MOF-derived porous carbon microspheres Ni@C-acid as solid-phase microextraction coating for extraction of polycyclic aromatic hydrocarbons from tea infusions.

The improvement of the stability and adsorption properties of materials on targets in sample pre-treatment has long been an objective. Extensive efforts have been made to achieve this goal. In this work, metal-organic framework Ni-MOF precursors were first synthesized by solvothermal method using polyvinylpyrrolidone (PVP) as an ideal templating agent, stabiliser and nanoparticle dispersant. After carbonization and acid washing, the nanoporous carbon microspheres material (Ni@C-acid) was obtained. Compared with the material without acid treatment (Ni@C), the specific surface area, pore volume, adsorption performance of Ni@C-acid were increased. Thanks to its excellent characteristics (high stability, abundant benzene rings), Ni@C-acid was used as fiber coatings in headspace solid-phase microextraction (HS-SPME) technology for extraction and preconcentration of polycyclic aromatic hydrocarbons (PAHs) prior to gas chromatography-flame ionization detector (GC-FID) analysis. The experimental parameters of extraction temperature, extraction time, agitation speed, desorption temperature, desorption time and sodium chloride (NaCl) concentration were studied. Under optimal experimental conditions, the wide linear range (0.01-30 ng mL-1), the good correlation coefficient (0.9916-0.9984), the low detection limit (0.003-0.011 ng mL-1), and the high enrichment factor (5273-13793) were obtained. The established method was successfully used for the detection of trace PAHs in actual tea infusions samples and satisfied recoveries ranging from 80.94-118.62 % were achieved. The present work provides a simple method for the preparation of highly stable and adsorbable porous carbon microsphere materials with potential applications in the extraction of environmental pollutants.

Flexible filament winding strategy to prepare COF@polyionic liquid-coated fibers for non-selective exclusion of macromolecules in electro-enhanced solid-phase microextraction.

BACKGROUND: Accurate quantitative analysis of small molecule metabolites in biological samples is of great significance. Hydroxypolycyclic aromatic hydrocarbons (OH-PAHs) are metabolic derivatives of emerging pollutants, reflecting exposure to polycyclic aromatic hydrocarbons (PAHs). Macromolecules such as proteins and enzymes in biological samples will interfere with the accurate quantification of OH-PAHs, making direct analysis impossible, requiring a series of complex treatments such as enzymatic hydrolysis. Therefore, the development of matrix-compatible fiber coatings that can exclude macromolecules is of great significance to improve the ability of solid-phase microextraction (SPME) technology to selectively quantify small molecules in complex matrices and achieve rapid and direct analysis. RESULTS: We have developed an innovative coating with a stable macromolecular barrier using electrospinning and flexible filament winding (FW) technologies. This coating, referred to as the hollow fibrous covalent organic framework@polyionic liquid (F-COF@polyILs), demonstrates outstanding conductivity and stability. It accelerates the adsorption equilibrium time (25 min) for polar OH-PAHs through electrically enhanced solid-phase microextraction (EE-SPME) technology. Compared to the powder form, F-COF@polyILs coating displays effective non-selective large-size molecular sieving. Combining gas chromatography-tandem triple quadrupole mass spectrometry (GC-MS/MS), we have established a simple, efficient quantitative analysis method for OH-PAHs with a low detection limit (0.008-0.05 ng L-1), wide linear range (0.02-1000 ng L-1), and good repeatability (1.0%-7.3 %). Experimental results show that the coated fiber exhibits good resistance to matrix interference (2.5%-16.7 %) in complex biological matrices, and has been successfully used for OH-PAHs analysis in human urine and plasma. SIGNIFICANCE: FW technology realizes the transformation of the traditional powder form of COF in SPME coating to a uniform non-powder coating, giving its ability to exclude large molecules in complex biological matrices. A method for quantitatively detecting OH-PAHs in real biological samples was also developed. Therefore, the filament winding preparation method for F-COF@polyILs coated fibers, along with fibrous COFs' morphology control, has substantial implications for efficiently extracting target compounds from complex matrices.

