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. Organic solvents are inefficient for extracting the whole range of chlorophenols whereas solid-phase extractions are expensive and labour-intensive. So, an efficient, fast and cheap extraction of chlorophenols, amenable to any lab, would help to cope with their worldwide analytical control in natural waters. RESULTS: A supramolecular solvent (SUPRAS) was tailored for providing mixed interaction mechanisms aimed at the efficient extraction of chlorophenols prior to LC-UV. The SUPRAS was synthesized from the self-assembly of hexylphosphonic acid under acidic conditions and consisted of sponge-like nanostructures made up of amphiphile and water. The phosphoryl (PO) group was selected as the major driver of the extraction because of its ability to act as halogen and hydrogen bond acceptor for chlorophenols. Additional interactions were hydrogen bonds from O-H amphiphilic groups and the surrounding water, and dispersion and CH-π interactions in the hydrocarbon chains. The number of binding sites in the SUPRAS could be modulated by addition of salt. The SUPRAS formed in situ in the sample, the extraction took 5 min, the concentration factor was around 220, quantification limits (0.1-0.3 µg L-1) were below the EU standards, and the method worked for natural waters. SIGNIFICANCE: A fast, low-cost, and organic solvent-free sample processing only requiring conventional lab equipment (stirrers and centrifuges) provided SUPRAS extracts that could be directly analyzed by LC-UV. SUPRAS synthesis occurred spontaneously in the water sample under addition of hexylphosphonic acid and the whole process required low skills. The method meets the analytical and operational performances for the analytical control of chlorophenols in natural waters and it is within the reach of any lab.

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. Analysis was done with liquid chromatography and high resolution mass spectrometry. Twelve samples from public buildings (six educative buildings, two food stores, two nightclubs, one office and a coffee shop) were collected in South Spain. A total of 146 compounds were detected by target (∼33 %), suspect (∼55 %) and non-target screening (∼12 %). Around 86 % of all the compounds were identified (or tentatively identified) with levels of confidence equal or higher than 3. Novel designer drugs of abuse, unreported organophosphorus compounds and well-known organic contaminants, such as bisphenols, parabens, phthalates and flame retardants are reported. Differences with previous studies on wide screening of indoor dust reveal the influence of the employed databases for data processing and of the extraction method together with the different contamination profiles given by the sample location.

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. For this purpose, a SUPRAS made up of 1,2-hexanediol, sodium sulphate and water was synthesized directly in the urine and applied to compound extraction and interference removal in the screening of eighty prohibited substances in sports by LC-electrospray ionization-time of flight mass spectrometry. Selected substances included a wide range of polarities (log P from -2.4 to 9.2) and functionalities (e.g. alcohol, amine, amide, carboxyl, ether, ester, ketone, sulfonyl, etc.). No interfering peaks were observed for any of the 80 substances investigated. Around 84-93% of drugs were efficiently extracted (recoveries 70-120%) and 83-94% of the analytes did not show matrix effects (±20%) in the ten tested urines. Method detection limits for the drugs were in the interval 0.002-12.9 ng mL-1, which are in accordance with the Minimum Required Performance Levels values established by the World Anti-Doping Agency. The applicability of the method was evaluated by the screening of thirty-six blinded and anonymized urine samples, previously analyzed by gas or liquid chromatography-triple quadrupole. Seven of the samples lead to an adverse analytical finding in line with the results obtained by the conventional methods. This research proves that LLME based on SUPRAS constitutes an efficient, economic, and simple sample treatment in multiclass screening methods, an application that is unaffordable for conventional organic solvents.

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. The methodology was applied to 40 FCMs. Target compounds were quantitated using ASAP (atmospheric solids analysis probe)-low resolution MS and a broad-spectrum screening of contaminants was performed through spectral library search using direct injection probe (DIP) and high resolution MS (HRMS). The results showed the ubiquity of bisphenols and of some flame retardants, as well as the presence of other additives and unknown compounds in about half of the analyzed samples, which highlight the complex composition of FCMs and the possible associated health risks.

