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.

Fabrication of UMCM-1 based monolithic and hollow fiber - Metal-organic framework deep eutectic solvents/molecularly imprinted polymers and their use in solid phase microextraction of phthalate esters in yogurt, water and edible oil by GC-FID.

In this study, for the first time, hollow fiber and monolithic fiber were fabricated based on metal-organic framework deep eutectic solvents/molecularly imprinted polymers (MOF- DES/MIPs) and were used for microextraction of phthalate esters under termed hollow fiber liquid membrane-protected solid-phase microextraction (HFLMP-SPME) followed by gas chromatography- flame ionization detection. Several parameters influencing extraction recoveries of phthalate esters including adsorption and desorption parameters were investigated and optimized using fabricated MOF- DES/MIPs monolithic fiber. Under optimal conditions, detection limits (S/N = 3) of the method were in a range of 0.008-0.03 µg L-1 and limits of quantification (S/N = 10) were between 0.028 and 0.12 µg L-1. RSD (%) for intra-day and inter-day precisions were between 2.4-4.7% and 2.6-3.4%, respectively. Subsequently, this procedure was successfully applied with satisfactory results in the determination of phthalate esters in yogurt, water, and soybean oil samples. The R (%) ranged from 95.5 to 100.0% in different samples.

Comparison and application of two microextractions based on syringe membrane filter.

Two proposed syringe membrane filter solid phase microextraction and syringe membrane filter liquid/solid phase microextraction, coupled separately with high performance liquid chromatography, were developed for simultaneous enrichment and determination of the trace level of flavonoids in traditional Chinese medicine. In syringe membrane filter solid phase microextraction, the membrane of syringe membrane filter was served as a solid adsorption film to adsorb target analytes. And in syringe membrane filter liquid/solid phase microextraction, the membrane of syringe membrane filter was used as not only an adsorption phase, but also as a holder of extraction solvent to realize liquid-solid synergistic extraction. The simple operation, rapid extraction, and little or no organic solvent consumption make the two approaches very interesting. To evaluate the two proposed approaches, the crucial parameters affecting the enrichment factors of target analytes were investigated and optimized, and the two microextractions were intercompared. Moreover, their microextraction mechanisms were analyzed and described. Under the optimized conditions, both the new approaches achieved good linearities, accuracies, precisions, and low limits of detection, and the two methods were successfully applied for concentration of the flavonoids in traditional Chinese medicines.

Bio template route for fabrication of a hybrid material composed of hierarchical boehmite, layered double hydroxides (Mg-Al) and porous carbon on a steel fiber for solid phase microextraction of agrochemicals.

Nanosheets of a porous layered double hydroxide were directionally arranged on boehmite nanowires and porous carbon and used as a coating for solid-phase microextraction (SPME) method. Porous carbon tubes were prepared from goat grass and then coated with layered double hydroxide nanosheets and boehmite nanowires. The nanomaterial was placed on a stainless-steel wire which then was used for the extraction of fifteen agrochemicals from aqueous sample solutions. The extraction temperature, extraction time, ionic strength, stirring rate, and desorption temperature and time were optimized. Following thermal desorption of the agrochemicals in the injector of the gas chromatograph, they were quantified by GC/MS. Under optimum conditions, the repeatability for one fiber, expressed as relative standard deviation, was between 2.9 and 11.1%. The detection limits for the agrochemicals are between 2-29 ng L-1. The method is simple, fast, and inexpensive (in terms of equipment). The fiber is thermally stable, and the relative recoveries from spiked samples are better compared to conventional methods of extraction. Graphical abstract Schematic illustration of the preparation of three-dimensional hierarchical boehmite/ layered double hydroxides/ porous carbon (Boeh/LDH/pC) SPME fibers and application for the extraction of fifteen agrochemicals from aqueous sample solutions following quantification by GC/MS.

Multineuromodulator measurements across fronto-striatal network areas of the behaving macaque using solid-phase microextraction.