Adjustable chromatographic performance of silica-based mixed-mode stationary phase through the control of co-grafting amounts of imidazole and C18 chain.

In this paper, three imidazole- and C18- bifunctional silica stationary phases (Sil-Im-C18) were prepared by adjusting introduction interval of octadecyltrichlorosilane (ODS) and 3-imidazol-1-ylpropyl(trimethoxy)silane (TMPImS), which can be used for reversed-phase liquid chromatography (RPLC) and ion exchange chromatography (IEC) with adjustable performance. The successful preparation of Sil-Im-C18 were confirmed by the characterizations of elemental analysis, infrared spectroscopy (FTIR) and contact angle (CA). Chromatographic performance of Sil-Im-C18 were evaluated by the separation of Tanaka test mixture, alkylbenzenes, linear PAHs and a set of analytes with different properties (uracil, phenol, 1,2-dinitrobenzene and naphthalene), and compared with commonly used C18 column. It was found that the chromatographic performance of Sil-Im-C18 changed significantly with the difference in bonding amount of imidazole and C18. Sil-Im-C18 demonstrated the excellent separation performance towards polycyclic aromatic hydrocarbons (PAHs), phenylesters, phenylamines, phenols and inorganic anions, and notably, nucleobases and nucleosides can be separated using pure water as mobile phases. The van Deemter plot showed that the column efficiency of Sil-Im-C18-3 was 64,933 plate·m-1 for naphthalene, indicated that Sil-Im-C18 was reasonably chromatographic columns. The RSD values of retention time were 0.22 %-0.61 % for 10 needles alkylbenzenes injected continuously at 50 °C to investigate thermal stability and repeatability, all the fluctuations of k of naphthalene were less than 2.3 % for Sil-Im-C18-1 during flushing 24 h with the mobile phase at different pH values (pH = 3 and 8), the retention time of alkylbenzenes were almost same for Sil-Im-C18-1 at different time, the RSD values of retention time of alkylbenzenes were 0.45 %-2.28 % for two batches Sil-Im-C18-1, revealing the excellent repeatability, thermal stability, durability and reproducibility of Sil-Im-C18, and implying a commercial prospect.

Liquid-liquid extraction combined with online cleanup for the simultaneous determination of PAHs by GC-MS/MS and their hydroxylated metabolites by LC-MS/MS in human fingernails.

A method was developed for the simultaneous determination of polycyclic aromatic hydrocarbons (PAHs) and their hydroxylated metabolites (OH-PAHs) in human fingernails using liquid-liquid extraction and online purification. After surface decontamination by rinsing with acetone, the fingernails were digested with sodium hydroxide and subjected to liquid-liquid extraction with a mixture of n-hexane and methyl tertbutyl ether. The organic extract was then fractionated using a silica-based solid-phase extraction (SPE) cartridge to obtain a PAH fraction eluted with n-hexane/dichloromethane (v/v, 95:5) and an OH-PAH fraction eluted with dichloromethane/ethyl acetate (v/v, 50:50). The PAH fraction was directly injected into an online gel permeation chromatography-gas chromatography-triple quadrupole tandem mass spectrometry (GPC-GC-MS/MS) system, enabling rapid determination of 16 PAHs. A parallel online SPE liquid chromatography tandem mass spectrometry (LC-MS/MS) method was used to determine 12 OH-PAHs. Validation experiments showed that the recovery of PAH and OH-PAH were within range of 67.4%-105.1% (RSD ≤ 10.1%) and 72.8%-102.3% (RSD ≤ 10.9%), respectively, with limits of quantitation (LOQ) of 0.06-0.8 ng/g and 0.15-3.1 ng/g, respectively. Forty-two human fingernail samples from residents of Southern China were analyzed to establish background PAH and OH-PAH levels in this region. Several PAHs and OH-PAHs were detected, at concentrations of 97.5 to 3,687 ng/g for PAHs and 24.2 to 767 ng/g for OH-PAHs. The dominant homologues were two- and three-ring PAH isomers, notably naphthalene (Nap), fluorene (Flu), and phenanthrene (Phe), as well as the corresponding hydroxylated metabolites 2-OH-Nap, OH-Flu, and OH-Phe. Smoking, consuming barbecued food, and age had no significant effects on PAH exposure, but a larger sample would be required to confirm this finding. The online purification strategy presented here expedites cleanup and purification during analysis of human fingernails and should facilitate non-invasive biomonitoring of PAHs in humans, particularly when analyzing large numbers of samples.

