakes owing to inefficient removal at wastewater treatment and water purification plants. This work was aimed at setting a starting point for assessing the health risks of exposure to twelve drugs of abuse through consumption of tap water in the European population.

Supramolecular solvent-based sample treatment workflow for determination of multi-class drugs of abuse in hair by liquid chromatography-tandem mass spectrometry.

Hair is becoming a main matrix for forensic drug analyses due to its large detection window compared to traditional matrices (i.e. urine & blood) and the possibility of establishing the temporal pattern of drug consumption.

Cubosomic Supramolecular Solvents: Synthesis, Characterization, and Potential for High-Throughput Multiclass Testing of Banned Substances in Urine.

This paper was intended to efficiently extract multiclass prohibited substances in human sport drug testing by using supramolecular solvents (SUPRASs) made up of cubosomes. These SUPRASs, here first reported, are synthesized by the salt-induced coacervation of 1,2-hexanediol in urine. The formation of square and rounded cubosomes with a size range of 140-240 nm was confirmed by electron microscopy.

Methanetriyl-pi hydrogen bonding in nonpolar domains of supramolecular nanostructures: An efficient mechanism for extraction of carcinogenic polycyclic aromatic hydrocarbons from soils.

Methanetriyl-pi hydrogen bonding (CH-π HB) in nonpolar domains of supramolecular nanostructures is proposed here as a new mechanism to increase the extraction efficiency of aromatic compounds. The approach is illustrated by the extraction of priority carcinogenic polycyclic aromatic hydrocarbons (CPAHs) in soils using supramolecular nanostructures of carboxylic acids with nonpolar domains consisting of hydrocarbon chains (C6-C10) dispersed in tetrahydrofuran (THF). The high concentration of CH-groups available in the supramolecular nanostructures (38.

Identification of bisphenols and derivatives in greenhouse dust as a potential source for human occupational exposure.

Bisphenol A (BPA) and alternative bisphenols are widely used in the industrial production of polycarbonates and resin polymers. Adverse effects on human health have been described for BPA and owing to the structural similarity of alternative bisphenols and derivatives, a similar toxicity profile is expectable. Dust can act as a sink for bisphenols owing to the large surface area to mass ratio.

Supramolecular solvent-based microextraction probe for fast detection of bisphenols by ambient mass spectrometry.

In this study, we investigated for the first time the suitability of supramolecular solvent (SUPRAS)-based microextraction probe for the development of generic and fast sample treatment prior to qualitative analysis by ambient mass spectrometry (AMS) based on ASAP (atmospheric solids analysis probe). SUPRAS are nanostructured liquids formed by the self-assembly of amphiphilic aggregates with multiple binding sites and microenvironments of different polarity for the efficient extraction of multiple compounds. Different types of SUPRAS were evaluated as a simple and single step sample treatment for ASAP.

Uterus transplantation in a sheep model: novel surgical technique with long-term survival and uterus vitality. First case series in Argentina.

Objective: To develop a sheep autologous uterus transplantation (UT) program with an innovative surgical technique and assess long term uterus vitality and animal survival.

Methods: A novel surgical technique consisting of the procurement of the complete uterus and the two ovaries, back table vascular reconstruction, and subsequent implantation in the same animal, performing only two arterial and two venous anastomoses.

Results: Four autologous transplantations were performed; anesthesia and surgery were well tolerated by all the animals without complications.

A comprehensive study on the performance of different retention mechanisms in sport drug testing by liquid chromatography tandem mass spectrometry.

Anti-doping substances listed by the World Anti-Doping Agency (WADA) include hundreds of compounds of very different physico-chemical properties. Anti-doping control laboratories need to screen all these substances in the so-called Initial Testing Procedures (ITPs) what is very challenging from an analytical point of view. ITPs are mostly based on reversed-phase (RP) liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) using C18 columns, which feature poor retention and peak tailing for polar and basic compounds, respectively.

Interference-Free Method for Determination of Benzodiazepines in Urine Based on Restricted-Access Supramolecular Solvents and LC-MS-MS.

Supramolecular solvents with restricted-access properties (SUPRAS-RAMs) are proposed as a new approach for integrating extraction and sample cleanup in the quantification of benzodiazepines (BDZs) in urine by liquid chromatography-tandem mass spectrometry (LC-MS-MS). The SUPRAS-RAM was synthesized in situ in the urine by the addition of 1-hexanol (154 µL) and tetrahydrofuran (THF) (600 µL). BDZ extraction was driven by both hydrogen bonds and dispersion interactions.