Different neuromodulators rarely act independent from each other to modify neural processes but are instead coreleased, gated, or modulated. To understand this interdependence of neuromodulators and their collective influence on local circuits during different brain states, it is necessary to reliably extract local concentrations of multiple neuromodulators in vivo. Here we describe results using solid-phase microextraction (SPME), a method providing sensitive, multineuromodulator measurements. SPME is a sampling method that is coupled with mass spectrometry to quantify collected analytes. Reliable measurements of glutamate, dopamine, acetylcholine, and choline were made simultaneously within frontal cortex and striatum of two macaque monkeys (Macaca mulatta) during goal-directed behavior. We find glutamate concentrations several orders of magnitude higher than acetylcholine and dopamine in all brain regions. Dopamine was reliably detected in the striatum at tenfold higher concentrations than acetylcholine. Acetylcholine and choline concentrations were detected with high consistency across brain areas within monkeys and between monkeys. These findings illustrate that SPME microprobes provide a versatile novel tool to characterize multiple neuromodulators across different brain areas in vivo to understand the interdependence and covariation of neuromodulators during goal-directed behavior. Such data would be important to better distinguish between different behavioral states and characterize dysfunctional brain states that may be evident in psychiatric disorders.NEW & NOTEWORTHY Our paper reports a reliable and sensitive novel method for measuring the absolute concentrations of glutamate, acetylcholine, choline, dopamine, and serotonin in brain circuits in vivo. We show that this method reliably samples multiple neurochemicals in three brain areas simultaneously while nonhuman primates are engaged in goal-directed behavior. We further describe how the methodology we describe here may be used by electrophysiologists as a low-barrier-to-entry tool for measuring multiple neurochemicals.

Accurate and sensitive determination of lead in black tea samples using cobalt magnetic particles based dispersive solid-phase microextraction prior to slotted quartz tube-flame atomic absorption spectrometry.

Newly developed combination of magnetic cobalt particles based dispersive solid-phase microextraction (Co-MP-DSPME) and slotted quartz tube attached flame atomic absorption spectrometry (SQT-FAAS) was utilized to determine lead at trace levels in tea samples. Co-MPs' adsorbent properties were tested and validated for their selectiveness to lead. Only with a few and short extraction steps (i.e. adding MPs, mixing, decanting and eluting) analyte was extracted from sample solution rapidly and efficiently. Limit of detection (LOD) and limit of quantification (LOQ) for the developed method (Co-MP-DSPME-SQT-FAAS) were found to be 7.77 µg/L and 25.9 µg/L, respectively. Matrix matching strategy was performed and outcomes indicated that the developed method is applicable with the high percent recovery values of 110.1 ±â€¯4.5 and %102.9 ±â€¯4.2 for 100 and 300 µg/kg lead standard spiked black tea samples, respectively. The method was also applied to standard reference material to check the accuracy of the method.

[An automated direct immersion solid-phase micro extraction-gas chromatography-mass spectrometry (DI-SPME-GCMS) method for determination pesticides in liquid Chinese herbal health food].

OBJECTIVE: To establish a method to determinate 25 pesticides in liquid health food from Chinese herbal medicines by direct immersion solid phase micro extraction coupled with gas chromatography-mass spectrometry. METHODS: The sample was diluted with ultrapure water, adjusted p H with acetic acid, and then filtered by 0. 45µm filter. The target compounds were extracted and concentrated by the method of on-line immersion solid phase micro extraction( SPME) coupled with 65 µm PDMS/DVB extraction fiber. The sample was separated by GC-MS with TG-5 MS( 30 m × 0. 25 mm ×0. 25 µm) capillary column. RESULTS: The method showed a good linearity R2 above 0. 99 in the range of 20-200 µg/kg for 25 organic phosphorus pesticides analytes with average recovery rates of 77. 9%-97. 9%( n = 6) and the relative standard deviation( RSD)within 1. 72%-13. 57%. The limits of detection( LOD) were between 3-10 µg/kg. CONCLUSION: The method is simple, accurate, sensitive and very environmental friendly. It is suitable for the determination of 25 pesticides in liquid health food from Chinese herbal medicines.

