Polyester fabric-based nano copper-polyhedral oligomeric silsesquioxanes sorbent for thin film extraction of non-steroidal anti-inflammatory drugs.

In this study, in-situ preparation of copper nanoparticles under sonoheating conditions followed by coating on commercial polyester fabric is reported. Through the self-assembly interaction of thiol groups and copper nanoparticles, the modified polyhedral oligomeric silsesquioxanes (POSS) was deposited on the fabric's surface. In the next step, radical thiol-ene click reactions were implemented to create more layers of POSSs. Subsequently, the modified fabric was applied for sorptive thin film extraction of non-steroidal anti-inflammatory drugs (NSAIDs) including naproxen, ibuprofen, diclofenac, and mefenamic acid from urine samples, followed by high-performance liquid chromatography equipped with a UV detector. The morphology of the prepared fabric phase was characterized by scanning electron microscopy, water angle contact, energy dispersive spectrometry mapping, analysis of nitrogen adsorption-desorption isotherms, and attenuated total reflectance Fourier transform infrared spectroscopy. The significant extraction parameters, including the acidity of the sample solution, desorption solvent and its volume, extraction time, and desorption time, were investigated using the one-variable-at-a-time approach. Under the optimal condition, NSAIDs' detection limit was 0.3-1 ng mL-1 with a wide linear range of 1-1000 ng mL-1. The recovery values were between 94.0% and 110.0%, with relative standard deviations of less than 6.3%. The prepared fabric phase exhibited acceptable repeatability, stability, and sorption property toward NSAIDs in urine samples.

Perylene bisimide-based nanocubes for selective vapour phase ultra-trace detection of aniline derivatives.

Rapid and selective detection of biomarkers at trace levels is a highly coveted objective in the early diagnosis of cancer. Herein, we disclose the design and synthesis of a polyhedral oligomeric silsesquioxane (POSS) substituted perylene diimide. This compound is fully characterized in solution by multi nuclear NMR, as well as in gas state by ESI-MS. Surprisingly, solid-state characterization revealed an unusual cubic morphology with particle dimensions of 80-160 nm. Fluorescence studies indicate that the bulky POSS units effectively prevent perylene's aggregation caused quenching, yielding quantum yields as high as 92%. Exposing the sensor droplet-cast on quartz to anline and o-toluidine, two important biomarkers for lung cancer, results in very highly reproducible, reversible and selective fluorescence quenching responses, with LODs as low as 19 and 8 ng L-1, and linear ranges of 65-350 and 25-450 ng L-1 respectively. Mechanistic investigations point to photoinduced electron transfer (PET) as the operative pathway responsible for fluorescence quenching.

From waste to health: Application of MOF modified walnut biochars for the determination of twenty pesticides in wheat flour by ultra-high performance liquid chromatography-tandem mass spectrometry.

In this research, walnut shell along with a Ni-metal organic framework (Ni-MOF) was thermally treated to obtain a highly efficient biochar. A µ-solid phase extraction (µ-SPE) setup containing the optimized walnut modified biochar was implemented for the extraction of 20 wheat specified pesticides with a wide range of polarities. The modified biochars were characterized and the role of Ni-MOF on the porosity of the obtained biochars was investigated. After optimizing the extraction parameters, the 50 %-Ni-MOF-walnut shell biochar was selected. Accordingly, the precision for intra-day (2.4-25 %), inter-day (7-28.3 %) and synthesis procedure (4.1-26.7 %) was calculated. The limits of detection and quantification were in the range of 0.01-12.1 µg/L and 0.03-40.5 µg/L, respectively. This method was applied for the analysis of 29 wheat samples. The risk assessment study demonstrates that the contaminated wheat samples cannot cause non-carcinogenic harm to adults but might have an impact on children.

Perylene diimide-POSS network for semi selective solid-phase microextraction of lung cancer biomarkers in exhaled breath.

