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.

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 Novel Brominated Compounds in Flame Retarded Plastics Containing TBBPA by Combining Isotope Pattern and Mass Defect Cluster Analysis.

The study of not only main flame retardants but also of related degradation products or impurities has gained attention in the last years and is relevant to assess the safety of our consumer products and the emission of potential contaminants into the environment. In this study, we show that plastics casings of electric/electronic devices containing TBBPA contain also a complex mixture of related brominated chemicals. These compounds were most probably coming from impurities, byproducts, or degradation products of TBBPA and TBBPA derivatives. A total of 14 brominated compounds were identified based on accurate mass measurements (formulas and tentative structures proposed). The formulas (or number of bromine elements) for 19 other brominated compounds of minor intensity are also provided. A new script for the recognition of halogenated compounds based on combining a simplified isotope pattern and mass defect cluster analysis was developed in R for the screening. The identified compounds could be relevant from an environmental and industrial point of view.

Determination of monoamine neurotransmitters in zebrafish (Danio rerio) by gas chromatography coupled to mass spectrometry with a two-step derivatization.

A sensitive analytical method for the determination of monoamine neurotransmitters (MNTs) in zebrafish larvae was developed using gas chromatography coupled to mass spectrometry. Six MNTs were selected as target compounds for neurotoxicity testing. MNTs underwent a two-step derivatization with hexamethyldisilazane (HDMS) for O-silylation followed by N-methyl-bis-heptafluorobutyramide (MBHFBA) for N-perfluoroacylation. Derivatization conditions were optimized by an experimental design approach. Method validation showed linear calibration curves (r 2 > 0.9976) in the range of 1-100 ng for all the compounds. The recovery rates were between 92 and 119%. The method was repeatable and reproducible with relative standard deviations (RSD) in the range of 2.5-9.3% for intra-day and 4.8-12% for inter-day variation. The limits of detection and the limits of quantitation were 0.4-0.8 and 1.2-2.7 ng/mL, respectively. The method was successfully applied to detect and quantify trace levels of MNTs in 5-day-old zebrafish larvae that were exposed to low concentrations of neurotoxic chemicals such as pesticides and methylmercury. Although visual malformations were not detected, the MNT levels varied significantly during early zebrafish development. These results show that exposure to neurotoxic chemicals can alter neurotransmitter levels and thereby may influence early brain development. Graphical abstract ᅟ.

Does Biotransformation of Aryl Phosphate Flame Retardants in Blood Cast a New Perspective on Their Debated Biomarkers?

Aryl phosphate flame retardants (aryl-PFRs), such as triphenyl phosphate (TPHP) and 2-ethylhexyl diphenyl phosphate (EHDPHP), are emerging contaminants that can exhibit toxic properties, including severe aquatic toxicity and endocrine disruptive effects. Monitoring exposure to aryl-PFRs through specific biomarkers is necessary to assess the health risk associated with chronic exposure. Hydrolytic serum enzymes could play an important role in the formation of the hydrolysis product diphenyl phosphate (DPHP), the seemingly most abundant in vivo biomarker of TPHP in urine. Here, we assess whether serum enzymes have an impact on the toxicokinetics of TPHP and EHDPHP and on the contribution of both aryl-PFRs to in vivo DPHP levels. TPHP and EHDPHP were incubated separately with pooled human serum to measure the formation of hydrolysis products DPHP and 2-ethylhexyl phenyl phosphate (EHPHP) by liquid chromatography-tandem mass spectrometry. Clearance of TPHP and EHDPHP was 70 and 8.6 mL/min/L serum (as measured by formation of DPHP and EHPHP, respectively). No discernible amount of DPHP was produced from EHDPHP by serum hydrolases. Our results suggest that serum hydrolases can significantly contribute to the in vivo levels of DPHP formed from TPHP and can play an important role in the toxicokinetics, toxicity, and selection of biomarkers for aryl-PFRs.

Impurities of Resorcinol Bis(diphenyl phosphate) in Plastics and Dust Collected on Electric/Electronic Material.

