Search Results (31)

A simple and efficient dispersive micro solid-phase extraction (DMSPE) method using nano-TiO₂ as a sorbent was developed for the separation and preconcentration of (ultra) trace levels of lead in water samples prior to quantification by electrothermal atomic absorption spectrometry (ETAAS). Key experimental parameters affecting the DMSPE process, including pH, ionic strength, sorbent dosage, and preconcentration factor, were optimized. The optimized method demonstrated a preconcentration factor of 20, a relative standard deviation below 4.5%, and a detection limit of 0.11 µg/L. The procedure was validated using certified reference material (CRM TM-25.5) and applied to real water samples from a lake, a residential well, and industrial wastewater. Satisfactory recoveries (89–103%) confirmed the reliability of the method for the determination of low lead concentrations in complex matrices. Full article

The preparation of samples for instrumental analysis is the most essential and time-consuming stage of the entire analytical process; it also has the greatest impact on the analysis results. Concentrating the sample, changing its matrix, and removing interferents are often necessary. Techniques for preparing samples for analysis are constantly being developed and modified to meet new challenges, facilitate work, and enable the determination of analytes in the most comprehensive concentration range possible. This paper focuses on using metal-organic frameworks (MOFs) as sorbents in the most popular techniques for preparing liquid samples for analysis, based on liquid-solid extraction. An increase in interest in MOFs-type materials has been observed for about 20 years, mainly due to their sorption properties, resulting, among others, from the high specific surface area, tunable pore size, and the theoretically wide possibility of their modification. This paper presents certain advantages and disadvantages of the most popular sample preparation techniques based on liquid-solid extraction, the newest trends in the application of MOFs as sorbents in those techniques, and, most importantly, presents the reader with a summary, which a specific technique and MOF for the desired application. To make a tailor-made and well-informed choice as to the extraction technique. Full article

Despite advancements in the sensitivity and performance of analytical instruments, sample preparation remains a bottleneck in the analytical process. Currently, solid-phase extraction is more widely used than traditional organic solvent extraction due to its ease of use and lower solvent requirements. Moreover, various microextraction techniques such as micro solid-phase extraction, dispersive micro solid-phase extraction, solid-phase microextraction, stir bar sorptive extraction, liquid-phase microextraction, and magnetic bead extraction have been developed to minimize sample size, reduce solvent usage, and enable automation. Among these, in-tube solid-phase microextraction (IT-SPME) using capillaries as extraction devices has gained attention as an advanced “green extraction technique” that combines miniaturization, on-line automation, and reduced solvent consumption. Capillary tubes in IT-SPME are categorized into configurations: inner-wall-coated, particle-packed, fiber-packed, and rod monolith, operating either in a draw/eject system or a flow-through system. Additionally, the developments of novel adsorbents such as monoliths, ionic liquids, restricted-access materials, molecularly imprinted polymers (MIPs), graphene, carbon nanotubes, inorganic nanoparticles, and organometallic frameworks have improved extraction efficiency and selectivity. MIPs, in particular, are stable, custom-made polymers with molecular recognition capabilities formed during synthesis, making them exceptional “smart adsorbents” for selective sample preparation. The MIP fabrication process involves three main stages: pre-arrangement for recognition capability, polymerization, and template removal. After forming the template-monomer complex, polymerization creates a polymer network where the template molecules are anchored, and the final step involves removing the template to produce an MIP with cavities complementary to the template molecules. This review is the first paper to focus on advanced MIP-based IT-SPME, which integrates the selectivity of MIPs into efficient IT-SPME, and summarizes its recent developments and applications. Full article

The advancement of traditional sample preparation techniques has brought about miniaturization systems designed to scale down conventional methods and advocate for environmentally friendly analytical approaches. Although often referred to as green analytical strategies, the effectiveness of these methods is intricately linked to the properties of the sorbent utilized. Moreover, to fully embrace implementing these methods, it is crucial to innovate and develop new sorbent or solid phases that enhance the adaptability of miniaturized techniques across various matrices and analytes. Graphene-based materials exhibit remarkable versatility and modification potential, making them ideal sorbents for miniaturized strategies due to their high surface area and functional groups. Their notable adsorption capability and alignment with green synthesis approaches, such as bio-based graphene materials, enable the use of less sorbent and the creation of biodegradable materials, enhancing their eco-friendly aspects towards green analytical practices. Therefore, this study provides an overview of different types of hybrid graphene-based materials as well as their applications in crucial miniaturized techniques, focusing on offline methodologies such as stir bar sorptive extraction (SBSE), microextraction by packed sorbent (MEPS), pipette-tip solid-phase extraction (PT-SPE), disposable pipette extraction (DPX), dispersive micro-solid-phase extraction (d-µ-SPE), and magnetic solid-phase extraction (MSPE). Full article