Lung cancer (LC) is the leading cause of cancer mortality so, the analysis of exhaled human breath has great significance for early non-invasive diagnosis. Poor selectivity and strong humidity are two bottlenecks for the application of gas sensors to exhaled breath analysis. The development of novel extractive phases for the analysis of exhaled breath by chromatography is therefore a lucrative object. Polyhedral oligomeric silsesquioxanes (POSS) are among the 3D porous materials whose unique properties make them promising coatings for solid-phase microextraction (SPME). Selective enrichment of polar or nonpolar targets depends on the pore size and functional groups on the POSSs. Herein, we disclosed 3D network of POSS-naphthalene diimide (POSS-NDI) and perylene diimide (POSS-PDI) as extractive phases for analysis of lung cancer biomarkers with the capability of capturing different volatile organic compounds (VOCs). The synthesized diimides were fully characterized by FT-IR, multinuclear NMR, SEM, TEM, TGA, and BET analysis. After optimization of all the influential parameters on sorption/desorption, figures of merit for three aldehydes as biomarkers of LC were obtained. The exhaled breath of twelve participants including seven healthy candidates and five cases with LC were examined. The partial least squares-discriminant analysis (PLS-DA) was implemented which led to the proper classification of healthy and LC patients with R2 calibration and cross-validation of 0.9738 and o.7882, respectively.

Preparation and evaluation of various banana-based biochars together with ultra-high performance liquid chromatography-tandem mass spectrometry for determination of diverse pesticides in fruiting vegetables.

Biomass, originates from plant- or animal-based materials with a huge potential to be reused. Here we report a simple, rapid and inexpensive method for preparation of modified biochars derived from the banana peel followed by their applications in pipette-tip micro solid-phase extraction (PT-µSPE). Due to the contribution of various effective parameters on modification of banana peel biochars (BPBs), Taguchi design was used to optimize activation temperature, activation repetition, treatment material and impregnation ratio. Efficiency of the prepared BPBs were studied by extraction of twelve various pesticides, as model analytes with an extended range of log P values (1.4-5.7), followed by their determination using ultra-high performance liquid chromatography-tandem mass spectrometry. After finding the most suitable BPB, the affecting parameters on the PT-µSPE performance were optimized. Accordingly, the LOD values of 0.03-10 µg L-1, linear dynamic range of 0.1-200 µg L-1 and a range of RSD values of 5.3-19% were obtained. Eventually, five fruiting vegetables were analyzed and screened for their possible contaminations. Among the tested pesticides, chlorpyrifos, diazinon, malathion, phosalone, propargite and thiophanate-methyl were detected in eggplant, sweet pepper, zucchini and tomato.

Preparation of amine-modified lignin and its applicability toward online micro-solid phase extraction of valsartan and losartan in urine samples.

In the present work, with the focus on an environmentally-friendly approach, some gels were prepared by synthesizing amine-modified lignin, extracted from sugarcane bagasse, and further esterification and subsequent freeze-drying. These lignin-based gels were implemented as extractive phases in an online micro-solid phase extraction (µSPE) setup in conjunction with high performance liquid chromatography (HPLC) with UV detector. The developed method was used for analytical determination of valsartan and losartan in urine samples. To study the effect of the functionalization process, the efficiency of the unmodified lignin and the functionalized lignin were compared both in the absence and the presence of graphene oxide (GO), presumably as a suitable doping agent. Surprisingly, higher extraction efficiency for the functionalized lignin, compared to both unmodified lignin and GO was observed. The amination process for the prepared gel was analyzed and proved by CHNS elemental analysis and Fourier transform infrared (FT-IR) spectroscopy. The morphology of sorbet was investigated via scanning electron microscope (SEM) imaging and a nanoscale cauliflower feature was observed. The method was optimized and subsequently applied to the analysis of the urine samples. Limits of detection (LOD) of 8 and 6 µg L - 1, limits of quantification (LOQ) of 27 and 20 µg L - 1 and linear dynamic range (LDR) of 27-2000 and 20-2000 µg L - 1 with intraday relative standard deviations (RSD%) of 4 and 3% were obtained for valsartan and losartan, respectively. The whole online µSPE-HPLC setup was conveniently used for the analysis of a patient urine sample and a quantity of 352 µg L - 1 of losartan was found. Acceptable relative recoveries (109-108 and 95-94% for valsartan and losartan) revealed the analytical potential of the method for the determination of drugs in complex urine samples.