Chemical characteristics and cancer risk assessment of smokeless tobacco used in Tunisia (neffa).

INTRODUCTION: neffa, a form of air-dried smokeless tobacco used in North Africa, is spuriously perceived as a lower risk alternative to smoking. The objective of this study was to provide information on some harmful constituents of neffa and to use them for cancer risk assessment. METHODS: a high-performance liquid chromatography method coupled with fluorescence detector was used to determine polycyclic aromatic hydrocarbons (PAHs) in one sample of neffa. An atomic absorption spectrometry was performed to determine the concentrations of lead and cadmium in three samples of neffa. The levels of toxicants found in neffa were used to assess for lifetime cancer risk as advocated by the US Environment Protection Agency. RESULTS: the determination of PAHs in neffa allowed the identification of phenanthrene and anthracene. However, the higher molecular weight PAHs such as Benzo(a)Pyrene B(a)P were not detected. The concentrations of cadmium and lead varied between 1.3 to 2.8µg/g and 1.7 to 4.6µg/g respectively. Cancer risk for cadmium and lead varied between 4.2E-03 to 9.3E-03 and 2.5E-06 to 6.4E-06 respectively. Cancer risk for Cd exceeded the range of 10E-04 to 10E-06 of an acceptable risk. CONCLUSION: neffa is not a healthy alternative for overcoming smoking addiction. It contains mineral and organic pulmonary toxicants. This study could serve as a scientific basis to inform consumers about the products´ toxicity and help them to quit smokeless tobacco (SLT) use.

Novel nanohybrids for effervescence enhanced magnetic solid-phase microextraction of wide-polarity organic pollutants in roasted meat samples.

To simultaneously and efficiently extract pollutants with differential polarities, we herein fabricated and characterized a multifunctional nanocomposite. The novel nanohybrids used NiFe2 O4 as magnetic cores, and NH2 -MIL-101(Al), ß-cyclodextrin and graphene oxide as functional components combined with magnetic cores. With the aid of graphene oxide's large π-conjugated system, NH2 -MIL-101(Al)'s strong adsorption to moderately/strongly polar chemicals, and ß-cyclodextrin's specific recognition effect, the nanohybrids realized synergistically efficient extraction of polyaromatic hydrocarbons and bisphenols with a logKow range of 3-6. Combined with acidic and alkaline sources, the nanohybrids-based effervescent tablets were prepared. Based on effervescent reaction-enhanced nanohybrids-based efficient adsorption/extraction and high performance liquid chromatography and fluorescence detection, we successfully developed an excellent microextraction method for the simultaneous determination of both polyaromatic hydrocarbons and bisphenols in roasted meat samples. Several important variables were optimized as follows: Na2 CO3 and tartaric acid as acidic and alkaline sources, 900 µLof the mixed solvent (acetone and hexane at 2:1 by v/v) as the eluent, 5 min of elution time. Under optimized conditions, the novel method gave low limits of detection (0.07-0.30 µg kg-1 ), satisfactory recoveries (86.9-103.9%), and high precision (relative standard deviations of 1.9-6.7%) in roasted lamb, beef, pork, chicken, and sausage samples.

Simultaneous analysis of PAH urinary mono- and dihydroxylated metabolites by GC-MS-MS following SPE and two-stage derivatization.