Resorcinol bis(diphenylphosphate) (RDP) is an organophosphorus flame retardant widely used in electric and electronic equipment. It has been detected in house dust of several European countries according to recent literature. Similar to other flame retardants, RDP formulations and products treated with RDP, such as plastics, can contain RDP impurities, byproducts and breakdown products. In this study, we use screening methods based on wide scope solvent extraction and high resolution time-of-flight mass spectrometry for the identification of RDP related compounds in products and in dust. We analyzed both plastics from electrical/electronic equipment that contained RDP and indoor dust collected on and around surfaces of this equipment. A variety of compounds, namely TPHP, hydroxylated TPHP and RDP (meta-HO-TPHP and meta-HO-RDP), dihydroxylated TPHP, RDP with the loss of a phenyl group (RDP-[Phe]) and RDP oligomers were detected in plastics containing high levels of RDP. Regarding dust samples collected on electronics, TPHP meta-HO-TPHP, meta-HO-RDP, RDP-[Phe] and RDP oligomers were detected. High concentrations of meta-HO-TPHP (20-14 227 ng/g), TPHP (222-50 728 ng/g) and RDP (23-29 118 ng/g) were found in many of the dust samples, so that these compounds seem to easily migrate into the environment. These RDP impurities, byproducts and breakdown products are for the first time reported in indoor dust. Meta-HO-TPHP could be relevant for future biomonitoring studies concerning flame retardants.

Highly Selective Screening of Estrogenic Compounds in Consumer-Electronics Plastics by Liquid Chromatography in Parallel Combined with Nanofractionation-Bioactivity Detection and Mass Spectrometry.

The chemical safety of consumer products is an issue of emerging concern. Plastics are widely used, e.g. as casings of consumer electronics (TVs, computers, routers, etc.), which are present in houses and offices in continuously increasing numbers. In this study, we investigate the estrogenic activity of components of plastics coming from electronics' casings. A recently developed fractionation platform for effect-directed analysis (EDA) was used. This platform combines reversed-phase liquid chromatography in parallel with bioassay detection via nanofractionation and with online high-resolution time-of-flight mass spectrometry (TOFMS) for the identification of bioactives. Four out of eight of the analyzed plastics samples showed the presence of estrogenic compounds. Based on the MS results these were assigned to bisphenol A (BPA), 2,4-di-tert-butylphenol, and a possible bisphenol A analog. All samples contained flame retardants, but these did not show any estrogenicity. The observed BPA, however, could be an impurity of tetrabromo-BPA (TBBPA) or TBBPA-based flame retardants. Due to the plausible migration of additives from plastics into the environment, plastics from consumer electronics likely constitute a source of estrogenic compound contamination in the indoor environment.

Screening of additives in plastics with high resolution time-of-flight mass spectrometry and different ionization sources: direct probe injection (DIP)-APCI, LC-APCI, and LC-ion booster ESI.

Plastics are complex mixtures consisting of a polymer and additives with different physico-chemical properties. We developed a broad screening method to elucidate the nature of compounds present in plastics used in electrical/electronic equipment commonly found at homes (e.g., electrical adaptors, computer casings, heaters). The analysis was done by (a) solvent extraction followed by liquid chromatography coupled to high accuracy/resolution time-of-flight mass spectrometry (TOFMS) with different ionization sources or (b) direct analysis of the solid by ambient mass spectrometry high accuracy/resolution TOFMS. The different ionization methods showed different selectivity and sensitivity for the different compound classes and were complementary. A variety of antioxidants, phthalates, UV filters, and flame retardants were found in most samples. Furthermore, some recently reported impurities or degradation products derived from flame retardants were identified, such as hydroxylated triphenyl phosphate and tetrabromobisphenol A monoglycidyl ether.

Prenatal exposure to bisphenol A and phthalates and childhood respiratory tract infections and allergy.

BACKGROUND: There is growing concern that prenatal exposure to bisphenol A (BPA) and phthalates, which are widely used in consumer products, might affect susceptibility to infections and the development of allergy and asthma in children, but there are currently very few prospective studies. OBJECTIVE: We sought to evaluate whether prenatal exposure to BPA and phthalates increases the risk of respiratory and allergic outcomes in children at various ages from birth to 7 years. METHODS: We measured BPA and metabolites of high-molecular-weight phthalates, 4 di-(2-ethylhexyl) phthalate (DEHP) metabolites (Σ4DEHP) and mono-benzyl phthalate (MBzP), and 3 low-molecular-weight phthalate (LMWP) metabolites (Σ3LMWP) in urine samples collected during the first and third trimesters in pregnant women participating in the Infancia y Medio Ambiente-Sabadell birth cohort study. The occurrence of chest infections, bronchitis, wheeze, and eczema in children was assessed at ages 6 and 14 months and 4 and 7 years through questionnaires given to the mothers. Atopy (specific IgE measurement) and asthma (questionnaire) were assessed at ages 4 and 7 years, respectively. RESULTS: The relative risks (RRs) of wheeze (RR, 1.20; 95% CI, 1.03-1.40; P = .02), chest infections (RR, 1.15; 95% CI, 1.00-1.32; P = .05), and bronchitis (RR, 1.18; 95% CI, 1.01-1.37; P = .04) at any age increased for each doubling in concentration of maternal urinary BPA. Σ4DEHP metabolites were associated with the same outcomes (wheeze: RR, 1.25; 95% CI, 1.04-1.50, P = .02; chest infections: RR, 1.15; 95% CI, 0.97-1.35; P = .11; bronchitis: RR, 1.20; 95% CI, 1.01-1.43; P = .04). MBzP was associated with higher risk of wheeze (RR, 1.15; 95% CI, 1.00-1.33; P = .05). The risk of asthma at age 7 years was also increased with increasing prenatal BPA, Σ4DEHP, and MBzP exposure. There were no other exposure-outcome associations. CONCLUSIONS: Prenatal exposure to BPA and high-molecular-weight phthalates might increase the risk of asthma symptoms and respiratory tract infections throughout childhood.