Hydrothermally tailor-made chitosan fiber for micro-solid phase extraction of petroleum acids in crude oils.

Tailor-made chitosan fiber was prepared via hydrothermal treatment to serve as a micro-solid phase extraction (micro-SPE) sorbent for the analysis of petroleum acids (PAs) in crude oils. Chitosan fiber, which is commercial and cheap, has a diameter of about 10 µm and a length of a few centimeters. The fibrous property of the sorbent enables the micro-SPE to deal with viscous crude oil samples because of the low back-pressure during extraction, while the abundant hydroxyl groups and amino groups on the surface of chitosan fiber can provide high density of specific sites for adsorption of PAs. Moreover, it was found that hydrothermal treatment at certain conditions could tune the surface properties of chitosan fiber, leading to significant improvement of the capacity of the fiber in adsorption of PAs. Using hydrothermally treated chitosan fiber as sorbent, the micro-SPE was applied to the determination of PAs in crude oils, with the advantages of easy-operation, rapidness and high sensitivity (the limits of detection range from 0.7 ng/g to 5.4 ng/g). Furthermore, coupled with comprehensive two dimensional gas chromatography-mass spectrometry (GC × GCMS), the treated chitosan fiber packed micro-SPE method showed a great potential for comprehensive profiling of PAs in crude oils.

Layered double hydroxide films on nanoporous anodic aluminum oxide/aluminum wire: a new fiber for rapid analysis of Origanum vulgare essential oils.

Zn/Al layered double hydroxide (LDH) films were fabricated in situ with anodic aluminium oxide aluminium as both the substrate and the sole aluminium source by means of urea hydrolysis. Headspace solid phase microextraction using LDH fibre in combination with capillary GC-MS was utilised as a monitoring technique for the collection and detection of the volatile compounds of Origanum vulgare. Experimental parameters, including the sample weight, microwave power, extraction time and humidity effect, were examined and optimised.

Graphene deposited onto aligned zinc oxide nanorods as an efficient coating for headspace solid-phase microextraction of gasoline fractions from oil samples.

The content of gasoline fraction in oil samples is not only an important indicator of oil quality, but also an indispensable fundamental data for oil refining and processing. Before its determination, efficient preconcentration and separation of gasoline fractions from complicated matrices is essential. In this work, a thin layer of graphene (G) was deposited onto oriented ZnO nanorods (ZNRs) as a SPME coating. By this approach, the surface area of G was greatly enhanced by the aligned ZNRs, and the surface polarity of ZNRs was changed from polar to less polar, which were both beneficial for the extraction of gasoline fractions. In addition, the ZNRs were well protected by the mechanically and chemically stable G, making the coating highly durable for use. With headspace SPME (HS-SPME) mode, the G/ZNRs coating can effectively extract gasoline fractions from various oil samples, whose extraction efficiency achieved 1.5-5.4 and 2.1-8.2 times higher than those of a G and commercial 7-µm PDMS coating respectively. Coupled with GC-FID, the developed method is sensitive, simple, cost effective and easily accessible for the analysis of gasoline fractions. Moreover, the method is also feasible for the detection of gasoline markers in simulated oil-polluted water, which provides an option for the monitoring of oil spill accident.

Carbon nanotube-polymer composite for effervescent pipette tip solid phase microextraction of alkaloids and flavonoids from Epimedii herba in biological samples.