Super-porous semi-interpenetrating polymeric composite prepared in straw for micro solid phase extraction of antibiotics from honey, urine and wastewater.

A cryogel-based semi-interpenetrating polymer network (Cryo-SIPN) was prepared in which conductive polymers such as polyaniline (PANI) and polypyrrole (PPy) were formed within the super porous network of acrylic acid cryogel. For completion of cryo-polymerization, all the constituent solutions were severely mixed and placed into the plastic straws and kept at -20°C and then the synthesized cyrogels were cut into the 1-cm length and freeze dried after washing with water. The Cryo-SIPN polymeric composite was applied in micro solid phase extraction (µSPE) of some selected antibiotic residues from various samples. The µSPE method combined with a high performance liquid chromatography-ultraviolet (HPLC-UV) system allowed trace quantification of antibiotic residues in the honey and water samples while the significant variables were optimized using a central composite design (CCD) to find optimum conditions. The method performance was satisfactory with recovery ranges from 70.0 to 109%. The limits of detection (S/N = 3) and quantification (S/N = 10) for all samples were within the 17-50 µg kg-1 and 47-140 µg kg-1 range, respectively. The relative standard deviation was less than 10 % for antibiotics in the foodstuff and water samples. The validated Cryo-SIPN-µSPE in conjunction with HPLC-UV, proved to be versatile, efficient and robust while its capability toward the trace determination of drugs residues in real-life samples is demonstrated in this work.

Immobilization of synthesized phenyl-enriched magnetic nanoparticles in a fabricated Y-Y shaped micro-channel containing microscaled hedges as a microextraction platform.

In this survey, a reliable and applicable Y-Y shaped micro-channel in a microfluidic device was designed and manufactured. A number of micro-scaled hedges were precisely fabricated inside the micro-channel to facilitate the immobilization of synthesized core-shell Fe3O4@SiO2 magnetic nanoparticles (MNPs), functionalized by triethoxyphenylsilane (TEPS) by sol-gel technique. Both sample and reagents were introduced into the microfluidic device by a syringe pump to perform the extraction and desorption steps. The functionalized MNPs were characterized by transmission electron microscopy, X-ray diffraction spectroscopy and Fourier transform infrared spectroscopy. By adopting the strategy of extraction-on-chip using this microfluidic device, we were benefited from implementing the entire analyses with the minimum amount of desorbing solvent, MNPs, and aqueous/fruit juice samples. In contrast to dispersive solid phase extraction, dispersion of MNPs during experiment is prevented by fabrication of micro-scaled hedges in the micro-channel. Consequently the stabilized MNPs are reused for the entire runs. The microfluidic device was successfully exploited as an efficient extracting plateau to evaluate the extraction/desorption capability in analysis of some organophosphorus pesticides (OPPs) as model compounds. Our results indicate that the functionalization of Fe3O4@SiO2 with TEPS, improved their extraction capability due to the existence of phenyl and hydroxyl groups for more efficient π-π and hydrogen bonding interactions. Eventually, µL-scale of the organic solvent was injected into a gas chromatography-mass spectrometry system. The limits of detection (3Sb) and quantification (10Sb) for the OPPs were 0.03-0.1 and 0.1-0.35 ng mL-1, respectively. In addition, the interday and intraday precisions were lower than 5.3% (n = 3). The obtained recovery was 95-99% for water samples and 88-96% for fruit juice samples while satisfactory regression coefficients of 0.9949-0.9991, could be achieved.

Amine/phenyl gradient derived base layer as a comprehensive extractive phase for headspace cooled in-tube microextraction of volatile organic compounds in saliva.