In vitro human metabolism of the flame retardant resorcinol bis(diphenylphosphate) (RDP).

Resorcinol bis(diphenylphosphate) (RDP) is widely used as a flame retardant in electrical/electronic products and constitutes a suitable alternative to decabrominated diphenyl ether. Due to its toxicity and its recently reported ubiquity in electronics and house dust, there are increasing concerns about human exposure to this emerging contaminant. With the aim of identifying human-specific biomarkers, the in vitro metabolism of RDP and its oligomers was investigated using human liver microsomes and human liver cytosol. Mono- and dihydroxy-metabolites, together with glucuronidated and sulfated metabolites, were detected. Regarding RDP oligomers, only a hydroxy-metabolite of the dimer could be detected. RDP and its oligomers were also readily hydrolyzed, giving rise to a variety of compounds, such as diphenyl phosphate, para-hydroxy-triphenyl phosphate, and para-hydroxy RDP, which were further metabolized. These degradation products or impurities are possibly of environmental importance in future studies.

Exposure to bisphenol A during pregnancy and child neuropsychological development in the INMA-Sabadell cohort.

BACKGROUND: Bisphenol A (BPA) may be a neurodevelopmental toxicant, but evidence is not consistent in terms of the sex-specific patterns of the associations and the specific behavioral or cognitive domains most affected. OBJECTIVE: To examine the effects of prenatal BPA exposure on cognitive, psychomotor, and behavioral development in 438 children at 1, 4 and 7 years of age. METHODS: BPA was measured in spot urine samples collected in trimester 1 and 3 of pregnancy from women participating in the INMA-Sabadell birth cohort study. Cognitive and psychomotor development was assessed at 1 and 4 years using psychologist-based scales. Attention deficit hyperactivity disorder (ADHD) symptoms and other behavioral problems were assessed at 4 years by teachers and at 7 years by parents using questionnaire-based rating scales. RESULTS: Geometric mean creatinine-adjusted BPA concentration of the averaged samples was 2.6 µg/g creatinine. BPA exposure was not associated with the cognitive scores or their subscales at 1 and 4 years of age. At 1 year of age, exposure in the highest tertile of BPA concentrations was associated with a reduction of psychomotor scores (T3 vs T1 ß=-4.28 points, 95% CI: -8.15, -0.41), but there was no association with psychomotor outcomes at 4 years. At 4 years, BPA exposure was associated with an increased risk of ADHD-hyperactivity symptoms (Incidence Rate Ratio (IRR) per log10 µg BPA/g creatinine increase=1.72; 1.08, 2.73) and this association was stronger in boys than in girls. Further, boys had an increased risk of ADHD-inattention symptoms whereas girls showed a reduced risk (p for interaction <0.1). At 7 years, these associations were not statistically significant nor were any other behavioral problems. CONCLUSIONS: These results suggest that prenatal BPA exposure does not affect cognitive development up to age 4 years. Associations are observed with psychomotor development and ADHD-related symptoms at early ages, but these do not appear to persist until later ages.

Comprehensive characterisation of flame retardants in textile furnishings by ambient high resolution mass spectrometry, gas chromatography-mass spectrometry and environmental forensic microscopy.

The presence and levels of flame retardants (FRs), such as polybrominated diphenyl ethers (PBDEs) and organophosphate flame retardants (PFRs), was determined in textile home furnishings, such as carpets and curtains from stores in Belgium. A comprehensive characterisation of FRs in textile was done by ambient high resolution mass spectrometry (qualitative screening), gas chromatography-mass spectrometry (GC-MS) (quantitation), and environmental forensic microscopy (surface distribution). Ambient ionisation coupled to a time-of-flight (TOF) high resolution mass spectrometer (direct probe-TOF-MS) was investigated for the rapid screening of FRs. Direct probe-TOF-MS proved to be useful for a first screening step of textiles to detect FRs below the levels required to impart flame retardancy and to reduce, in this way, the number of samples for further quantitative analysis. Samples were analysed by GC-MS to confirm the results obtained by ambient mass spectrometry and to obtain quantitative information. The levels of PBDEs and PFRs were typically too low to impart flame retardancy. Only high levels of BDE-209 (11-18% by weight) were discovered and investigated in localised hotspots by employing forensic microscopy techniques. Most of the samples were made of polymeric materials known to be inherently flame retarded to some extent, so it is likely that other alternative and halogen-free FR treatments/solutions are preferred for the textiles on the Belgian market.

