Solid-phase microextraction Arrow combined with comprehensive two-dimensional gas chromatography-mass spectrometry for the elucidation of the volatile composition of honey samples.

In this work, a solid-phase microextraction (SPME) Arrow method combined with comprehensive two-dimensional gas chromatography-mass spectrometry (GC × GC-MS) was developed for the elucidation of the volatile composition of honey samples. The sample preparation protocol was optimized to ensure high extraction efficiency of the volatile organic compounds (VOCs) which are directly associated with the organoleptic properties of honey and its acceptance by the consumers. Following its optimization, SPME Arrow was compared to conventional SPME in terms of sensitivity, precision, and number of extracted VOCs. The utilization of SPME Arrow fibers enabled the determination of 203, 147, and 149 compounds in honeydew honey, flower honey, and pine honey, respectively, while a significantly lower number of compounds (124, 94, and 111 for honeydew honey, flower honey, and pine honey, respectively) was determined using conventional SPME. At the same time, the utilization of SPME Arrow resulted in enhanced sensitivity and precision. All things considered, SPME Arrow and GC × GC-MS can be considered as highly suitable for the elucidation of the volatile composition of complex food samples resulting in high sensitivity and separation efficiency.

Fabricating a designer capsule phase microextraction platform based on sol-gel Carbowax 20M-zwitterionic ionic liquid composite sorbent for the extraction of lipid-lowering drugs from human urine samples.

A sol-gel Carbowax 20 M/3-[(3-Cholamidopropyl) dimethyl ammonio]-1-propanesulfonate composite sorbent-based capsule phase microextraction device has been fabricated and characterized for the determination of four statins (pravastatin, rosuvastatin, pitavastatin, and atorvastatin) in human urine. The presence of ionizable carboxyl functional groups in statins requires pH adjustment of the sample matrix to ensure that the target molecules are in their protonated form (pH should be 2 units below their pKa values) which not only is cumbersome but also risks unintended contamination of the sample. This challenge was addressed by introducing zwitterionic ionic liquid in addition to neutral, polar Carbowax 20 M polymer in the sol-gel-derived composite sorbent. As such, the composite zwitterionic multi-modal sorbent can simultaneously extract neutral, cationic, and anionic species. This particular attribute of the composite sorbent eliminates the necessity of the matrix pH adjustment and consequently simplifies the overall sample preparation workflow. Various experimental parameters such as the sample amount, extraction time, salt addition, stirring rate, and elution solvent type that may affect the extraction performance of the statins were investigated using a central composite design and the one-parameter-at-a-time approach. The analytes and the internal standard were separated on a C18 column with gradient elution using phosphate buffer (20 mM, pH 3) and acetonitrile as mobile phase. The analytes were detected at 237 nm. The method was validated, and linearity was observed in the range 0.10-2.0 µg mL-1 for all compounds. The method precision was better 9.9% and 10.4% for intra-day and inter-day, respectively, while the relative recoveries were acceptable, ranging between 83.4 and 116% in all cases. Method greenness was assessed using the ComplexGAPI index. Finally, the method's applicability was demonstrated in the determination of the statins in authentic human urine after oral administration of pitavastatin and rosuvastatin-containing tablets.

Sol-Gel Graphene Oxide-Coated Fabric Disks as Sorbents for the Automatic Sequential-Injection Column Preconcentration for Toxic Metal Determination in Distilled Spirit Drinks.

Sol-gel graphene oxide-coated polyester fabric platforms were synthesized and used for the on-line sequential injection fabric disk sorptive extraction (SI-FDSE) of toxic (i.e., Cd(II), Cu(II) and Pb(II)) metals in different distilled spirit drinks prior to their determination by electrothermal atomic absorption spectrometry (ETAAS). The main parameters that could potentially influence the extraction efficiency of the automatic on-line column preconcentration system were optimized and the SI-FDSE-ETAAS method was validated. Under optimum conditions, enhancement factors of 38, 120 and 85 were achieved for Cd(II), Cu(II) and Pb(II), respectively. Method precision (in terms of relative standard deviation) was lower than 2.9% for all analytes. The limits of detection for Cd(II), Cu(II) and Pb(II) were 1.9, 7.1 and 17.3 ng L-1, respectively. As a proof of concept, the proposed protocol was employed for the monitoring of Cd(II), Cu(II), and Pb(II) in distilled spirit drinks of different types.