An effervescent pipette tip solid phase microextraction based on carbon nanotube-polymer composite microspheres was developed for the simultaneous extraction and determination of four alkaloids (magnoflorine, epiberberine, palmatine, and jatrorrhizine) and four flavonoids (epimedin A/B/C and icariin) from Epimedii herba in biological samples. In this work, the polymeric sorbent was prepared by incorporating carbon nanotube in sulfonated polystyrene-divinylbenzene microspheres. During the extraction, the dispersion of the sorbents at milligram level was achieved by the in situ generation of carbon dioxide. The effervescence enhanced the interaction between the sorbent and the analytes. Langmuir and Freundlich models were used to evaluate adsorption processes. Under the optimum analytical conditions, the method showed good linearity (3-300µgL-1), acceptable precision (RSD <5%), low limits of quantification (1.02-2.98µgL-1) and satisfactory recoveries (90.05-99.85%). The proposed method was successfully applied to the analysis of alkaloids and flavonoids from Epimedii herba in cell culture fluids, rat urine and feces obtained at the different time intervals.

Unbiased profiling of volatile organic compounds in the headspace of Allium plants using an in-tube extraction device.

BACKGROUND: Plants produce and emit important volatile organic compounds (VOCs), which have an essential role in biotic and abiotic stress responses and in plant-plant and plant-insect interactions. In order to study the bouquets from plants qualitatively and quantitatively, a comprehensive, analytical method yielding reproducible results is required. RESULTS: We applied in-tube extraction (ITEX) and solid-phase microextraction (SPME) for studying the emissions of Allium plants. The collected HS samples were analyzed by gas chromatography-time-of-flight-mass spectrometry (GC-TOF-MS), and the results were subjected to multivariate analysis. In case of ITEX-method Allium cultivars released more than 300 VOCs, out of which we provisionally identified 50 volatiles. We also used the VOC profiles of Allium samples to discriminate among groups of A. fistulosum, A. chinense (rakkyo), and A. tuberosum (Oriental garlic). As we found 12 metabolite peaks including dipropyl disulphide with significant changes in A. chinense and A. tuberosum when compared to the control cultivar, these metabolite peaks can be used for chemotaxonomic classification of A. chinense, tuberosum, and A. fistulosum. CONCLUSIONS: Compared to SPME-method our ITEX-based VOC profiling technique contributes to automatic and reproducible analyses. Hence, it can be applied to high-throughput analyses such as metabolite profiling.

Hollow-fiber double-solvent synergistic microextraction with high-performance liquid chromatography for the determination of antitumor alkaloids in Coptis chinensis.

A new hollow-fiber double-solvent synergistic microextraction method was proposed for the extraction and concentration of trace active compounds in traditional Chinese medicine. The main variables affecting the method were investigated and optimized. Under the optimized conditions, linearities were 0.01-10 µg/mL, detection limits were lower than 0.8 ng/mL, and interday, and intraday relative standard deviations were <9.20%. Furthermore, average recoveries ranged from 102.8 to 104.1%, and enrichment factors were 6-70 for the four alkaloids tested. The antitumor alkaloid group in Coptis chinensis was screened and identified by hollow-fiber cell fishing with high-performance liquid chromatography. The four alkaloids were then enriched and quantified by hollow-fiber double-solvent synergistic microextraction with high-performance liquid chromatography. The mechanism of the proposed microextraction method was described, and results demonstrated that the approach was a simple and reliable sample-preparation procedure. This method, as well as hollow-fiber cell fishing combined with high-performance liquid chromatography can be adopted to study the different characteristic effects of the multiple components and multiple targets of traditional Chinese medicine. The approach can also be used to conduct tailored quality control of the active compounds associated with therapeutic efficacy.

A solid-phase microextraction platinized stainless steel fiber coated with a multiwalled carbon nanotube-polyaniline nanocomposite film for the extraction of thymol and carvacrol in medicinal plants and honey.