A novel brominated triazine-based flame retardant (TTBP-TAZ) in plastic consumer products and indoor dust.

The presence of a novel brominated flame retardant named 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine (TTBP-TAZ) is reported for the first time in plastic parts of consumer products and indoor dust samples. TTBP-TAZ was identified by untargeted screening and can be a replacement of the banned polybrominated diphenyl ethers. Analysis techniques based on ambient mass spectrometry and on liquid chromatography with atmospheric pressure chemical ionization combined with high resolution time-of-flight mass spectrometry were developed for the screening, detection and quantification of this low volatility and high molecular weight compound. TTBP-TAZ was present in 8 of 13 plastic parts of consumer products (from mainly electric and electronic equipment acquired in 2012) at estimated concentrations of 0.01-1.9% by weight of the product (%, w/w). It was not present in any of the older 13 plastic samples that were collected in a recycling park (manufacture date before 2006), this suggests a recent use of TTBP-TAZ. It was also found in 9 of 17 house dust samples in the range of 160-22150 ng g(-1), with the highest levels being found in samples collected on electronic and electrical equipment. These preliminary results highlight the need for further research on TTBP-TAZ and the potential of using alternative analysis methods for the identification of new flame retardants.

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.

Novel analytical methods for flame retardants and plasticizers based on gas chromatography, comprehensive two-dimensional gas chromatography, and direct probe coupled to atmospheric pressure chemical ionization-high resolution time-of-flight-mass spectrometry.

In this study, we assess the applicability of different analytical techniques, namely, direct probe (DP), gas chromatography (GC), and comprehensive two-dimensional gas chromatography (GC × GC) coupled to atmospheric pressure chemical ionization (APCI) with a high resolution (HR)-time-of-flight (TOF)-mass spectrometry (MS) for the analysis of flame retardants and plasticizers in electronic waste and car interiors. APCI-HRTOFMS is a combination scarcely exploited yet with GC or with a direct probe for screening purposes and to the best of our knowledge, never with GC × GC to provide comprehensive information. Because of the increasing number of flame retardants and questions about their environmental fate, there is a need for the development of wider target and untargeted screening techniques to assess human exposure to these compounds. With the use of the APCI source, we took the advantage of using a soft ionization technique that provides mainly molecular ions, in addition to the accuracy of HRMS for identification. The direct probe provided a very easy and inexpensive method for the identification of flame retardants without any sample preparation. This technique seems extremely useful for the screening of solid materials such as electrical devices, electronics and other waste. GC-APCI-HRTOF-MS appeared to be more sensitive compared to liquid chromatography (LC)-APCI/atmospheric pressure photoionization (APPI)-HRTOF-MS for a wider range of flame retardants with absolute detection limits in the range of 0.5-25 pg. A variety of tri- to decabromodiphenyl ethers, phosphorus flame retardants and new flame retardants were found in the samples at levels from microgram per gram to milligram per gram levels.

Prenatal bisphenol a urine concentrations and early rapid growth and overweight risk in the offspring.

BACKGROUND: Increasing experimental evidence suggests that prenatal bisphenol A (BPA) exposure induces offspring weight gain, but these effects remain largely unexplored in humans. We examined the effects of prenatal BPA exposure on postnatal growth and obesity. METHODS: BPA concentrations were measured in two spot-urine samples collected in the 1st and 3rd trimesters of pregnancy from mothers in a Spanish birth cohort study (n = 402). We used the average of the two creatinine-adjusted BPA concentrations as the exposure variable. Rapid child growth was defined as a weight gain Z score >0.67 in the first 6 months of life. Age- and sex-specific Z scores for body mass index (BMI) were calculated at age 14 months and 4 years, based on the World Health Organization referent; overweight was defined as a BMI Z score greater than or equal to the 85th percentile. Age- and sex-specific waist circumference Z scores were calculated at age 14 months and 4 years using the analysis population mean. RESULTS: Twenty-six percent of children were rapid growers; 25% were overweight at 14 months and 21% at 4 years. Geometric mean BPA concentrations were 2.6 µg/g creatinine (standard deviation = 2.3) in 1st trimester and 2.0 (2.3) in 3rd trimester samples (Pearson r = 0.13). At 4 years, BPA exposure was associated with increased waist circumference (ß per log10 µg/g = 0.28 [95% confidence interval = 0.01 to 0.57]) and BMI (ß = 0.28 [-0.06 to 0.63]). BPA was not associated with obesity-related outcomes at earlier ages. CONCLUSIONS: This study provides some evidence for an association between prenatal BPA exposure and obesity-related outcomes in childhood, although not in infancy. The large uncertainties in BPA exposure assessment require that findings be interpreted with caution.