A new gas chromatography-tandem mass spectrometry method for the determination of mono- and dihydroxylated polycyclic aromatic hydrocarbon metabolites (OH-PAHs and diol-PAHs) in urine was developed and validated. Various sample preparation procedures were compared, namely liquid-liquid extraction (LLE), dispersive solid-phase extraction (dSPE), and SPE, alone or combined. A novel two-stage derivatization approach using 2 silylation reagents was developed, and an experimental procedure design was used to optimize the programmed temperature vaporization-solvent vent injection (PTV-SV) GC parameters. The method focused on 11 target compounds resulting from four- to five-ring suspected carcinogenic PAHs. SPE was identified as an acceptable and more convenient extraction method for all tested metabolites, with extraction rates ranging from 63 to 86% and relative standard deviations lower than 20%. The two-stage derivatization approach successfully allowed first the derivatization of OH-PAHs by MTBSTFA (N-tert-butyldimethylsilyl-N-methyltrifluoroacetamide) and then diol-PAHs by BSTFA (N,O-bis(trimethylsilyl)trifluoroacetamide) in a single run. The limits of quantification were in the range of 0.01-0.02 µg l-1 for OH-PAHs and 0.02-0.2 µg l-1 for diol-PAHs. The intra- and interday precisions were lower than 10%. The method was applied to determine PAH metabolites in urine collected at the beginning and at the end of the working week from 6 workers involved in aluminum production. The mean diol-PAH levels at the end of the week were 10 to 20 times higher (0.86-2.34 µg g-1 creatinine) than those of OH-PAHs (0.03-0.30 µg g-1). These results confirmed the usefulness of this new analytical technique for detecting and characterizing metabolic patterns of PAHs in urine and assessing carcinogenic occupational exposures.

Application of curcumin as a green and new sorbent in deep eutectic solvent-based dispersive micro-solid phase extraction of several polycyclic aromatic hydrocarbons from honey samples prior to gas chromatography-mass spectrometry determination.

A green, simple, and efficient dispersive micro-solid phase extraction method was developed for the extraction of polycyclic aromatic hydrocarbons from honey samples. In this method, for the first time, curcumin was used as an efficient and green sorbent to extract the analytes from the sample. After that the adsorbed analytes were eluted using a deep eutectic solvent prepared by mixing tetrabutylammonium chloride: ethylene glycol and analyzed by gas chromatography-mass spectrometry. Important experimental factors affecting adsorption and desorption steps of the method were optimized and under optimal experimental conditions, low limits of detection (0.14-0.37 ng/g) and quantification (0.49-1.3 ng/g), wide linear range (1.3-500 ng/g) with a coefficient of determination ≥0.994 were obtained. Relative standard deviation values for intra- and interday precisions were ≤7.5% for all of the analytes at a concentration of 2 ng/g for each analyte (n = 6). Extraction recovery of the method was in the range of 72-81%. Finally, 20 honey samples were analyzed and the analytes were successfully detected. The method is environment friendly because of the use of curcumin as a sorbent. Also, biodegradability of the used deep eutectic solvent components is another advantage of the method.

A polymer-based dispersive solid phase extraction combined with deep eutectic solvent based-dispersive liquid-liquid microextraction for the determination of four hydroxylated polycyclic aromatic hydrocarbons from urine samples.

A new and efficient extraction procedure was proposed and used for the simultaneous extraction of four hydroxylated metabolites polycyclic aromatic hydrocarbons from urine samples. The extraction procedure was started by dissolving an organic polymer into a water-miscible organic solvent (iso-propanol) and its injection into the sample solution. The sorbent was re-precipitated in all parts of the solution as tiny particles and the analytes were adsorbed onto the sorbent. After that, the sorbent was separated and the adsorbed analytes were eluted by choline chloride: dichloroacetic acid deep eutectic solvent. The elution solvent was mixed with choline chloride-3,3-dimethyl butyric acid deep eutectic solvent and the mixture was applied in dispersive liquid-liquid microextraction procedure for more concentration of the analytes. After optimization, the method validation was followed according to International Council Harmonization guidelines and the results showed that wide linear ranges (26-500 000 ng/L) and low limits of detection (3.6-7.2 ng/L) and quantification (11-26 ng/L) were obtained. Satisfactory enrichment factors (435-475) and extraction recoveries (87-95%), and acceptable relative standard deviations (equal or less than 8.6%) were obtained. Finally, the introduced method was successfully applied for determination of the analytes in urine samples obtained from tobacco smokers.