A mechanically hard and cohesive porous fiber, with large surface area, for more strong attachment of the coating was provided by platinizing a stainless steel wire. Then, the platinized stainless steel fiber was coated with a multiwalled carbon nanotube/polyaniline (MWCNT/PANI) nanocomposite using electrophoretic deposition (EPD) method and applied for the extraction of thymol and carvacrol with direct-immersion solid-phase microextraction (DI-SPME) method followed by high-performance liquid chromatography-ultraviolet detection (HPLC-UV) quantification. To provide a larger coarse surface for the tightened attachment of coating on the fiber, a stainless steel wire was platinized using a suitable optimized EPD method. Different experimental parameters were studied and the optimal conditions were obtained as: pH of the sample solution: 2; extraction time: 60min; salt content in the sample solution: 1% w/v NaNO3; desorption time: 60min; type and volume of the desorption solvent: acetonitrile, 100µL. Under the optimized conditions, limits of detection (LODs) were 0.6 and 0.8µgmL(-1) for thymol and carvacrol, respectively. Linear dynamic range (LDR) for the calibration curves of both analytes were 1-80µgmL(-1). Relative standard deviation (RSD%, n=6) was 6.8 for thymol and 12.7 for carvacrol. The proposed fiber was successfully applied for the recovery and determination of thymol and carvacrol in thyme, savory, and honey samples.

Simultaneous quantification of Aroclor mixtures in soil samples by gas chromatography/mass spectrometry with solid phase microextraction using partial least-squares regression.

Multivariate partial least-squares (PLS) method was applied to the quantification of two complex polychlorinated biphenyls (PCBs) commercial mixtures, Aroclor 1254 and 1260, in a soil matrix. PCBs in soil samples were extracted by headspace solid phase microextraction (SPME) and determined by gas chromatography/mass spectrometry (GC/MS). Decachlorinated biphenyl (deca-CB) was used as internal standard. After the baseline correction was applied, four data representations including extracted ion chromatograms (EIC) for Aroclor 1254, EIC for Aroclor 1260, EIC for both Aroclors and two-way data sets were constructed for PLS-1 and PLS-2 calibrations and evaluated with respect to quantitative prediction accuracy. The PLS model was optimized with respect to the number of latent variables using cross validation of the calibration data set. The validation of the method was performed with certified soil samples and real field soil samples and the predicted concentrations for both Aroclors using EIC data sets agreed with the certified values. The linear range of the method was from 10µgkg(-1) to 1000µgkg(-1) for both Aroclor 1254 and 1260 in soil matrices and the detection limit was 4µgkg(-1) for Aroclor 1254 and 6µgkg(-1) for Aroclor 1260. This holistic approach for the determination of mixtures of complex samples has broad application to environmental forensics and modeling.

Fast determination of Ziziphora tenuior L. essential oil by inorganic-organic hybrid material based on ZnO nanoparticles anchored to a composite made from polythiophene and hexagonally ordered silica.

In this paper, for the first time, an inorganic-organic hybrid material based on ZnO nanoparticles was anchored to a composite made from polythiophene and hexagonally ordered silica (ZnO/PT/SBA-15) for use in solid-phase fibre microextraction (SPME) of medicinal plants. A homemade SPME apparatus was used for the extraction of volatile components of Ziziphora tenuior L. A simplex method was used for optimisation of five different parameters affecting the efficiency of the extraction. The main constituents extracted by ZnO/PT/SBA-15 and PDMS fibres and hydrodistillation (HD) methods, respectively, included pulegone (51.25%, 53.64% and 56.68%), limonene (6.73%, 6.58% and 8.3%), caryophyllene oxide (5.33%, 4.31% and 4.53%) and 1,8-cineole (4.21%, 3.31% and 3.18%). In comparison with the HD method, the proposed technique could equally monitor almost all the components of the sample, in an easier way, in a shorter time and requiring a much lower amount of the sample.

Facile preparation and applications of graphitic carbon nitride coating in solid-phase microextraction.

In this study, graphitic carbon nitride (g-C3N4) was used as a coating material for solid-phase microextraction (SPME) applications. Coupled to gas chromatography (GC), the extraction ability of the SPME fiber was investigated and compared with the commercial fibers of 100 µm PDMS and 85 µm CAR/PDMS using six target analytes including deltamethrin, nerolidol, amphetamine, dodecane, ametryn and acrylamide. The g-C3N4 coating revealed excellent extraction ability and durability comparing with those of the commercial fibers due to its loose structure and unique physicochemical properties. The repeatability for each single fiber was found to be 3.46% and reproducibility for fiber to fiber was 8.53%. The g-C3N4 SPME fiber was applied to the determination of acrylamide in potato chips, the linearity and detection limit was 0.5-250 µg g(-1) and 0.018 µg g(-1), respectively.