Dual Lab-in-Syringe Flow-Batch Platform for Automatic Fabric Disk Sorptive Extraction/Back-extraction as a Front End to Inductively Coupled Plasma Atomic Emission Spectrometry.

A novel dual lab-in-syringe flow-batch (D-LIS-FB) platform for automatic fabric-disk-in-syringe sorptive extraction followed by oxidative back-extraction as a front end to inductively coupled plasma atomic emission spectrometry (ICP-AES) is presented for the first time. Sol-gel poly(caprolactone)-poly(dimethylsiloxane)-poly(caprolactone)-coated polyester fabric disks were packed at the top of the glass barrel of a microsyringe pump as an alternative to column preconcentration. Herein lie multiple significant advantages including effectiveness, compactness, lower back-pressure, and lower time of analysis. Copper, lead, and cadmium were used as model analytes for the exploration of the capabilities of the developed platform. The online retained metal-diethyldithiophosphate complexes were eluted using diisopropyl ketone prior to atomization. Undesirable incompatibility of organic solvents for direct injection into the ICP-AES system was overcome ingeniously in a flow manner by oxidative back-extraction of the analytes utilizing a second lab-in-syringe setup. Following its optimization, the D-LIS-FB platform showed excellent linearity, in combination with good method precision (i.e., RSD < 3.4%) and trueness. Moreover, the limits of detection were 0.25 µg L-1 for Cd(II), 0.13 µg L-1 for Cu(II), and 0.37 µg L-1 for Pb(II), confirming the applicability of the proposed system for metal analysis at trace levels. As a proof-of-concept, the developed versatile system was utilized for the analysis of different environmental, food, and biological samples.

Recent advances in the extraction of triazine herbicides from water samples.

Pesticides are excessively used in agriculture to improve the quality of crops by eliminating the negative effects of pests. Among the different groups of pesticides, triazine pesticides are a group of compounds that contain a substituted C3 H3 N3 heterocyclic ring, and they are widely used. Triazine pesticides can be dangerous for humans as well as for the aquatic environment because of their high toxicity and endocrine disrupting effect. However, the concentration of these chemical compounds in water samples is low. Moreover, other compounds that may exist in the water samples can interfere with the determination of triazine pesticides. As a result, it is important to develop sample preparation methods that provide preconcentration of the target analyte and sufficient clean-up of the samples. Recently, a wide variety of novel microextraction and miniaturized extraction techniques (e.g., solid-phase microextraction and liquid-phase microextraction, stir bar sorptive extraction, fabric phase sorptive extraction, dispersive solid-phase extraction, and magnetic solid-phase extraction) have been developed. In this review, we aim to discuss the recent advances regarding the extraction of triazine pesticides from environmental water samples. Emphasis will be given to novel sample preparation methods and novel sorbents developed for sorbent-based extraction techniques.

Salting-out homogeneous liquid-liquid microextraction for the determination of azole drugs in human urine: Validation using total error concept.

A salting-out homogeneous liquid-liquid microextraction was proposed for the quantification of four azole drugs in human urine prior to high-performance liquid chromatography analysis. The procedure involved the mixing of the sample with acetonitrile in appropriate volumes followed by the addition of sodium sulfate solution in order to facilitate phase separation. The parameters influencing the extraction performance were studied and optimized using a two-step experimental design. The analytical procedure was thoroughly validated using the accuracy profiles as a graphical decision-making tool. The ß-expectation tolerance intervals did not exceed the acceptance criteria of ±15% meaning that 95% of future results will be included in the defined bias limits. The limits of detection of the procedure were satisfactory, ranging between 0.01 and 0.03 µg/mL. The mean analytical bias in the spiking levels was satisfactory and ranged between -10.3 and 4.2% while the relative standard deviation was lower than 5.6%. Monte-Carlo simulations followed by capability analysis were employed to investigate the ruggedness of the sample preparation protocol. The developed method offers advantages compared to previously reported approaches for the same type of analysis including extraction efficiency and scaling down of the sample volume and extraction time.

