Automated and semi-automated packed sorbent solid phase (micro) extraction methods for extraction of organic and inorganic pollutants.

In this study, the packed sorbent solid phase (micro) extraction methods from manual to automated modes are reviewed. The automatic methods have several remarkable advantages such as high sample throughput, reproducibility, sensitivity, and extraction efficiency. These methods include solid-phase extraction, pipette tip micro-solid phase extraction, microextraction by packed sorbent, in-tip solid phase microextraction, in-tube solid phase microextraction, lab-on-a-chip, and lab-on-a-valve. The recent application of these methods for the extraction of organic and inorganic compounds are discussed. Also, the combination of novel technologies (3D printing and robotic platforms) with the (semi)automated methods are investigated as the future trend.

A miniaturized analytical system with packed epoxy-functionalized mesoporous organosilica for copper determination using a customized Android-based software.

A smartphone-assisted determination of copper ions is introduced by using a down-scaled microfluidic mixer. The system was coupled with a micro-column packed with a periodic mesoporous organosilica (PMO) material for preconcentration of copper ions. Copper ions were reduced to Cu(I) on-chip to selectively form an orange-colored complex with neocuproine. A novel Android-based software was made to determine the color change of the adsorbent by analyzing red-green-blue (RGB) components of images from the packed PMO material. Four porous framework materials with high porosity and chemical stability were synthesized and compared for the extraction of the Cu-neocuproine complex. The main parameters influencing the complex extraction efficiency were optimized. The analytical performance of the method showed limit of detection and quantification of 0.2 µg L-1 and 0.5 µg L-1, respectively. The accuracy and precision of the method were determined as recovery > 92% and relative standard deviations < 5.2% at medium concentration level (n = 5). Due to accumulation of the retained analyte in a single point and elimination of the stripping step, the RGB-based method showed sensitivity and precision higher than inductively coupled plasma-atomic emission spectrometry (ICP-AES) for determination of copper ions. To investigate the applicability of the method, six different water samples were analyzed. The t-test on the data showed that the method has no significant difference when compared with ICP-AES determination.

Ethane-bridge periodic mesoporous organosilica materials as a novel fiber coating in headspace solid-phase microextraction of phthalate esters from saliva and PET container samples.

The current study presents a periodic mesoporous organosilica (PMO) with a high surface area and uniform-porosity material. The PMO materials were successfully synthesized and modified. The resultant material was characterized by different characterization techniques. The prepared PMO was immobilized on a stainless steel wire surface and was evaluated for headspace solid-phase microextraction of the ultra-trace amount of phthalate esters from saliva and polyethylene terephthalate containers which were in contact with hot and cold water. Separation and determination of the phthalate esters (PEs) were performed by the GC-FID and GC-MS instruments. The key parameters affecting the extraction efficiencies, including extraction temperature, extraction time, ionic strength, and desorption temperature and time, were investigated and optimized. Under optimum conditions, the repeatability for one fiber (n = 7) was 4.8-8.7%, and fiber-to-fiber reproducibility (n = 3) was 7.5-10.6% for the extracted compounds. The limits of detection of the developed method for the studied compounds were between 0.01 and 1 µg L-1. The results showed suitable coefficients of determination (R2 ≥ 0.99) for all of the analytes in the 0.05-300 µg L-1 calibration range. Acceptable recovery values of 91-107%, 82-110%, and 98-104% were obtained in saliva, polyethylene terephthalate containers hot water, and cold water, respectively.

A review of green solvent extraction techniques and their use in antibiotic residue analysis.

Antibiotic residues are being continuously recognized in the aquatic environment and in food. Though the concentration of antibiotic residues is typically low, adverse effects on the environment and human health have been observed. Hence, an efficient method to determine numerous antibiotic residues should be simple, inexpensive, selective, with high throughput and with low detection limits. Liquid-based extractions have been exceedingly used for clean-up and preconcentration of antibiotics prior to chromatographic analysis. In order to make methods more green and environmentally sustainable, conventional hazardous organic solvents can be replaced with green solvents. This review presents sampling strategies as well as comprehensive and up-to-date methods for chemical analysis of antibiotic residues in different sample matrices. Particularly, solvent-based sample preparation techniques using green solvents are discussed along with applications in antibiotic residue analysis.