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.

Determination of several PFAS groups in food packaging material from fast-food restaurants in France.

Per- and polyfluoroalkylated substances (PFAS) are a large group of toxic compounds which have been widely used in industrial and consumer applications, from where they can migrate into the environment. They can pose a risk to human health because they have been associated with several diseases. To obtain more information on the risk of PFAS in fast food packaging materials, several PFAS (perfluorocarboxylic acids or PFCAs (n = 16), perfluorosulfonic acids or PFSAs (n = 14), and a miscellaneous group constituted by sulfonamides (n = 5) and fluorotelomer phosphate esters or PAPs (n = 5)) were quantified in food contact materials (FCMs) from fast-food restaurants in France. Perfluorohexanoic acid (PFHxA), 6:2 fluorotelomer sulfonic acid (6:2 FTS) and 6:2/6:2 fluorotelomer phosphate diester (6:2/6:2 diPAP) were detected in all samples. PFCAs with shorter chain lengths (C4-C6) showed the highest concentrations compared to median (C7-C10) and longer chain length PFCAs (C11-C18). However, they had lower detection frequencies (DFs) (except for PFHxA, DF = 100%) with values of 36 and 34% for C4 and C5 PFCAs, respectively. The DF of longer chain length PFCAs was higher, especially those of the median chain length PFCAs (C8-C10, with DF = 79-98%). Analytes from the PFSA group with high DFs (70-98%) were perfluorobutane sulfonic acid (PFBS), perfluorohexane sulfonic acid (PFHxS), perfluorooctane sulfonic acid (PFOS, linear and branched) and 10:2 fluorotelomer sulfonic acid (10:2 FTS), with concentrations similar to some analytes from the PFCA group. 4:2 Fluorotelomer phosphate monoester (4:2 mPAP), 8:2 fluorotelomer phosphate monoester (8:2 mPAP) and 8:2/8:2 fluorotelomer phosphate diester (8:2/8:2 diPAP) were found with the highest concentrations (<0.006-42.7 ng g-1, <0.001-2.7 ng g-1 and <0.001-287 ng g-1, respectively) and the highest DFs (ranged 68-94%). Some correlations between analytes were found, indicating similar degradation routes or a common origin.

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.

Environment-responsive alkanol-based supramolecular solvents: characterization and potential as restricted access property and mixed-mode extractants.

Self-assembly, the process by which supramolecular solvents (SUPRAS) with an ordered structure are produced, provides unique opportunities to obtain tailored solvents with advanced functional features. In this work, environment-responsive (C(7)-C(14)) alkanol-based SUPRAS were synthesized and their potential for analytical extractions was assessed. The global composition of the solvent, the size of the coacervate droplets that form it, and the aqueous cavities of the inverted hexagonal arrangement of the alkanols can be tailored by controlling the environment [specifically, the tetrahydrofuran (THF):water ratio in the bulk solution] for alkanol self-assembly. Interestingly, supramolecular solvents are highly adaptive and the previous features can all be reversed by modifying the environment. The spontaneous self-assembly of these solvents followed predictable routes, and their composition and volume can be accurately predicted from equations derived in this work. The solvents were structurally elucidated by light and cryo-scanning electron microscopy. Extractive applications exploiting the molecular size-based restricted access properties of SUPRAS were developed and their ability to engage in mixed-mode mechanisms for solute solubilization was established. Thus, solutes of increasing molecular weight were extracted from food and environmental samples with recoveries dependent on vacuole size in the SUPRAS, while macromolecules such as proteins, carbohydrates, and humic acids were excluded. The ability of SUPRAS to establish hydrogen-bonding and dispersion interactions was exploited to extract carcinogenic chlorophenols (CCPs) from environmental waters, and a simple and fast method was developed with quantitation limits (e.g., 0.21-0.23 µg·L(-1)) low enough to comply with legislation (e.g., maximum permitted levels for pentachlorophenol are in the range 0.4-1 µg·L(-1)).