A simple and green liquid chromatography method for the determination of ibuprofen in milk-containing simulated gastrointestinal media for monitoring the dissolution studies of three-dimensional-printed formulations.

A fast and green ultra-high-performance liquid chromatographic method was developed for the determination of ibuprofen in milk-containing simulated gastrointestinal media to monitor the dissolution of three-dimensional printed formulations. To remove interfering compounds, protein precipitation using methanol as a precipitation reagent was performed. The separation of the target analyte was performed on a C18 column using a mobile phase consisting of 0.05% v/v aqueous phosphoric acid solution: methanol, 25:75% v/v. Method validation was conducted using the total error concept. The ß-expectation tolerance intervals did not exceed the acceptance criteria of ±15%, meaning that 95% of future results will be included in the defined bias limits. The relative bias ranged between ─1.1 and +3.2% for all analytes, while the relative standard deviation values for repeatability and intermediate precision were less than 2.8% and 3.9%, respectively. The achieved limit of detection was 0.01 µg/ml and the lower limit of quantitation was established as 2 µg/ml. The proposed method was simple, and it required reduced organic solvent consumption following the requirements of Green Analytical Chemistry. The method was successfully employed for the determination of ibuprofen in real biorelevant media obtained from dissolution studies.

Multi-Element Analysis Based on an Automated On-Line Microcolumn Separation/Preconcentration System Using a Novel Sol-Gel Thiocyanatopropyl-Functionalized Silica Sorbent Prior to ICP-AES for Environmental Water Samples.

A sol-gel thiocyanatopropyl-functionalized silica sorbent was synthesized and employed for an automated on-line microcolumn preconcentration platform as a front-end to inductively coupled plasma atomic emission spectroscopy (ICP-AES) for the simultaneous determination of Cd(II), Pb(II), Cu(II), Cr(III), Co(II), Ni(II), Zn(II), Mn(II), Hg(II), and V(II). The developed system is based on an easy-to-repack microcolumn construction integrated into a flow injection manifold coupled directly to ICP-AES's nebulizer. After on-line extraction/preconcentration of the target analyte onto the surface of the sorbent, successive elution with 1.0 mol L-1 HNO3 was performed. All main chemical and hydrodynamic factors affecting the effectiveness of the system were thoroughly investigated and optimized. Under optimized experimental conditions, for 60 s preconcentration time, the enhancement factor achieved for the target analytes was between 31 to 53. The limits of detection varied in the range of 0.05 to 0.24 µg L-1, while the limits of quantification ranged from 0.17 to 0.79 µg L-1. The precision of the method was expressed in terms of relative standard deviation (RSD%) and was less than 7.9%. Furthermore, good method accuracy was observed by analyzing three certified reference materials. The proposed method was also successfully employed for the analysis of environmental water samples.

Green Bioanalytical Applications of Graphene Oxide for the Extraction of Small Organic Molecules.

Bioanalysis is the scientific field of the quantitative determination of xenobiotics (e.g., drugs and their metabolites) and biotics (e.g., macromolecules) in biological matrices. The most common samples in bioanalysis include blood (i.e., serum, plasma and whole blood) and urine. However, the analysis of alternative biosamples, such as hair and nails are gaining more and more attention. The main limitations for the determination of small organic compounds in biological samples is their low concentration in these matrices, in combination with the sample complexity. Therefore, a sample preparation/analyte preconcentration step is typically required. Currently, the development of novel microextraction and miniaturized extraction techniques, as well as novel adsorbents for the analysis of biosamples, in compliance with the requirements of Green Analytical Chemistry, is in the forefront of research in analytical chemistry. Graphene oxide (GO) is undoubtedly a powerful adsorbent for sample preparation that has been successfully coupled with a plethora of green extraction techniques. GO is composed of carbon atoms in a sp2 single-atom layer of a hybrid connection, and it exhibits high surface area, as well as good mechanical and thermal stability. In this review, we aim to discuss the applications of GO and functionalized GO derivatives in microextraction and miniaturized extraction techniques for the determination of small organic molecules in biological samples.

Recent Advances in the Extraction of Polycyclic Aromatic Hydrocarbons from Environmental Samples.