Plugged bifunctional periodic mesoporous organosilica as a high-performance solid phase microextraction coating for improving extraction efficiency of chlorophenols in different matrices.

In this study, a sensitive solid phase microextraction (SPME) coating was developed based on two kinds of plugged and non-plugged bifunctional periodic mesoporous organosilicas (BFPMO) with ionic liquid and ethyl units. The extraction efficiency of all plugged and unplugged sorbents was investigated for the extraction of chlorophenols (CPs) in water and honey samples by emphasizing the effect of different physicochemical properties. The separation and determination of the CPs was performed by gas chromatography-mass spectrometry (GC-MS). The extraction results showed that plugged BFPMO coating exhibited outstanding enrichment ability for the extraction of CPs as model analytes with different polarities. This can be attributed to a valuable hydrophobic-hydrophilic balance in the mesochanels of the plugged BFPMO, which is the result of the combination of plug technology and bridged organic groups. Low limits of detection in the range of 5-70 ng L-1, wide linearity, and good reproducibility (RSD = 8.1-10.1 % for n = 6) under the optimized extraction conditions were achieved. Finally, the BFPMOs coated fiber was successfully used for determination of CPs in real water samples. The relative recoveries for the five CPs were in the range of 92.3-104.0 %, which proved the applicability of the method.

Applications of porous frameworks in solid-phase microextraction.

Porous frameworks are a term of attracting solid materials assembled by interconnection of molecules and ions. These trendy materials due to high chemical and thermal stability, well-defined pore size and structure, and high effective surface area gained attention to employ as extraction phase in sample pretreatment methods before analytical analysis. Solid-phase microextraction is an important subclass of sample preparation technique that up to now different configurations of this method have been introduced to get adaptable with different environments and analytical instruments. In this review, theoretical aspect and different modes of solid-phase microextraction method are investigated. Different classes of porous frameworks and their applications as extraction phase in the proposed microextraction method are evaluated. Types and features of supporting substrates and coating procedures of porous frameworks on them are reviewed. At the end, the prospective and the challenges ahead in this field are discussed.

Covalent organic framework and montomorillonite nanocomposite as advanced adsorbent: synthesis, characterization, and application in simultaneous adsorption of cationic and anionic dyes.

In this work, Schiff base network-1 (SNW-1), as a new generation of covalent organic frameworks (COFs), was synthesized and modified by fabrication of a composite with clay mineral montomorillonite (Mt). It was used for simultaneous removal of anionic and cationic dyes from aqueous solutions. The fabricated composite was characterized successfully with various techniques. Tartrazine (TT) and methylene blue (MB) were selected as model anionic and cationic dyes, respectively. The effects of the percentage of each component in the composite, initial pH, and initial dye concentration were evaluated on the adsorption capacity. Adsorption reaction models and adsorption diffusion models were used to study the kinetic process of adsorption. Adsorption of both dyes reached equilibrium after 40 min. The obtained results were fitted to Langmuir, Freundlich, Temkin, and Dubinin-Radushkevich (D-R) models to predict the isotherms of adsorption. Under optimum conditions for removal of each dye with the composite, the maximum adsorption capacity of 519.2 and 602.7 mg g-1 were obtained for TT and MB, respectively. The used SNW-1/Mt composite could be regenerated by salty methanol. The high adsorption capacity and excellent reusability make SNW-1/Mt composite attractive for the simultaneous removal of anionic and cationic dyes from aqueous solutions.

Reduced graphene-decorated covalent organic framework as a novel coating for solid-phase microextraction of phthalate esters coupled to gas chromatography-mass spectrometry.