A gradient derived base layer extractive phase was synthesized and applied for the determination of volatile organic compounds (VOCs) in saliva samples using the headspace cooled in-tube microextraction (HS-CITME) method. The base layers from three different sols of phenyltriethoxysilane (PTES), octyltrimethoxysilane (OTMS) and methyltrimethoxysilane (MTMS) as nonpolar precursors were individually dip coated on the stainless steel wires (SSW). Then, the hydrolyzed polar precursor aminopropyltriethoxysilane (APTES) reacted with the silanol groups already formed on the surface of SSWs via controlled rate infusion (CRI) method. The presence of polar and non-polar functional groups on the surface of substrate was evaluated by Fourier-transform infrared spectroscopy (FTIR) while the morphology and thickness of the most suitable gradient coating (amine/phenyl) were also investigated by scanning electron microscopy (SEM). Assessment of the gradient extractive phase efficiency was carried out determining a group of VOCs with different polarities coupled with gas chromatography-mass spectrometry (GCMS) and the improved performance of the synthesized base layer coatings was observed. Furthermore, a cooling device was designed and implemented to the extracting system to improve the efficiency by influencing the exothermic nature of process. The data were analyzed by principal component analysis (PCA), and hierarchical cluster analysis (HCA) and the results were interpreted by polarities of analytes. Finally, under the optimized conditions, the limits of detection (LOD) and limits of quantification (LOQ) were 0.15 and 0.50 ng L-1, respectively. The intra-day and inter-day relative standard deviations (RSDs) at 5 and 50 ng L-1 (n = 3) using a single extractive phase were 2-6 and 10-17, respectively. The data associated with RSDs% for three extractive phases were between 16 and 19 %. Eventually, the method was conveniently applied to the extraction of VOCs from saliva samples of smokers and satisfactory relative recoveries (RR%) (95-108 %) were achieved and low quantities of VOCs were detected.

Silane-based modified papers and their extractive phase roles in a microfluidic platform.

Herein, some (modified) paper-based substrates were prepared and utilized as extractive phases in a microfluidic device and their extraction performances examined for analytes with different polarities. Reagents including hexadecyltrimethoxysilane (HDTMS), phenyltrimethoxysilane (PTES), (3-aminopropyl) triethoxysilane (APTES) and 3-(2,3-epoxypropoxy) propyltrimethoxysilane (EPPTMOS) were implemented for the modification process. Due to the induction of different silane functional groups, it was anticipated to have various interactions for the tested analytes. Eventually, the prepared paper sheets were used as extractive phases for solid-phase extraction within a microfluidic system. The microfluidic setup not only improves the mechanical stability of the paper-based phases but also facilitated the mass transfer process and decreases the energy consumption. The selected analytes contained antidepressant drugs, organophosphates and triazine toxins, having different structures and polarities. Afterward, the existing interactions between the paper-based sorbents and the selected analytes were investigated by Principal Component Analysis (PCA) and Hierarchical Clustering Analysis (HCA) for data analysis. According to the obtained data, the PTES modified surface paper was selected for quantitative investigation and optimization. The major parameters associated with the extraction performance were studied. A linear range was obtained for amitriptyline and trimipramine, 0.05-200 µg L-1, and the calibration graph for clomipramine was linear in the range of 0.02-200 µg L-1. The employment of microfluidic device in conjunction with gas chromatography-mass spectrometry led to the limits of detections of 0.005-0.01 µgL-1 for the antidepressant drugs. The relative recoveries for the tested drugs in urine samples were in the range of 95-103%.

Roles of metal, ligand and post synthetic modification on metal organic frameworks to extend their hydrophobicity and applicability toward ultra-trace determination of priority organic pollutants.