Polycyclic aromatic hydrocarbons (PAHs) comprise a group of chemical compounds consisting of two or more fused benzene rings. PAHs exhibit hydrophobicity and low water solubility, while some of their members are toxic substances resistant to degradation. Due to their low levels in environmental matrices, a preconcentration step is usually required for their determination. Nowadays, there is a wide variety of sample preparation techniques, including micro-extraction techniques (e.g., solid-phase microextraction and liquid phase microextraction) and miniaturized extraction techniques (e.g., dispersive solid-phase extraction, magnetic solid-phase extraction, stir bar sorptive extraction, fabric phase sorptive extraction etc.). Compared to the conventional sample preparation techniques, these novel techniques show some benefits, including reduced organic solvent consumption, while they are time and cost efficient. A plethora of adsorbents, such as metal-organic frameworks, carbon-based materials and molecularly imprinted polymers, have been successfully coupled with a wide variety of extraction techniques. This review focuses on the recent advances in the extraction techniques of PAHs from environmental matrices, utilizing novel sample preparation approaches and adsorbents.

Sample Preparation Using Graphene-Oxide-Derived Nanomaterials for the Extraction of Metals.

Graphene oxide is a compound with a form similar to graphene, composed of carbon atoms in a sp2 single-atom layer of a hybrid connection. Due to its significant surface area and its good mechanical and thermal stability, graphene oxide has a plethora of applications in various scientific fields including heterogenous catalysis, gas storage, environmental remediation, etc. In analytical chemistry, graphene oxide has been successfully employed for the extraction and preconcentration of organic compounds, metal ions, and proteins. Since graphene oxide sheets are negatively charged in aqueous solutions, the material and its derivatives are ideal sorbents to bind with metal ions. To date, various graphene oxide nanocomposites have been successfully synthesized and evaluated for the extraction and preconcentration of metal ions from biological, environmental, agricultural, and food samples. In this review article, we aim to discuss the application of graphene oxide and functionalized graphene oxide nanocomposites for the extraction of metal ions prior to their determination via an instrumental analytical technique. Applications of ionic liquids and deep eutectic solvents for the modification of graphene oxide and its functionalized derivatives are also discussed.

Novel Approaches Utilizing Metal-Organic Framework Composites for the Extraction of Organic Compounds and Metal Traces from Fish and Seafood.

The determination of organic and inorganic pollutants in fish samples is a complex and demanding process, due to their high protein and fat content. Various novel sorbents including graphene, graphene oxide, molecular imprinted polymers, carbon nanotubes and metal-organic frameworks (MOFs) have been reported for the extraction and preconcentration of a wide range of contaminants from fish tissue. MOFs are crystalline porous materials that are composed of metal ions or clusters coordinated with organic linkers. Those materials exhibit extraordinary properties including high surface area, tunable pore size as well as good thermal and chemical stability. Therefore, metal-organic frameworks have been recently used in many fields of analytical chemistry including sample pretreatment, fabrication of stationary phases and chiral separations. Various MOFs, and especially their composites or hybrids, have been successfully utilized for the sample preparation of fish samples for the determination of organic (i.e., antibiotics, antimicrobial compounds, polycyclic aromatic hydrocarbons, etc.) and inorganic pollutants (i.e., mercury, palladium, cadmium, lead, etc.) as such or after functionalization with organic compounds.

Magnetic Solid-Phase Extraction of Organic Compounds Based on Graphene Oxide Nanocomposites.

Graphene oxide (GO) is a chemical compound with a form similar to graphene that consists of one-atom-thick two-dimensional layers of sp2-bonded carbon. Graphene oxide exhibits high hydrophilicity and dispersibility. Thus, it is difficult to be separated from aqueous solutions. Therefore, functionalization with magnetic nanoparticles is performed in order to prepare a magnetic GO nanocomposite that combines the sufficient adsorption capacity of graphene oxide and the convenience of magnetic separation. Moreover, the magnetic material can be further functionalized with different groups to prevent aggregation and extends its potential application. Until today, a plethora of magnetic GO hybrid materials have been synthesized and successfully employed for the magnetic solid-phase extraction of organic compounds from environmental, agricultural, biological, and food samples. The developed GO nanocomposites exhibit satisfactory stability in aqueous solutions, as well as sufficient surface area. Thus, they are considered as an alternative to conventional sorbents by enriching the analytical toolbox for the analysis of trace organic compounds.