Temperature and time-controlled hydrothermal growth and sorption selectivity of titania nanowires on titanium fiber for highly efficient solid-phase microextraction.

Two kinds of TiO2 nanowires (TiO2NWs) with different orientation were in-situ grown on Ti substrates by controlling temperature and time during the hydrothermal process. The adsorption performance was evaluated by using typical aromatic compounds as model analytes coupled to HPLC with UV detection. The results demonstrated that the TiO2NWs coating grown at higher temperature within longer time had better affinity towards PAHs. For this purpose, the key experimental factors affecting the adsorption performance of the TiO2NWs coating fabricated at 200 °C for 10 h were further investigated and optimized for the extraction of PAHs. Under the optimized conditions, the proposed method presented linear responses in the concentration ranges of 0.05 to 200 µg·L-1 PAHs with correlation coefficients more than 0.998. LODs (S/N=3) were 0.008 to 0.034 µg·L-1. Moreover, RSDs for the single fiber repeatability of the intra-day and the inter-day analyses were less than 5.6% (n=5) and 5.8%, respectively. RSDs for the fiber-to-fiber reproducibility were between 5.1% and 6.5%. Finally, the proposed method was successfully applied to the selective preconcentration and determination of trace PAHs in environmental water samples. In addition, The fabricated Ti fiber can be used at least 200 times due to its high mechanical and chemical stability.

Fabrication of magnetic polydopamine@naphthyl microporous organic network nanosphere for efficient extraction of hydroxylated polycyclic aromatic hydrocarbons and p-nitrophenol from wastewater samples.

Herein, we report the fabrication of a novel, well-defined core-double-shell-structured magnetic Fe3O4@polydopamine@naphthyl microporous organic network (MON), Fe3O4@PDA@NMON, for the efficient magnetic extraction of hydroxylated polycyclic aromatic hydrocarbons (OH-PAHs) and p-nitrophenol (p-Npn) from wastewater samples. The hierarchical nanospheres were designed and constructed with the Fe3O4 nanoparticle core, the inner shell of a polydopamine (PDA) layer, and the outer shell of a porous naphthyl MON (NMON) coating, allowing efficient and synergistic extraction of OH-PAHs and p-Npn via hydrophobic, hydrogen bonding, and π-π interactions. The Fe3O4@PDA@NMON nanospheres were well characterized and employed as an efficient sorbent for magnetic solid-phase extraction (MSPE) coupled with high performance liquid chromatography (HPLC) for analyzing of OH-PAHs and p-Npn. Under optimal conditions, the Fe3O4@PDA@NMON-based-MSPE-HPLC-UV method afforded wide linear range (0.18-500 µg L-1), low limits of detection (0.070 µg L-1 for p-Npn, 0.090 µg L-1 for 2-OH-Nap, 0.090 µg L-1 for 9-OH-Fluo and 0.055 µg L-1 for 9-OH-Phe, respectively), large enrichment factors (92.6-98.4), good precisions (intra-day and inter-day relative standard deviations (RSDs); <6.4%, n=6) and less consumption of the adsorbent. Furthermore, trace OH-PAHs and p-Npn with concentrations of 0.29-0.80 µg L-1 were successfully detected in various wastewater samples. Fe3O4@PDA@NMON also functioned as a good adsorbent to enrich a wide scope of trace contaminants containing hydrogen bonding sites and aromatic structures, highlighting the potential of functional MONs in sample pretreatment.

Biodegradation and Removal of PAHs by Bacillus velezensis Isolated from Fermented Food.