A dispersive micro-solid phase extraction (Dµ-SPE) method for the preconcentration of trace metal ions (Pb, Cd, Cr, Mn, Fe, Co, Ni, Cu, Zn) on graphene oxide with the complexing reagents neocuproine or batocuproine is presented here. Metal ions form cationic complexes with neocuproine and batocuproine. These compounds are adsorbed on the GO surface via electrostatic interactions. The factors affecting the separation and preconcentration of analytes such as pH, eluent (concentration, type, volume), amount of neocuproine, batocuproine and GO, mixing time, and sample volume were optimized. The optimal sorption pH was 8. The adsorbed ions were effectively eluted with 5 mL 0.5 mol L⁻¹ HNO₃ solution and determined by the ICP-OES technique. The preconcentration factor for the GO/neocuproine and GO/batocuproine in the range 10–100 and 40–200 was obtained for the analytes, with detection limits of 0.035–0.84 ng mL⁻¹ and 0.047–0.54 ng mL⁻¹, respectively. The method was validated by the analysis of the three certified reference materials: M-3 HerTis, M-4 CormTis, and M-5 CodTis. The procedure was applied to determine metal levels in food samples. Full article

Charantin is a mixture of β-sitosterol and stigmastadienol glucosides, which effectively lowers high blood glucose. Novel molecularly imprinted polymers coated magnetic nanoparticles (Fe₃O₄@MIPs) and filter paper (paper@MIPs) were synthesized by sol-gel polymerization to selectively extract charantin. β-sitosterol glucoside was selected as a template for imprinting a specific recognition owing to its larger molecular surface area than that of 5,25-stigmastadienol glucoside. Factorial designs were used to examine the effects of the types of porogenic solvents and cross-linkers on the extraction efficiency and imprinting factor before investigating other factors (for example, amounts of template and coated MIPs, and types of substrates for MIP immobilization). Compared to traditional liquid–liquid extraction, the optimal Fe₃O₄@MIP-based dispersive micro-solid phase extraction and paper@MIP extraction provided excellent extraction efficiency (87.5 ± 2.1% and 85.0 ± 2.9%, respectively) and selectivity. Charantin was well separated, and a new unidentified sterol glucoside was observed using the developed high-performance liquid chromatography with diode-array detection (Rs ≥ 2.0, n > 16,400). The developed methods were successfully utilized to extract and quantify charantin from M. charantia fruit powder and herbal products. Moreover, these methods are rapid (<10 min), inexpensive, simple, reproducible, and environmentally friendly. Full article

In this study, a novel dispersive micro-solid phase extraction (D-μSPE) technique with H-ZSM-5 zeolite as an adsorbent was developed for the determination of 21 trace pesticides in tea beverages. The adsorption and desorption of H-ZSM-5 zeolites were investigated based on structural characteristics and adsorption properties similar to those of H-beta zeolites. In combination with the properties of the adsorbates, it was explained that the adsorption reaction occurred on the microporous surface and mesopores of H-ZSM-5. Based on optimal parameters, the beverage samples were extracted by 50 mg of zeolite within 1 min. The zeolite was eluted with 2 mL of an acetonitrile-water mixture after separation, and the eluent was filtered prior to HPLC-MS/MS analysis. The D-μSPE protocol demonstrated acceptable accuracy and precision, with recoveries between 62.1% and 106.6% and relative standard deviations of 1.4% to 12.6%, as validated by analytical reliability. The correlation coefficient in the linear range of 0.2–50 ng·mL⁻¹ was greater than 0.98, with limits of detection of 0.05–0.1 ng·mL⁻¹ and limits of quantification of 0.1–0.2 ng·mL⁻¹. The matrix effects ranged from 76.2% to 112.7%. The results indicate that the novel D-μSPE technique based on H-ZSM-5 is a rapid, simple, green and economical method for the determination of pesticide residues in tea beverages. The proposed method achieved simultaneously low adsorbent dosage, 20-fold enrichment factor, rapid pre-concentration in 12 min, minimal organic wastes, and effective reduction of matrix interference. Full article