Comprehensive supramolecular solvent-based sample treatment platform for evaluation of combined exposure to mixtures of bisphenols and derivatives by liquid chromatography-tandem mass spectrometry.

The growing demand for a better understanding of the effects of chemical mixtures on human health has fostered the need for extensive estimation of uptake rates from identified sources and/or biomonitoring, which has encouraged the development of analyte- and matrix-independent analytical methods. In this paper, we report a comprehensive sample treatment platform for the efficient extraction and interference removal in the determination of twenty-one bisphenols and derivatives (log K from 1.254 to 6.

Exploring polar hydrophobicity in organized media for extracting oligopeptides: application to the extraction of opiorphin in human saliva.

Supramolecular solvents (dubbed SUPRAS) are gaining momentum as extractants of compounds of interest from complex matrixes such as foodstuff and biological and environmental samples. However, their powerful extraction mechanism, based on multiligand ability for solute binding, fails when applied to very polar compounds, hindering their applicability to the extraction of highly polar metabolites. In this work, we introduce the synthesis, characterization, and application of a new kind of SUPRAS formed by heptafluorobutyric acid (HFBA).

Supramolecular solvent-based high-throughput sample treatment for monitoring phytohormones in plant tissues.

Quantification of endogenous hormones in plants is essential to understand their growth, development and response to biotic and abiotic stresses. However, it is challenging to develop high-throughput sample treatments from complex plant tissues containing low amounts of structurally unrelated and labile phytohormones while delivering clean and analyte-enriched extracts. In this paper we propose the use of supramolecular solvents (SUPRASs) made up or inverted hexagonal nanostructures of alkanols to address this challenge.

Quick and Sensitive Enantioselective Determination of Permethrin in Fruits and Vegetables by Combining Supramolecular Solvents and Chiral Liquid Chromatography-Tandem Mass Spectrometry.

Permethrin (PM) is one of the chiral insecticides most widely used around the world. The significant differential toxicity of its four enantiomers and its important adverse effects on human health highlights the need for determination of PM enantiomers. The aim of this work was to develop the first enantioselective method for quantification of PM in fruits and vegetables.

Supramolecular solvent-based microextraction of aryl-phosphate flame retardants in indoor dust from houses and education buildings in Spain.

Aryl-phosphate flame retardants (aryl-OPFRs) are flame retardants or plasticizers (among other functions) that can be found in a wide variety of products, from furniture and textiles to cars and electronic equipment. There is an increasing concern about the human exposure to these contaminants due to their ubiquity (as additives they can be easily released from the product to the environment) and potential toxicity. In this study, we investigated the presence of six representative aryl-OPFRs, two well-known aryl-OPFRs (triphenyl phosphate, TPHP and 2-ethylhexyl diphenyl phosphate, EHDPP), two novel aryl-OPFRs (cresyl diphenyl phosphate, CDP and isodecyl diphenyl phosphate, IDPP) and two oligomeric aryl-OPFRs [bisphenol A bis(diphenyl phosphate), BDP and resorcinol bis(diphenyl phosphate, RDP] in indoor dust from houses and education buildings from Spain.

Twenty years of supramolecular solvents in sample preparation for chromatography: achievements and challenges ahead.

Supramolecular solvents (SUPRAS) have progressively become a suitable alternative to organic solvents for sample preparation in chromatographic analysis. The inherent properties of these nanostructured solvents (e.g.

Supramolecular solvent-based high-throughput sample treatment platform for the biomonitoring of PAH metabolites in urine by liquid chromatography-tandem mass spectrometry.

Monohydroxylated polycyclic aromatic hydrocarbons (OH-PAHs), present in human urine at trace concentrations (viz. from ng L to μg L), are considered the main biomarkers of human exposure to PAHs. In this work, we report a simple and high-throughput sample treatment platform to facilitate the biomonitoring of OH-PAHs by making it easier, greener and most cost-effective.

Saliva-induced coacervation of inverted aggregates of hexanol for simplifying human biomonitoring: Application to the determination of free bisphenols.

Saliva is progressively becoming a useful alternative to urine and blood to assess human exposure to toxics in biomonitoring campaigns, because of its easy and stress-free collection by unskilled personnel. This evaluation is highly challenging owing to the large number of compounds and individuals involved. In this article, we propose a new strategy to simplify sample treatment in the human biomonitoring of toxics in saliva.