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous in the environment. They are highly toxigenic and carcinogenic. Probiotic bacteria isolated from fermented foods were tested to check their ability to degrade and/or detoxify PAHs. Five probiotic bacteria with distinct morphologies were isolated from a mixture of 26 fermented foods co-cultured with benzo(a)pyrene (BaP) containing Bushnell Haas minimal broth. Among them, B. velezensis (PMC10) significantly reduced the abundance of BaP in the broth. PMC10 completely degraded BaP presented at a lower concentration in broth culture. B. velezensis also showed a clear zone of degradation on a BaP-coated Bushnell Haas agar plate. Gene expression profiling showed significant increases of PAH ringhydroxylating dioxygenases and 4-hydroxybenzoate 3-monooxygenase genes in B. velezensis in response to BaP treatment. In addtion, both live and heat-killed B. velezensis removed BaP and naphthalene (Nap) from phosphate buffer solution. Live B. velezensis did not show any cytotoxicity to macrophage or human dermal fibroblast cells. Live-cell and cell-free supernatant of B. velezensis showed potential anti-inflammatory effects. Cell-free supernatant and extract of B. velezensis also showed free radical scavenging effects. These results highlight the prospective ability of B. velezensis to biodegrade and remove toxic PAHs from the human body and suggest that the biodegradation of BaP might be regulated by ring-hydroxylating dioxygenase-initiated metabolic pathway.

Development of a syringe membrane-based microextraction method based on metal-organic framework mixed-matrix membranes for preconcentration/extraction of polycyclic aromatic hydrocarbons in tea infusion.

Inevitably, the residues of polycyclic aromatic hydrocarbons (PAHs) in tea leaves will be transferred to hot tea infusion, constituting a certain drinking risk; consequently, it is imperative to develop rapid, sensitive, and robust approaches for their trace-level detection. Herein, we developed a syringe membrane-based microextraction (SMME) method for preconcentration/extraction of PAHs in tea infusions. This method utilized metal-organic framework-mixed matrix membranes (MOF-MMMs) as adsorbents, which anchored the nanoparticles of MOFs onto the surface of PVDF membrane. The UiO-66 (Zr)-based MMM possessed high Brunauer-Emmett-Teller (BET) surface area (320.5 m2 g-1) and pore volume (0.18 cm3 g-1), thus enhancing extraction/adsorption efficiency. Under optimized conditions, the limits of detection for PAHs reached as low as 0.02-0.08 µg L-1 with extraction recoveries of 85.5-102.1%, and the inter-day and intra-day precision was lower than 8.4% in tea infusions. Consequently, the SMME/HPLC-DAD method shows a great potential in conventional monitoring of PAHs in tea samples.

High crystalline magnetic covalent organic framework with three-dimensional grapevine structure for ultrasensitive extraction of nitro-polycyclic aromatic hydrocarbons in food and environmental samples.

Developing and establishing an efficient pre-treatment approach for the precise extraction of nitrated-polycyclic aromatic hydrocarbons (N-PAHs) from real-life samples is critical for ensuring their safety. In this study, a novel crystalline magnetic covalent organic framework with a grapevine structure not a single core-shell, Fe3O4@TAPT-DMTA-COF, was fabricated via chemical bonding. Unchanging the reticulated structure and high crystallinity of TAPT-DMTA-COF, the combination made this material possess not only simple operation via magnetic decantation but also remarkable chemical stability. Fe3O4@TAPT-DMTA-COF had a large surface area (1578.45 m2/g), and rich electronegative triazine-groups, which makes it become a superior magnetic enrichment material for trace N-PAHs. For N-PAHs analysis, low limits of detection (LODs) (1.43-17.24 ng/L), excellent relative standard deviations (RSDs ≤ 11.52%), and wide linearity (10-5000 ng/L) were obtained. Real-life applications based on this composite have been successfully explored by capturing the N-PAHs emitted from food and environmental samples.

Multi-Target Strategy to Uncover Unexpected Compounds in Rinse-Off and Leave-On Cosmetics.