Implementation of metal organic frameworks (MOFs) in the separation science has attracted many researchers attention. In this study, the role of metal, ligand, the reaction condition and modification on the extraction efficiency of some MOFs was investigated. Among the prevalent reported MOFs, some members of the MIL and MOF-5 families were chosen, and eleven MOF-based sorbents were prepared by changing the metal and ligand type, reaction condition, and/or functionality through post synthetic modification (PSM). MIL-101 and MIL-101-NH2 based structures were initially synthesized based on the chromium and iron salts. Also, three zinc-based structures including MOF-5, [NH2(CH3)2]2 [Zn3(C6H4(CO2)2)4].DMF.H2O and [NH2(CH3)2]2 [Zn3((C6H4)2(CO2)2)4].5DMF were synthesized. The PSM hydrophobic-oriented products of MILs were obtained by their reactions with benzyl alcohol. The resulted MOFs were characterized by FT-IR, PXRD, SEM, BET, BJH, water contact angle and TG analyses. The extraction trends of these nanostructures were studied toward some priority environmental pollutants such as polycyclic aromatic hydrocarbons (PAHs), chlorobenzenes (CBs), and benzene homologs. The extraction procedures were performed via adapting a home-made headspace needle trap extraction (HS-NTE) setup, and determinations were followed by gas chromatography-mass spectrometry (GC-MS). Among all the synthesized nanostructures, the chromium-based PSM product of MIL-101-NH-CH2C6H5 proves its improved extraction capability for most of the model compounds. Eventually, the superior MOF was applied as the extractive phase in a HS-NTE-GC-MS method for isolation and trace determination of PAHs, in tea, coffee, and some other environmental water samples. Under the optimized conditions, the linear dynamic range (LDR) was in the range of 1-1000 ng L-1 (R2 > 0.992) while the limits of detection (LOD) and limits of quantification (LOQ) values were 0.1-0.2 and 0.3-0.7 ng L-1, respectively. Also, the extraction capability of the Cr-based MIL-101-NH-CH2C6H5 was compared with commercial polydimethyl siloxane-divinyl benzene (PDMS-DVB) fiber coating. The intra-and inter-day relative standard deviations for three replicates at the concentration levels of 20 and 500 ng L-1 were in the range of 4-7% and 5-10%, respectively. The needle-to-needle reproducibility was also found to be in the range of 6-10%. Acceptable relative recovery values at the concentration levels of 20 and 500 ng L-1 ranged from 89 to 98%, showing no significant matrix effect.

The geometrical characteristics of nickel-based metal organic framework on its entrapment capability.

Here, a three dimensional nickel-based metal organic framework (MOF) was synthesized via solvothermal and room temperature protocols. In order to study the effects of the synthesis conditions on the physical properties such as pore sizes and shapes of the prepared MOFs, their extraction capabilities were examined. Both MOFs were characterized by Fourier transform infrared spectroscopy, powder X-ray diffraction, scanning electron microscopy, Brunauer-Emmett-Teller and thermogravimetric analyses. Brilliant properties such as porous structure, high surface area and considerable thermal stability make them reasonable candidates to be employed as efficient extractive phases. The efficiency of the superior nickel-based MOF was evaluated for headspace needle trap extraction of chlorobenzenes as model compounds in conjunction with gas chromatography-mass spectrometry (GC-MS). The MOF-based extractive phase was conveniently packed in a needle trap device and after extraction, the desorption process was performed via direct insertion of needle into the GC inlet. After optimizing the extraction/desorption conditions, the figures of merit such as linear dynamic range was in the range of 5-1000 ng L-1 (R2 > 0.987) while the limits of detection and quantification values were 2-10 and 6-30 ng L-1, respectively. The intra- and inter-day relative standard deviations for three replicates at the concentration level of 50 ng L-1 were in the range of 7-9% and 9-12%, respectively. The needle-to-needle reproducibility was also found to be in the range of 5-11%. Acceptable relative recovery values at the concentration level of 50 ng L-1 ranged from 85 to 96%, showing no significant matrix effect.

A turn-on graphene quantum dot and graphene oxide based fluorometric aptasensor for the determination of telomerase activity.