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. For this purpose, a variety of SUPRASs were produced at room temperature by simply mixing alkyl phosphonates (A6-12PO3H- and A6-12PO3-2) and tetrahexylammonium (He4N+) ions in aqueous media. Among them, the SUPRASs produced from decyl hydrogen phosphonate (DePO3H-) and He4N+ allowed, for the first time, the development of SUPRAS-based LLMEs where the SUPRAS previously synthesized was added to the liquid sample, instead of being formed in situ as usual, which was proved particularly advantageous for analyses involving large sample/SUPRAS volume ratios. At near equimolar amounts of DePO3H- and He4N+, the amphiphile arranged in the SUPRAS as planar ribbons consisting of water (21 ± 3%, w/v) and DePO3H- and He4N+ in the concentration range 1.0-1.4 M. The application of these SUPRASs to LLMEs was proved by extracting carcinogenic polycyclic aromatic hydrocarbons (CPAHs) from drinking (tap and bottled) and natural (river, reservoir and underground) water (recoveries between 84 and 117% with standard deviations varying between 1 and 14%). The developed method was simple (it only required the addition of 500 µL of SUPRAS to 75 mL of sample, stirring and centrifugation), sensitive (method quantitation limits were below the maximum allowed limits set by the EU; were 0.6-7.1 ng L-1) and selective (SUPRAS extracts were directly analyzed by liquid chromatography-fluorimetry). This research proves that SUPRASs can be operationally used in LLMEs similarly to conventional solvents, which should favor their routine application in high-sample throughput laboratories.

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 1.0 mL of human urine containing 1 M Na2SO4. SUPRAS extracts were analyzed by LC-MS/MS. The method was fully validated for 23 DFSA compounds including 10 benzodiazepines, 1 z-hypnotic drug, 5 amphetamine derivatives, 3 cocaine metabolites, and 4 miscellaneous compounds. Extraction efficiency varied between 79 and 119%, and matrix effects were acceptable (-14.3/+21.5) for 87% of the compounds. Method detection and quantification limits ranged from 0.003 to 0.75 ng/mL and from 0.01 to 2.50 ng/mL, respectively. These values were low enough for the established minimum required performance limits (MRPL) of these substances. This simple and green method has a great potential to be implemented for the monitoring of illegal drugs involved in DFSA cases by forensic laboratories.

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 (C6-C10) 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. Analysis was made by liquid chromatography coupled to high resolution mass spectrometry. The method provided quantification limits in the range 0.4-4 ng g-1 with low consumption of reagents (200uL of SUPRAS per sample) and it was based on simple agitation and centrifugation without concentration/evaporation steps. All target compounds (except 11-H-benzo[b]fluoren-11-one) were found in 7 out of 19 samples, mainly in fish and seafood samples, with levels in the range n.d. - 8 ng g-1.

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. However, the extremely time- and solvent-consuming nature of conventional sample treatments render it difficult for routine use of hair analysis in forensics. In this paper, this drawback was intended to be addressed by the use of hexanol-based supramolecular solvents (SUPRAS) with restricted-access properties. The aim was to develop a fast and interference-free sample treatment workflow for the determination of opioids, cocaine, amphetamines and their metabolites in human hair. The main variables affecting the extraction were optimized and the method was validated following the European Medical Agency guideline. Major advantages of the proposed method were the straightforward sample preparation, which combines a high extraction yield (93-107%) and matrix effect removal (93-102%SSE) in a single step, the high sample throughput, and the reduced volume of organic solvent required (100 µL of SUPRAS per sample), which makes sample treatment cost-effective and eco-friendly. Method quantification limits were lower enough for all the target drugs (0.5-1.1 pg mg-1) to allow their quantitation in human hair routine analyses. The method was successfully applied to the determination of drugs of abuse in a human hair control sample.

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. For this purpose, a method using supramolecular solvents (SUPRAS) was developed to extract drugs in the opioid, amphetamine, cocaine and cannabinoid groups from tap water for their determination by liquid chromatography-tandem mass spectrometry (LC-MS/MS). A total of 119 tap water samples were collected from eight EU countries for analysis. Seven drugs were found at concentrations from 0.3 to 340 ng/L in 72 of the samples (60.5%). The mean exposure to the drugs through consumption of tap water was calculated to be 0.0064-3.531 ng/kg·day for adults and 0.0247-6.7580 ng/kg·day for children, whereas that resulting from dermal contact was estimated to be 4-7 orders of magnitude lower. Exposure values were compared with the minimum required performance levels (MRPL) for the drugs in urine set by the World Anti-Doping Agency (WADA). Based on the results, a need clearly exists for further research into the adverse effects on health of inadvertent, sustained exposure to low doses of drugs of abuse.