Bioanalytical HPLC Applications of In-Tube Solid Phase Microextraction: A Two-Decade Overview.

In-tube solid phase microextraction is a cutting-edge sample treatment technique offering significant advantages in terms of miniaturization, green character, automation, and preconcentration prior to analysis. During the past years, there has been a considerable increase in the reported publications, as well as in the research groups focusing their activities on this technique. In the present review article, HPLC bioanalytical applications of in-tube SPME are discussed, covering a wide time frame of twenty years of research reports. Instrumental aspects towards the coupling of in-tube SPME and HPLC are also discussed, and detailed information on materials/coatings and applications in biological samples are provided.

Determination of Volatile Compounds in Nut-Based Milk Alternative Beverages by HS-SPME Prior to GC-MS Analysis.

A reliable Headspace-Solid Phase Microextraction (HS-SPME) method was developed for the determination of polar volatile components of commercial nut-based milk alternative drinks prior to Gas Chromatography-Mass Spectrometry (GC-MS) analysis. Under the optimum extraction conditions, a divinylbenzene (DVB)/Carboxen™ CAR)/polydimethylsiloxane (PDMS) fiber was used and 2 mL of sample was heated at 60 °C for 40 min under stirring, without salt addition. Ten compounds from different chemical classes (heptane, a-pinene, toluene, 2-methylpyrazine, 3-heptanone, heptanal, 2-octanone, 1-heptanol, benzaldehyde and 1-octanol) were chosen as model analytes for quantification. Limits of detection and limits of quantification were found to be 0.33-1.67 ng g-1 and 1-5 ng g-1, accordingly. Good linearity, precision and accuracy were obtained as well as a wide linear range. The proposed method was successfully applied to various beverages including almond milk, walnut milk, peanut milk and almond chocolate milk. More than 70 volatile compounds were detected in the different samples. Most of the detected volatiles were aldehydes, ketones and alcohols. This technique can be used for the determination of volatile compounds in nut-based beverages, to detect compositional changes during storage and technological treatment used for their production.

Extraction of Metal Ions with Metal-Organic Frameworks.

Metal-organic frameworks (MOFs) are crystalline porous materials composed of metal ions or clusters coordinated with organic linkers. Due to their extraordinary properties such as high porosity with homogeneous and tunable in size pores/cages, as well as high thermal and chemical stability, MOFs have gained attention in diverse analytical applications. MOFs have been coupled with a wide variety of extraction techniques including solid-phase extraction (SPE), dispersive solid-phase extraction (d-SPE), and magnetic solid-phase extraction (MSPE) for the extraction and preconcentration of metal ions from complex matrices. The low concentration levels of metal ions in real samples including food samples, environmental samples, and biological samples, as well as the increased number of potentially interfering ions, make the determination of trace levels of metal ions still challenging. A wide variety of MOF materials have been employed for the extraction of metals from sample matrices prior to their determination with spectrometric techniques.

Applications of Metal-Organic Frameworks in Food Sample Preparation.

Food samples such as milk, beverages, meat and chicken products, fish, etc. are complex and demanding matrices. Various novel materials such as molecular imprinted polymers (MIPs), carbon-based nanomaterials carbon nanotubes, graphene oxide and metal-organic frameworks (MOFs) have been recently introduced in sample preparation to improve clean up as well as to achieve better recoveries, all complying with green analytical chemistry demands. Metal-organic frameworks are hybrid organic inorganic materials, which have been used for gas storage, separation, catalysis and drug delivery. The last few years MOFs have been used for sample preparation of pharmaceutical, environmental samples and food matrices. Due to their high surface area MOFs can be used as adsorbents for the development of sample preparation techniques of food matrices prior to their analysis with chromatographic and spectrometric techniques with great performance characteristics.

A continuous flow polyurethane foam solid phase microextraction lab-in-syringe platform for the automatic determination of toxic metals.