A turn-on fluorometric assay is described for determination of the activity of enzyme telomerase. For this purpose, graphene quantum dots (GQDs) were first modified with the telomeric sequence (5'-amino-AATCCGTCGAGCAGAGTT-3') via a condensation reaction. Injection of graphene oxide causes instant quenching of the blue fluorescence of the GQDs. Addition of cell extract containing telomerase, triggers the extension of telomer via addition of specific sequence (TTAGGG)n to its 3' end. Fluorescence, best measured at excitation/emission wavelengths of 390/446 nm, is subsequently restored due to folding of the extended telomeric sequence into G-quadruplex structure. The method was applied to the determination of telomerase activity in crude cell extracts of as little as 10 HeLa cells. The linear dynamic range extends from 10 to 6500 cells. Graphical abstractIn this study, a new turn-on graphene quantum dotm and graphene oxide based fluorometric assay is developed for the determination of telomerase activity.

Toward higher extraction and enrichment factors via a double-reservoirs microfluidic device as a micro-extractive platform.

In this study, firstly, a double-reservoir and switchable prototype of a micro-chip along with the respective holders were fabricated. A cyclic desorption process using microliter volume of organic solvent was adopted to prevent any outdoor contamination. As extractive phases, two identical sheets of electrospun polyamide/polypyrrole/titania nanofibers were synthesized using core-shell electro-spinning technique and utilized for determination of memantine in plasma samples. Field emission scanning electron microscopy images showed a high degree of porosity and homogeneity throughout the sheet structure. Also, energy dispersive X-ray analysis confirmed the presence of titania, while the recorded Fourier transform infrared spectra proved the chemical structures of the polymeric mats. The incorporation of titania as well as polypyrrole in the composition of polyamide nanofibers improved both mechanical stability and extraction capacity of the extractive phase and therefore facilitated the extraction/desorption process. The limits of detection and quantification were 0.01 and 0.04 ng/mL, respectively. In addition, the interday and intraday precisions were lower than 6.7% (n = 3). The linearity was in the range of 0.14-75.00 ng/mL, while recoveries were between 94.1 and 98.4% with the regression coefficient of 0.9987.

Amine modified magnetic polystyrene for extraction of drugs from urine samples.

Polystyrene is one of the best candidates as the extracting medium due to its high stability in different media and acceptable extraction capability. However, the hydrophobic nature and low wettability of polystyrene limits its application to non-polar analytes. To resolve this limitation, in this project, amine groups were chemically attached to the surface of magnetic polystyrene. The resulting hydrophilic magnetic particles were expected to be capable of extracting both polar and non-polar analytes. Non-steroidal anti-inflammatory drugs (NSAIDs) were chosen for testing the applicability of modified magnetic polystyrene according to the importance of their analysis and also their wide polarity range. Major parameters associated with the extraction procedure were optimized using central composite design (CCD) method and pH 3, extraction time of 15 min, desorption volume of 350 µL and desorption time of 4 min were chosen as optimized values. Under these conditions, figures of merit were calculated including: linear dynamic range (0.5-1000 µg L-1), linear equation and limits of detection (0.1-3 µg L-1). To investigate the method precision, inter-day, intra-day and synthesis-to-synthesis relative standard deviation (RSD) were studied (<12%). All studies were conducted using blank urine samples spiked with aspirin, salicylic acid, ibuprofen, diclofenac and mefenamic acid. Naproxen was chosen as the internal standard and high-performance liquid chromatography-UV-Vis (HPLC-UV) was employed for the subsequent determination after extraction. To evaluate the applicability of the method for real sample analysis, urine samples from patients under treatment were analyzed and acceptable results were obtained. The aminated magnetic polystyrene revealed superior extraction efficiency, much higher than polystyrene before functionalization. In addition, hospital wastewater sample was tested and acceptable extraction efficiencies were obtained.

Generic extraction medium: From highly polar to non-polar simultaneous determination.