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 (38.7-47.3 M) enabled the efficient extraction of CPAHs (recoveries between 89 and 106%), using a supramolecular solvent (SUPRAS) volume/soil amount ratio of 1.5 µL mg-1 and a simple and quick procedure (stirring for 15 min and centrifugation for 10 min). SUPRAS extracts were directly analysed by liquid chromatography-fluorimetry (LC-FL). No sample clean-up or solvent evaporation was required. Optimization of the composition of the nonpolar domains of the SUPRASs was carried out varying the length and concentration of the hydrocarbon chain of the carboxylic acid and the concentration of THF. Method detection limits were in the interval 0.07-0.4 µg kg-1. The relative standard deviations (n = 18, CPAH concentration = 300 µg kg-1), obtained under repeatability and reproducibility conditions, varied within the ranges 2.8-5.4% and 4.3-8.8%, respectively. The accuracy of the method was proved by analysing a certified reference material (CRM) from an industrial soil, contaminated with priority CPAHs at concentrations at the mg kg-1 level (BAM-U013c). The concentration of CPAHs found in soils taken in Southern Spain varied in the range 0.51-49 µg kg-1. The results here obtained demonstrate that CH-π HB is a valuable mechanism for increasing the extraction of aromatic compounds from soils.

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. These nanostructures consisted of 1,2-hexanediol, salt, and a high water content (36-61%, w/w). Their applicability in multiclass determinations was investigated by the extraction of 92 prohibited substances (log P from 2.4 to 9.2) belonging to the 10 categories of the World Anti-Doping Agency's (WADA) list. Variables influencing both recoveries and matrix effects were optimized. Cubosomic SUPRASs showed high extraction efficiency and interference removal capability, which was attributed to their large hydrophilicity and surface area. Both features were superior to those of the other 11 SUPRASs that were based on sponge droplets and inverted hexagonal aggregates and to those of conventional organic solvents. A sport drug-testing method based on cubosomic SUPRAS-LC-ESI-MS/MS was proposed and validated. Around 82-95% of drugs were efficiently extracted (recoveries 70-120%) in urine samples, and 81-92% did not present matrix effects. The method detection limits (0.001-4.2 ng mL-1) were all far below WADA's limits. The proposed SUPRAS-based sample treatment is as simple as QuEChERS, but the distinctive features of cubosomes confer them high capability in multiclass determinations.

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. Human risk exposure to bisphenols via indoor dust has been widely assessed in the last decade. The environmental conditions inside greenhouses, among other factors, facilitate that chemicals are released from greenhouse building materials to dust. This study aims to explore for the first time the potential of greenhouse dust as a new source of bisphenols for human exposure. For this purpose, a supramolecular solvent-based method was applied to the extraction of twenty-one bisphenols from greenhouse dust, prior to their determination by liquid chromatography-tandem mass spectrometry. Nineteen bisphenols were found in the five greenhouse dust samples analysed, with concentrations ranging from 5275 ng g-1 (BPA) to 0.25 ng g-1 (trichlorobisphenol A). The average daily dose (ADD) via dust ingestion for bisphenol compounds was calculated, in order to estimate the occupational exposure for inadvertent dust ingestion. Despite the calculated ADD value for BPA (47.81 ng kg-1 day-1) being below the tolerable daily intake proposed by EFSA (4·103 ng kg-1 day-1), this value was considerably higher than those previously reported for indoor dust, which brings to light the importance of considering greenhouse dust as bisphenols source of exposure for greenhouse workers.