A novel fully automatic continuous flow polyurethane foam solid phase microextraction lab-in-syringe system for on-line sample preconcentration/separation has been developed as a front-end to flame atomic absorption spectrometry. For the first time lab-in-syringe in continuous flow has been adopted for the determination of toxic metals. The microextraction procedure was performed after on-line metal complexation with ammonium pyrrolidine dithiocarbamate, while the elution was conducted by 400 µL of methyl isobutyl ketone. The main chemical and hydrodynamic factors that affected the performance of the method were optimized using Cd and Pb as model analytes. For 90 s preconcentration time, the limits of the detection were 0.20 and 1.7 µg L-1 for Cd and Pb, respectively, while the enhancement factors were 79 for Cd and 150 for Pb. The relative standard deviation% values were lower than 2.8 % for all analytes. As a proof-of-concept the proposed system was used for environmental water analysis, providing relative recoveries within the range of 94.0 and 104.4 %. The Green Analytical Procedure Index and Blue Applicability Grade Index proved reduced environmental impact and high practicality for the proposed method.

A flow-batch lab-in-syringe foam microextraction platform for the simultaneous preconcentration and in situ membraneless gas-liquid separation of mercury prior to cold vapor atomic absorption spectrometry.

Herein, the proof-of-concept of a novel lab-in-syringe (LIS) foam microextraction platform is presented as a front-end to cold vapor atomic absorption spectrometry (CVAAS) for the simultaneous preconcentration and membraneless gas-liquid separation (GLS) of inorganic mercury in biological samples. The proposed method is based on the on-line formation of the ammonium pyrrolidine dithiocarbamate complex with mercury that was retained in the pores of polyurethane foam immobilized on the piston of the LIS system. Metal complex elution and in situ mercury vapor generation are accomplished inside the microsyringe in a flow-batch format, while the separation of vapor species is achieved via the membraneless GLS found at the top of the syringe's barrel. Under optimized operation conditions, for 90 s preconcentration time, the limit of detection was 0.02 µg L-1 and the repeatability (RSD) was 3.8% (at the 0.5 µg L-1 concentration level), within a working range extending up to 4.0 µg L-1. The practicality of the novel manifold was demonstrated using the Blue Applicability Grade Index, while the accuracy of the method was evaluated using certified reference materials and spiked samples.

Ionic-liquid/Carbowax 20 M functionalized capsule phase microextraction platform for the extraction of phosphodiesterase-5 inhibitors from human serum and urine prior to their determination by LC-MS.

Capsule phase microextraction (CPME) is an efficient bioanalytical technique that streamlines the sample preparation by integrating the filtration and stirring mechanism directly into the device. A novel composite sorbent designed to be selective towards the target analytes consisting of mixed-mode sorbent chemistry synthesized by sol-gel technology is found promising and superior to the conventional C18 sorbents. Herein we describe the encapsulation of an ionic liquid (IL)/Carbowax 20M-functionalized sol-gel sorbent (sol-gel IL/Carbowax 20 M) in the lumen of porous polypropylene tubes for the capsule phase microextraction of three phosphodiesterase-5 inhibitors namely avanafil, sildenafil, and tadalafil in human serum and urine samples. The CPME device was characterized by Scanning Electron Microscopy (SEM) and Fourier-Transform Infrared Spectroscopy (FT-IR). The experimental parameters of CPME procedure (e.g. sample pH and ionic strength, extraction time, stirring rate, elution solvent and volume) were carefully optimized to achieve the highest possible extraction efficiency for the analytes. Method validation was conducted in terms of precision, linearity, accuracy, matrix effect, lower limits of quantification, and limits of detection (LOD). The method linearity was investigated in the range of 50-1000 ng mL-1 for all analytes while the precision was less than 11.8 % in all cases. For all analytes, the LOD values were 17 ng mL-1. The IL/CW 20M-functionalized microextraction capsules could be reused at least 25 times both for urine and serum samples. The green character and the applicability of the proposed method were evaluated using the ComplexGAPI and BAGI indexes. The optimized CPME protocol exhibited reduced consumption of organic solvent and generation of waste, cost-effectiveness, and simplicity. Finally, the proposed method was successfully applied to the analysis of sildenafil in human urine after administration of drug-containing formulation.