Graphene/polydopamine-modified polytetrafluoroethylene microtube for the sensitive determination of three active components in Fructus Psoraleae by online solid-phase microextraction with high-performance liquid chromatography.

Determination of bioactive compounds in traditional Chinese medicines and biological samples is usually interfered with by coexisting components in matrices. In this work, we prepared novel multilayer functional graphene/polydopamine-modified polytetrafluoroethylene microtube for selective solid-phase microextraction of three bioactive compounds in Fructus Psoraleae. Functional graphene/polydopamine-modified polytetrafluoroethylene microtube showed good extraction efficiency toward bavachin, isobavachalcone, and bavachinin; enrichment from 357- to 737-fold was obtained for these compounds. For qualitative analysis, an online solid-phase microextraction with high-performance liquid chromatography method was developed, which showed low limits of detection of 0.02 ng/mL by using UV detection, which is significantly more sensitive than previously reported methods. The proposed method has been used to determine bavachin, isobavachalcone, and bavachinin in Fructus Psoraleae, the contents of three compounds were quantified to be 64.0, 324.0, and 384.5 µg/g; recoveries were 93.4-101.1%. The proposed method has also been applied to determine bavachin, isobavachalcone, and bavachinin in rat plasma samples after oral administration of Fructus Psoraleae.

Graphene-sensitized microporous membrane/solvent microextraction for the preconcentration of cinnamic acid derivatives in Rhizoma Typhonii.

A novel graphene-sensitized microporous membrane/solvent microextraction method named microporous membrane/graphene/solvent synergistic microextraction, coupled with high-performance liquid chromatography and UV detection, was developed and introduced for the extraction and determination of three cinnamic acid derivatives in Rhizoma Typhonii. Several factors affecting performance were investigated and optimized, including the types of graphene and extraction solvent, concentration of graphene dispersed in octanol, sample phase pH, ionic strength, stirring rate, extraction time, extraction temperature, and sample volume. Under optimized conditions, the enrichment factors of cinnamic acid derivatives ranged from 75 to 269. Good linearities were obtained from 0.01 to 10 µg/mL for all analytes with regression coefficients between 0.9927 and 0.9994. The limits of quantification were <1 ng/mL, and satisfactory recoveries (99-104%) and precision (1.1-10.8%) were also achieved. The synergistic microextraction mechanism based on graphene sensitization was analyzed and described. The experimental results showed that the method was simple, sensitive, practical, and effective for the preconcentration and determination of cinnamic acid derivatives in Rhizoma Typhonii.

Headspace solid-phase microextraction gas chromatography-mass spectrometry determination of volatile compounds in different varieties of African star apple fruit (Chrysophillum albidum).

The volatile compounds in four selected African star apple fruit (Chrysophyllum albidum) varieties were isolated and identified using the headspace solid-phase microextraction (HS-SPME) coupled with gas chromatography-mass spectrometry (GC-MS). A total of 59 compounds were identified. Application of the aroma extract dilution analysis (AEDA) to the aroma distillates from the fruits revealed 45 odour-active compounds in the flavour dilution (FD) factor range of 4-128. Among them, the highest odour activities (FD factors) were determined for methylhexanoate, acetophenone and ethyl dodecanoate. Moreover, aroma lipophilicity appears to reflect molecular conformation. Further analysis of the similarities and differences between the fruit varieties in terms of the key odourants by the application of PLS-DA and PLS-regression coefficient showed strong positive correlation between the very sweet/sweet varieties and 10 key odourants. The odourants included ethyl acetate, acetyl methyl carbinol, methylhexanoate, sabinene, p-cymene, methylbenzoate, ethylbenzoate, geraniol, cis-α-bergomotene, acetophenone, and ethyl dodecanoate.