In recent years, the wine industry has shown a considerable degree of interest in the occurrence of melatonin in wines. Sample pretreatment may be the most important step in trace analysis. Since wine is a complex matrix and melatonin is present in low amounts (ppb), an adequate extraction technique is required. In this study, the effect of several extraction methods, such as solid phase extraction (SPE), Quick, Easy, Cheap, Effective, Rugged, and Safe extraction (QuEChERS), and dispersive liquid–liquid micro-extraction (DLLME) was studied and the variable parameters that can arise throughout the extraction process were optimized to obtain the best results. A high-performance liquid chromatography with fluorescence detector (HPLC-FL) method was adapted and validated, including measurement uncertainty, for the analysis of melatonin in wines and to assess the efficiency of the extraction yield. After comparing the acquired results, the DLLME method was optimized. Extraction recoveries values ranging from 95 to 104% demonstrated that the approach may be successfully applied for the extraction and concentration (enrichment factor of almost eight) of melatonin in wine samples prior to HPLC-FL analysis. The first report of melatonin levels in Feteasca Neagra wines has been made. The data obtained for Cabernet Sauvignon revealed that the final levels of melatonin in the wines are dependent on the winemaking process. Full article

Hardened pastes with different mass percentages of steel slag (SS)/titanium-extracted tailing slag (TETS) were prepared under fixed CaO content to determine the influencing mechanism of TETS on the strength of CaO SS hardened paste. Furthermore, the effects and laws of curing time and SS/TETS ratios on the strength of hardened pastes were also investigated in this study. Importantly, hydration products, microstructures and the micro-area compositions of hardened pastes were analysed using X-ray diffraction, Fourier-transform infrared spectroscopy and scanning electron microscopy–energy dispersive spectrometer, respectively, to reveal the influencing mechanism of TETS on the CaO SS hardened pastes. The results demonstrated that the early strength of hardened pastes increases considerably following the inclusion of TETS. Specifically, the strength of the sample with an SS/TETS ratio of 22.5:67.5 at 1 d can be increased by more than 14 times. Notably, its strength at 90 days reached 19.36 MPa. Moreover, the diffraction peaks of calcite and C-S-H in the samples were also strengthened. Meanwhile, a diffraction peak of hydrocalumite appeared, and the calcites in the samples were curled up. When the SS/TETS ratio was equal to or more than 45:45, a diffraction peak of Ca(OH)₂ appeared in the sample. Only a diffraction peak of Ca(OH)₂ and weak diffraction peaks of calcite and C-S-H were observed in the samples without TETS, but there was no diffraction peak of hydrocalumite. The strength at 90 days was only 4.92 MPa. The increased strength of the hardened paste is closely related to the production of new phases after adding TETS. Solid particles in the hardened paste are cemented into a whole because of the hydration of C-S-H. Calcite forms the skeleton of the hardened pastes, whereas hydrocalumite fills in the pores among particles in hardened pastes, thus making them more compacted. As a result, there is increased. Full article

Based on the specific binding of sulfonic acid groups to melamine, β-agonists and other compounds, Fe₃O₄ nano-magnetic beads were coated with polystyrene using an improved micro-suspension emulsion polymerization method, thus forming core–shell magnetic polystyrene microspheres (Fe₃O₄@PS) with Fe₃O₄ as the core and polystyrene as the shell. These functionalized microspheres, which can be used as magnetic solid-phase extraction (MSPE) adsorbent, were prepared after further sulfonation. These microspheres were characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), particle size analysis and saturation magnetization measurement. The results showed that these sulfonated magnetic polystyrene microspheres had favorable sphericity. The particle size of these microspheres ranged from 1 μm to 10 μm. Additionally, these microspheres had good dispersion and magnetic responses in both inorganic and organic solvents. Moreover, these functionalized magnetic polystyrene microspheres were tested and evaluated by high performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS). The results indicated that these sulfonated magnetic polystyrene microspheres (Fe₃O₄@SPS) could effectively adsorb such illegal additives as β-agonists and melamine in the food matrix. Full article

The sample preparation of a cosmetic specimen in Cosmetic Science for the purpose of determining the analytical composition of heavy and toxic metals such as lead (Pb), mercury (Hg), cadmium (Cd), and arsenic (As) is of particular importance due to the difficulty of handling the sample. There are two main methods of sample preparation. The first method is the wet digestion of the sample with strong acids such as H₂SO₄, HNO₃, HF, and HNO₃/HCl (1:3) and the combination of a strong acid with H₂O₂. Liquid digestion of the sample under the influence of strong acids damages the organic material of the sample and converts the carbon into carbon dioxide. The contained metals are oxidized to the highest oxidizing step and converted to soluble salts. A problem with this method is the loss of metals during digestion because it occurs at high temperatures as well as the decrease in the concentration of the residual acid. The second method of preparation is the wet liquid digestion of the sample with strong acids in a microwave oven in a closed vessel. The acids that are used are mainly HNO₃ or mixtures of acids such as HNO₃–HCl and HNO₃–H₂SO₄. When the sample in the acid’s solvent is exposed to microwave energy, it can reach temperatures substantially above the boiling temperature of the acid solution. The result is the decomposition of the organic material, the oxidation of the metals, and their conversion to soluble nitrates. The advantages of using microwaves are the ability to control the temperature, pressure, and loss of metals and, thus, avoid erroneous measurement results. Simultaneously with the above, extraction methods have been, for almost a decade, very effective complementary processes that we can use to enrich a sample of a cosmetic product. Liquid–liquid dispersion micro-extraction (DLLME) and solid phase extraction (SPE) are the two main methods used in sample preparation and are usually applied after the digestion process. Full article