Sample preparation for non-target analysis is challenging due to the difficulty in the extraction of polar and non-polar analytes simultaneously. Most commercial solid sorbents lack the proper comprehensiveness for extraction of analytes with different physiochemical properties. A possible key is the combination of hydrophobic polymer and hydrophilic surface functional groups in solid based extraction methods in order to generate the susceptibility for retaining both polar and non-polar analytes. To pursue this goal, in this study, four polar groups including NH2, NO2, COOH, and COCH3 were chemically bound to Amberlite XAD-4 substrate in order to prepare a generic extraction platform. To validate the applicability of extractive phases, 22 analytes possessing wide range of polarities (LogP range between -2 and +7) were chosen for extraction using the synthesized polymers by online micro solid phase extraction (µ-SPE) and further analyzed with high-performance liquid chromatography and UV-Vis detection (HPLC-UV). The recovery data were compared with commercial sorbents by t-test, principal component analysis (PCA) and hierarchical cluster analysis (HCA). Amberlite XAD-4 modified with COOH group (XAD-COOH) revealed extraction efficiencies statistically better than commercially available sorbents including LiChrolut® EN, Oasis® HLB and Amberlite® XAD-4®. The reproducibility and repeatability of XAD-COOH were also studied and acceptable results were obtained. Furthermore, the swellability of polymers was also measured and the results were comparable with commercial ones. To evaluate the extraction ability of XAD-COOH in real sample matrix, water sample near a heavy crude oil spill, urine and hospital wastewater were analyzed. Comparison of the data with LiChrolut® EN corroborates the dominance of XAD-COOH for screening analysis.

Graphene oxide-starch-based micro-solid phase extraction of antibiotic residues from milk samples.

In this study, a method was described for the extraction of three antibiotic residues from cow milk samples using a graphene oxide-starch-based nanocomposite. The prepared nanocomposites were employed as an extractive phase for micro-solid phase extraction of antibiotics from cow milk samples. The extracted antibiotics, i.e. amoxicillin, ampicillin and cloxacillin, were subsequently analyzed by high-performance liquid chromatography-ultraviolet detection (HPLC-UV). Important variables associated with the extraction and desorption efficiency were optimized. High extraction efficiencies for the selected antibiotics were conveniently achieved using the starch-based nanocomposite as the extractive phase. The developed method was validated according to the European Commission Decision 2002/657/EC by spiking the selected antibiotics to the blank milk samples. The limits of quantitation (2.7-5.0 µg kg-1) were calculated for the selected penicillin group in milk samples and their quantities are lower than the maximum residue limits (MRLs). The obtained results indicate the remarkable efficiency of the graphene oxide-starch-based nanocomposite performance toward the selected antibiotics. The relative standard deviations of intra and inter-day analysis are less than 3.3 and 6.1%, respectively. Moreover, trueness of method was successfully accomplished via the recovery assays (88-102%) in the fortified blank milk samples with three different concentration levels (MRL, 1.5 MRL and 3 MRL µg kg-1). In overall, the proposed method was a promising alternative for analysis of selected three antibiotics in variety milk samples, due to the effective and easy-to-perform method and acceptable relative recovery in the range 83-105%.

Nanostructured molybdenum oxide in a 3D metal organic framework and in a 2D polyoxometalate network for extraction of chlorinated benzenes prior to their quantification by GC-MS.

A three-dimensional metal organic framework (3D-MOF) and a two-dimensional polyoxometalate (2D-POM), both incorporating nanostructured molybdenum (VI) oxide, were synthesized and implemented for headspace needle trap extraction of traces of chlorobenzenes (CBs). The 3D-MOF of type {(Mo2O6)(4,4'-bpy)}n and the 2D-POM of type [4,4'-bpy][Mo7O22] were synthesized by a solvothermal process and characterized by FT-IR, powder X-ray diffraction, scanning electron microscopy, transmission electron microscopy, thermogravimetry, energy dispersive X-ray, elemental mapping and Brunner-Emmet-Teller adsorption analyses. The 3D-MOF proved to be superior. Following thermal desorption, the CBs (monochlorobenzene, 1,4-dichlorobenzene, 1,2-dichlorobenzene, 1,2,4-trichlorobenzene and 1,2,3,4-tetrachlorobenzene) were quantified by GC-MS. Under optimized conditions, the calibration plots are linear in the 1-1000 ng.L-1 concentration range, and the limits of detection range from 0.2 to 2 ng.L-1. The intra- and inter-day relative standard deviations for three replicates at levels of 10 and 200 ng.L-1 are in the range of 5-12% and 10-15%, respectively. The needle-to-needle reproducibility was also found to be in the range of 6-13%. The application of the method to the analysis of various spiked real water samples resulted in recoveries between 84 and 114%. Graphical abstract A comparison of extraction efficiency between 3D-MOF and 2D-POM, in which 3D-MOF is superior to isolate organic pollutants, due to possession of more 4,4'-bpy ligands and interaction sites.