Schiff base network-1 (SNW-1), as a new generation of covalent organic frameworks (COFs), was synthesized and modified by fabrication of a composite with graphene oxide (GO). The fabricated nanocomposite was characterized with FT-IR spectroscopy, XRD, FE-SEM, EDX, TGA, and the nitrogen adsorption-desorption technique. Characterization results showed that SNW-1 can reduce GO during the fabrication procedure and produce an effective and stable nanocomposite. This nanocomposite was deposited on the surface of a stainless steel wire via a single phase inversion method with the help of polyethersulfone, as a porous adhesive material. This robust and stable coating was used for head space solid-phase microextraction of phthalate esters (PhEs) from water samples. Determination of the PhEs was performed with gas chromatography coupled to mass spectrometry. SNW-1 is N-rich, and reduced-GO is full of hexagonal conjugated rings. Therefore, due to hydrogen binding and π-interaction, the coating has a high tendency to PhEs. Effective adsorption and desorption parameters were optimized. The performance of the method was evaluated in terms of linear ranges (LRs from 0.05 to 100 µg L-1 with R2 ≥ 0.9942) and limits of detection (LODs in the range of 0.01-0.50 µg L-1). The average repeatability and fiber-to-fiber reproducibility were 6.8% and 9.2%, respectively. The method was employed to trace determination of PhEs in drinking water and pickled cucumber solution with good recovery (80.5-111.0%) and reliable reproducibility (5.5-9.5%). Graphical abstract Schematic representation of headspace-solid phase microextraction (HS-SPME) of phthalate esters (PhEs) from pickled cucumber solution and determination with gas chromatography-mass spectrometry (GC-MS).

3D Printing in analytical sample preparation.

In the last 5 years, additive manufacturing (three-dimensional printing) has emerged as a highly valuable technology to advance the field of analytical sample preparation. Three-dimensional printing enabled the cost-effective and rapid fabrication of devices for sample preparation, especially in flow-based mode, opening new possibilities for the development of automated analytical methods. Recent advances involve membrane-based three-dimensional printed separation devices fabricated by print-pause-print and multi-material three-dimensional printing, or improved three-dimensional printed holders for solid-phase extraction containing sorbent bead packings, extraction disks, fibers, and magnetic particles. Other recent developments rely on the direct three-dimensional printing of extraction sorbents, the functionalization of commercial three-dimensional printable resins, or the coating of three-dimensional printed devices with functional micro/nanomaterials. In addition, improved devices for liquid-liquid extraction such as extraction chambers, or phase separators are opening new possibilities for analytical method development combined with high-performance liquid chromatography. The present review outlines the current state-of-the-art of three-dimensional printing in analytical sample preparation.

Novel generation of deep eutectic solvent as an acceptor phase in three-phase hollow fiber liquid phase microextraction for extraction and preconcentration of steroidal hormones from biological fluids.

In this study, a novel generation of deep eutectic solvents (DESs) was used as an acceptor phase in three-phase hollow fiber liquid phase microextraction (HF-LPME) based on two immiscible organic phases. It was compared with other common DESs for extraction and preconcentration of dydrogesterone (DYD) and cyproterone acetate (CPA) from urine and plasma samples. The extracted analytes were analyzed by high performance liquid chromatography with UV-vis detector (HPLC-UV). This phosphonium based DES due to low volatility, low price and multifunctionality introduced itself as worthy next generation of acceptor phase in HF-LPME. The factors affected on extraction efficiency of the analytes were investigated and optimized. The performance of the proposed method was studied in terms of linear ranges (LRs from 1 to 500µgL-1 with R2 ≥ 0.9946), precision (RSD% ≤ 6.3) and limits of detection (LODs in the range of 0.5-2µgL-1). Under the optimized conditions, preconcentration factors in the range of 187-428 were obtained. Finally, the method was applied to the analysis of DYD and CPA in human urine and plasma samples and desirable results were obtained.