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. The method was applied to the screening of bisphenol A and structural analogues in thermal paper. Optimal results were achieved with SUPRAS synthesized with 1-decanol in mixtures of ethanol:water. SUPRAS (1.1-2 µL) were loaded onto glass probes and placed in contact with samples for 10 s before ASAP analysis. AMS signal peaks (width: 0.2-0.5 min) were easily integrated and normalized with internal standards (RSD: 2-25%). The method was applied to 62 samples of thermal paper. BPA and BPS were the most widely used, this highlighting the progressive industrial replacement of BPA by BPS.

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. Removal of proteins and polar macromolecules was performed by the action of the SUPRAS through chemical and physical mechanisms. Phospholipids were removed by precipitation during SUPRAS extract evaporation. A multivariate method was used for the optimization of the extraction process by applying Box-Behnken response surface design. The proposed method was validated according to the guiding principles of the European Commission Decision (2002/657/EC). Method detection and quantification limits for the target BDZs were in the intervals 0.21-0.85 and 0.67-2.79 ng/mL, respectively. The repeatability and reproducibility (expressed as relative standard deviations) were in the range 2-6% and 3-8%, respectively. The method enabled the simultaneous extraction of BDZs (recoveries in the range 84-105%) and the removal of matrix effects. The method was applied to the analysis of 13 urine samples using external calibration. Five out of 13 samples tested positive in alprazolam and lorazepam at concentrations in the range 5.4-74 ng/mL. The method allows simple and quick sample treatment with minimal solvent consumption while delivering accurate and precise data.

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. Direct observation and Doppler US performed a week after UT and laparoscopy performed three months later confirmed uterus vitality. All animals were alive more than a year after transplantation. CONCLUSIONS: Our study was the first to describe a novel surgical technique for sheep uterus autologous transplantation in Latin America, showing long-term survival and uterus vitality.

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. While studies on this field dealing with the comparison of stationary phases are focused on certain chemical classes, this research provides a wide multi-target approach. For this purpose, a representative group of 93 anti-doping agents (log P from -2.4 to 9.2) included in ten different classes of prohibited substances was selected. A comprehensive study on the performance of six columns and four eluents on different separation parameters (retention factors, asymmetry factors, co-elutions, total run times) and matrix effects (signal enhancement or suppression) was performed for LC-MS/MS-based ITPs. Columns working in both RP [C18, C8, phenyl hexyl (PH), pentafluorophenyl (PFP) and mixed-mode hydrophilic/RP (HILIC-RP)) and hydrophilic (HILIC)] modes were investigated. Eluents contained methanol or acetonitrile as organic modifiers, with or without the addition of ammonium acetate. The best column-mobile phase binomial for ITPs was PFP using water-methanol (0.1% formic acid) as eluent, while HILIC was the best option for highly polar non-aromatic anti-doping agents, which were poorly addressed by PFP. Excellent good peak shapes and relative acceptable matrix interferences were obtained for HILIC-RP, which was tested for the first time for the analysis of anti-doping agents, although the number of compounds eluting too fast was too high. On the whole, the alkyl phase C18 showed the worst performance and although C8 and PH were better, their performance did not surpass that of PFP. Possible retention mechanisms underlying separation in the different stationary phases were discussed. This research provides valuable information to anti-doping control labs for improving LC-MS/MS-based ITPs and it proposes PFP as a suitable alternative to the already established C18.

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 Kow from 1.254 to 6.564) in a variety of human exposure sources and biological fluids. Treatment of both liquid (canned beverages, urine and serum) and solid (canned food, dust) samples was based on the use of low volumes (190-200 µL) of a hexanol-based supramolecular solvent having properties of restricted access materials. The efficient extraction of bisphenol and derivatives (absolute recoveries 70-114%) was due to the mixed-mode mechanisms (hydrogen bonding, polar and dispersion interactions) and the huge number of binding sites offered by the supramolecular solvent with properties of restricted access materials for solute solubilization. Signal suppression or enhancement (SSE) values kept in the range 78-116% for samples encompassing a wide range of macromolecules content (e.g. protein, fat, carbohydrates, etc.). Quantification was carried out by liquid chromatography, electrospray tandem mass spectrometry using external calibration. Method quantitation limits for bisphenols in liquid and solid samples were in the interval 0.019-0.19 µg L-1 and 0.06-0.81 µg kg-1. The method was applied to the determination of bisphenols and derivatives in thirteen human exposure sources and biological fluids. Only four bisphenols out of twenty-one were not found in the analyzed samples. This supramolecular solvent-based bisphenol- and matrix-independent method constitutes a valuable strategy in terms of analytical and operational characteristics for the assessment of human exposure to mixtures of bisphenols and derivatives.