Gradient extractive phase prepared by controlled rate infusion method: An applicable approach in solid phase microextraction for non-targeted analysis.

The aim of this study is to introduce an extractive phase based on gradient concept by continuous changing in chemical functional groups for non-targeted analysis. For this purpose, three different two-component coatings containing (3-aminopropyl)trimethoxysilane (APTES) as polar and either phenyltriethoxysilane (PTES), octyl-trimethoxysilane (OTMS) or methyltrimethoxysilane (MTMS) as nonpolar precursors were formed on the modified stainless steel wires using controlled rate infusion (CRI) method. The presence of polar and/or non-polar functional groups on the surface of substrate was evaluated by Fourier-transform infrared spectroscopy (FTIR) together with contact angles determined alongside the gradient surface. The morphology and thickness of the prepared fibers were also investigated by scanning electron microscopy (SEM). Furthermore, uniform single-component fibers from polar (APTES) and nonpolar (PTES) coatings were fabricated in order to be compared with the gradient sorbent. The gradient phase was implemented as a fiber coating in headspace- or immersed-solid phase microextraction of various compounds including chlorobenzenes, polycyclic aromatic hydrocarbons, chlorophenols and volatile organic compounds (Log Kow range: -0.77 to 4.64). Under the optimized condition, the limits of detection and quantification were obtained in the range of 0.01-0.5 µg L-1 and 0.05-1.5 µg L-1, respectively. The intra-day and inter-day relative standard deviations of 2-10% and 11-17% were achieved, respectively. The method was successfully applied to the extraction of VOCs from real water sample and relative recoveries were between 89 and 105%. The capability and efficiency of the gradient coating appears to be quite appropriate for non-targeted analysis.

Porous eco-friendly fibers for on-line micro solid-phase extraction of nonsteroidal anti-inflammatory drugs from urine and plasma samples.

In this study, cellulose acetate (CA) fibers were prepared using different solvent systems in electrospinning. The recorded scanning electron microscopy micrographs indicated that the morphology of the prepared fibers is closely associated with the type of electrospinning solvents. The prepared CA fibers were used as an extractive phase for on-line micro-solid phase extraction (µ-SPE) of nonsteroidal-inflammatory drugs (NSAIDs) in biological samples pursued by HPLC-UV determination. Work conducted on this research ascertained that the use of dichloromethane:acetone (3:1, v/v) solvent system in the CA dissolution for electrospinning, leads to the formation of porous ribbon-like fibers and subsequent excellent extraction efficiencies for the selected drugs. Moreover, the effects of diverse parameters on the extraction efficiency were surveyed and optimized. The proposed method was used for determination of naproxen, diclofenac and mefenamic acid in human urine and plasma samples. The optimized method was validated and the limits of detection (1.0-2.4 µg L-1), limits of quantification (3.3-8.0 µg L-1) and linear dynamic range (4.0-1000.0 µg L-1) were obtained. The reproducibility (relative standard deviation: 2.6-7.9%) was in an acceptable range. Trueness of the procedure was accomplished through recovery assays in urine (94-105%) and plasma (85-102%) samples, indicating the minor contribution from the sample matrix. Finally, the CA porous fibers within the framework of the µ-SPE method were found to be appropriate for the separation and determination of the selected drugs in urine and plasma samples collected from treated patients. Also, the adsorption behavior of the porous fibers was well described by Freundlich isotherm and porous fibers showed acceptable adsorption capacity.