The wide range and complexity of cosmetic formulations currently available on the market poses a challenge from an analytical point of view. In addition, during cosmetics manufacture, impurities coming from raw materials or formed by reaction of different organic compounds present in the formulation may be present. Their identification is mandatory to assure product quality and consumer health. In this work, micro-matrix solid-phase dispersion (µMSPD) is proposed as a multi-target sample preparation strategy to analyze a wide number of unexpected families of compounds including polycyclic aromatic hydrocarbons (PAHs), pesticides, plasticizers, nitrosamines, alkylphenols (APs), and alkylphenol ethoxylates (APEOs). Analytical determination was performed by gas chromatography-mass spectrometry (GC-MS) for the determination of 51 target compounds in a single run, whereas liquid chromatography tandem mass spectrometry (LC-MS/MS) was employed for the analysis of six APs and APEOs. Both methodologies were successfully validated in terms of linearity, accuracy, and precision in leave-on and rinse-off cosmetics. Limits of detection (LODs) were calculated in the low ng g-1, showing their suitability to determine trace levels of impurities and banned compounds with different chemical natures, providing useful tools to cosmetic control laboratories and companies.

Solid phase extraction of 16 polycyclic aromatic hydrocarbons from environmental water samples by π-hole bonds.

Through theoretical computation, it was demonstrated that perfluorobenzene can form π-hole⋅⋅⋅π bonds with polycyclic aromatic hydrocarbons (PAHs). Then, the π-hole bond was firstly introduced in solid phase extraction in which perfluorobenzene-bonded silica sorbent was synthesized and used for the solid phase extraction of sixteen PAHs in water. Compared with the traditional octadecyl silica sorbent, the perfluorobenzene-bonded silica sorbent showed higher adsorbabilities for the PAHs with 4-6 benzene rings, for which the recoveries increased by approximately 20%. Under the optimized conditions, the proposed SPE-HPLC-FLD/UV method was successfully applied for the analysis of 16 PAHs in river water and waste water samples with the limits of detection ranged from 0.002 to 0.08 µg⋅L-1. In addition, when the perfluorobenzene-bonded silica sorbent compared with the phenyl-bonded silica sorbent, the results indicated that π-hole⋅⋅⋅π bonds between perfluorobenzene and PAHs were stronger than the π-π interactions between the PAHs and benzene in hexane solution, which highlights the remarkable potential for the application of the π-hole bond in the SPE field.

Ultrasound-assisted magnetic solid-phase extraction of polycyclic aromatic hydrocarbons and nitrated polycyclic aromatic hydrocarbons from water samples with a magnetic polyaniline modified graphene oxide nanocomposite.

A novel magnetic graphene oxide nanocomposite modified with polyaniline (Fe3O4@GO-PANI) was synthesized and applied for the magnetic solid-phase extraction of polycyclic aromatic hydrocarbons (PAHs) (i.e. fluorene, phenanthrene and pyrene) and nitrated polycyclic aromatic hydrocarbons (N-PAHs) (i.e. 2-nitrofluorene, 9-nitroanthracene, 1-nitropyrene and 3-nitrofluoranthene) prior to their determination by gas chromatography-mass spectrometry. The prepared nanomaterial was characterized by scanning electron microscopy, X-ray diffraction, and Fourier transform-infrared spectroscopy. The main experimental parameters affecting the extraction and desorption steps of the MSPE procedure were investigated and optimized. Under optimum conditions, coefficients of determination (r2) ranged between 0.9970 and 0.9995, limits of detection (LODs, S/N = 3) ranged between 0.04-0.05 ng mL-1 for PAHs and 0.01-0.11 ng mL-1 for N-PAHs, while the relative standard deviation for intra-day and inter-day repeatability were lower than 10.0% for PAHs and N-PAHs. The method was successfully applied to the analysis of tap, mineral and river water samples. Relative recoveries in spiked water samples ranged between from 91.6 to 114% and from 92.3 to 110% for PAHs and N-PAHs, respectively. The proposed method is simple, rapid, sensitive and the Fe3O4@GO-PANI sorbent can be reused for at least 15 times without significant decrease in extraction recovery.