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). The polar hydrophobicity of this perfluorinated acid results in a SUPRAS, which coacervates at acidic pHs, that shows a great capability to extract amino acids and oligopeptides (recoveries in the range 81-105%) with nonpolar alkyl, cyclic or aromatic side chain substituents (with log D > -3.62). To further demonstrate the potential of this novel SUPRAS, an analytical methodology for the determination of opiorphin in real saliva samples was developed and fully validated. The HFBA-based SUPRAS was synthetized in situ from 950 µL of stabilized saliva, by the addition of 150 µL of HFBA and 400 µL of HCl 37% (v/v). The resulting SUPRAS was directly injected into a LC-MS/MS system for further quantification. Quantitative recoveries in the range of 87-110% were obtained with relative standard deviations below 20%. The HFBA-based SUPRAS is, therefore, capable of efficiently extracting opiorphin from saliva samples and shows a high potential for the determination of several amino acids and oligopeptides from biological samples.

A review on contaminants of emerging concern in European raptors (2002-2020).

Raptors (birds of prey and owls) have been widely used as suitable bioindicators of environmental pollution. They occupy the highest trophic positions in their food chains and are documented to bioaccumulate high concentrations of persistent pollutants such as toxic metals and legacy persistent organic pollutants (POPs).Whereas raptors played a critical role in developing awareness of and policy for chemical pollution, they have thus far played a much smaller role in current research on contaminants of emerging concern (CECs). Given the critical knowledge obtained from monitoring 'legacy contaminants' in raptors, more information on the levels and effects of CECs on raptors is urgently needed. This study critically reviews studies on raptors from Europe reporting the occurrence of CECs with focus on the investigated species, the sampled matrices, and the bioanalytical methods applied. Based on this, we aimed to identify future needs for monitoring CECs in Europe. Perfluoroalkyl substances (PFASs), novel flame retardants (NFRs), and to a lesser extent UV-filters, neonicotinoids, chlorinated paraffins, parabens and bisphenols have been reported in European raptors. White-tailed Eagle (Haliaeetus albicilla), Peregrine falcon (Falco peregrinus) and Northern goshawk (Accipiter gentilis) were the most frequently studied raptor species. Among matrices, eggs, feathers and plasma were the most widely employed, although the potential role of the preen gland as an excretory organ for CECs has recently been proposed. This review highlights the following research priorities for pollution research on raptors in Europe: 1) studies covering all the main classes of CECs; 2) research in other European regions (mainly East Europe); 3) identification of the most suitable matrices and species for the analysis of different CECs; and 4) the application of alternative sample treatment strategies (e.g. QuEChERS or pressurized liquid extraction) is still limited and conventional solvent-extraction is the preferred choice.

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. The strategy was applied, as a proof of concept, to the quantification of stress-related phytohormones belonging to different categories (abscisic acid, salicylic acid, jasmonic acid, methyl jasmonate and 3-indoleacetic acid) in melon and pepper leaves. Sample treatment consisted in a single extraction-cleanup step involving the use of a low volume of SUPRAS (244 µL), the stirring (5 min) and centrifugation (15 min) of the sample at room temperature, and the direct analysis of the extract by liquid chromatography tandem mass spectrometry (LC-MS/MS). This high-throughput sample treatment method delivered excellent results for the target phytohormones regarding absolute recoveries (80-92%), method quantification limits (0.05-2 ng g-1), reproducibility (1-7%) and matrix effects (+13 to -31%), in both melon and pepper leaves, compared to reported methods based on repetitive solvent extraction, purification and solvent evaporation steps. The method was successfully applied to determine target hormones in melon and pepper plants for the evaluation of the effect of thermal stress. It was found that their concentration increased in the ranges 1.2-1.9 and 1.3-3.8 times in melon and pepper leaves, respectively, compared with control samples.