Automated liquid-liquid extraction of organic compounds from aqueous samples using a multifunction autosampler syringe.

Liquid-liquid extraction is one of the most widely used and simplest sample preparation techniques. However, consumption of large volumes of organic solvent and manual handling are two major drawbacks of this technique. A multifunction autosampler syringe is introduced which permits automated liquid-liquid extraction in an enclosed operating environment, with low consumption of organic solvents. The device described herein features a micromixer function in addition to common autosampler syringe features like accurate and precise aspirating and dispensing. To test the functionality of the micromixer syringe, manual extraction of caffeine from a tea infusion and semi-automated extraction of dichloroethane from water were carried out. Excellent recoveries of caffeine from a tea infusion (89% recovery with 1.3% RSD) and dichloroethane from water (107% recovery with 10% RSD) were obtained. Two automated workflows were tested using the micromixer syringe mounted in a laboratory autosampler. Standalone automated micro liquid-liquid extraction was performed for sample preparation of selected polychlorinated biphenyl (PCB) congeners prior to comprehensive two-dimensional gas chromatography - electron capture detection analysis. Extraction of PCBs using the described approach used substantially less solvent than a validated solid-phase extraction approach whilst delivering equivalent results for samples with high-level PCBs. Finally, fully automated extraction and GC-MS analysis of polynuclear aromatic hydrocarbons (PAHs) from water samples was performed. Mean recoveries of extraction for PCB and PAH analysis were > 70% using 4 min automated liquid-liquid extractions.

A density-tunable liquid-phase microextraction system based on deep eutectic solvents for the determination of polycyclic aromatic hydrocarbons in tea, medicinal herbs and liquid foods.

A novel density-tunable liquid-phase microextraction (DT-LPME) system was developed with high-density deep eutectic solvents (DESs) as extractant and low-density organic solvents as emulsifier and density regulator. DES-rich phase was induced to form in the bottom or in the top by adjusting the emulsifier amount. This system was used to directly extract polycyclic aromatic hydrocarbons (PAHs) from liquid and solid foods, and the obtained DES-rich phase was easy to be collected for quantification. The method (LPME with HPLC-fluorescence detector) has linearity (R2 > 0.9974), detection limits of 0.6-4.2 ng L-1 for liquid foods and 0.05-0.35 ng g-1 for solid foods, recoveries of 86.2-114.9%, and intra-day/inter-day RSDs below 6.6%. The method was applied to detect PAHs in real samples, and the PAHs residue was found in honey and five solid foods. The DT-LPME method is simple, fast, green and suitable for direct extraction of analytes from both liquid and solid samples.

Triazine-based covalent porous organic polymer for the online in-tube solid-phase microextraction of polycyclic aromatic hydrocarbons prior to high-performance liquid chromatography-diode array detection.

A triazine-based covalent organic porous polymer (COP) was synthesized from the monomers 1,3,5-triphenylbenzene and tricyanogen chloride via the Friedel-Crafts reaction and characterized in detail using Brunauer-Emmett-Teller analysis, X-ray photoelectron spectroscopy, elemental analysis, and scanning electron microscopy, which confirmed that the COP had a rough surface and suitable extraction site. It was then employed in in-tube solid-phase microextraction combined with a high-performance liquid chromatography-diode array detector. The COP adsorbent was evaluated with different types of analyte, including estrogens, polycyclic aromatic hydrocarbons (PAHs), and plasticizers. The COP produced its best performance with PAHs. In order to obtain the highest extraction efficiency for PAHs, the main influential factors were optimized. Furthermore, a sensitive analytical method was established with the limits of detection of 0.004-0.010 µg L-1, high enrichment factor of 1110-2763, and wide linear ranges (0.013-20.0 µg L-1, 0.016-20.0 µg L-1 and 0.033-20.0 µg L-1). The relative standard deviation in intra-day and inter-day tests was also controlled to be within 0.3-3.1%. The proposed method was employed in the online detection of trace PAHs in real water samples, with satisfactory results obtained.