Hybrid materials based on polystyrene (PS) and green metal-organic frameworks (MOFs) were synthesized, characterized, and evaluated as potential sorbents in dispersive micro-solid-phase extraction (µ-dSPE). Among the resulting materials, the hybrid PS/DUT-67(Zr) was selected as the adequate extraction material for the monitoring of six personal care products in micellar cosmetic samples, combining the µ-dSPE method with ultra-high performance liquid chromatography (UHPLC) coupled to ultraviolet/visible detection (UV/Vis). Univariate studies and a factorial design were performed in the optimization of the microextraction procedure. The compromise optimum extraction conditions included 20 mg of PS/DUT-67(Zr) for 10 mL of sample, 2 min of extraction time, and two desorption steps using 100 µL of acetonitrile and 5 min assisted by vortex in each one. The validated μ-dSPE-UHPLC-UV/Vis method presented limits of detection and quantification down to 3.00 and 10.0 μg·L⁻¹, respectively. The inter-day precision values were lower than 23.5 and 21.2% for concentration levels of 75 μg·L⁻¹ and 650 μg·L⁻¹, respectively. The hydrophobicity of the resulting PS/DUT-67(Zr) material was crucial for the improvement of its extraction capacity in comparison with its unitary components, showing the advantages of combining MOFs with other materials, getting new sorbents with interesting properties. Full article

Two environmentally friendly methodologies based on ultrasound-assisted extraction (UAE) and micro-matrix solid-phase dispersion (µMSPD) followed by gas chromatography-mass spectrometry (GC-MS) analysis are proposed for the first time for the simultaneous analysis of 17 glycols, glycol ethers, and their acetates in cosmetics. These sample preparation approaches result in efficient and low-cost extraction while employing small amounts of sample, with a low consumption of reagents and organic solvents. The use of a highly polar column allows for the direct analysis of the obtained extracts by GC-MS without a previous derivatization step, drastically reducing the sample preparation time and residues and thus complying with green analytical chemistry (GAC) principles. Both the UAE and µMSPD methodologies were validated in terms of linearity, accuracy, and precision, providing satisfactory results. LODs were found to be lower than 0.75 µg g⁻¹, allowing the determination of trace levels of the forbidden target compounds. Finally, the validated methodologies were applied to real cosmetics and personal care products, showing suitability, and providing a reliable and useful tool for cosmetics control laboratories. Full article

In the present study, acetaminophen (ACT) molecularly imprinted polymer (ACT-MIP) were successfully synthesized via surface imprinting polymerization. The structural and morphological properties of ACT-MIP were characterized using various analytical techniques. ACT-MIP were used as an adsorbent in a vortex-assisted dispersive molecularly imprinted solid-phase micro-extraction (VA-d-μ-MISPE), coupled with a high-performance liquid chromatography–diode array detector (HPLC-DAD) method for the determination of ACT in water samples. Influential parameters such as the mass of adsorbent, vortex speed, extraction time, desorption volume, and desorption time were optimized using a multivariate approach. Under optimum conditions, the maximum binding capacities of ACT-MIP and NIP (non-imprinted polymers) were 191 mg/g and 71.5 mg/g, respectively. The linearity was attained across concentrations ranging from 0.630 to 500 µg/L, with a coefficient of determination of 0.9959. For ACT-MIP, the limit of detection (LOD) and limit of quantification (LOQ), enhancement factor, and precision of the method were 0.19 ng/L, 0.63 ng/L, 79, and <5%, respectively. The method was applied in the analysis of spiked water samples, and satisfactory percentage recoveries in the range of 95.3–99.8% were obtained. Full article

The review describes the development of batch solid phase extraction procedures based on dispersive (micro)solid phase extraction with molecularly imprinted polymers (MIPs) and magnetic MIPs (MMIPs). Advantages and disadvantages of the various MIPs for dispersive solid phase extraction and dispersive (micro)solid phase extraction are discussed. In addition, an effort has also been made to condense the information regarding MMIPs since there are a great variety of supports (magnetite and magnetite composites with carbon nanotubes, graphene oxide, or organic metal framework) and magnetite surface functionalization mechanisms for enhancing MIP synthesis, including reversible addition-fragmentation chain-transfer (RAFT) polymerization. Finally, drawbacks and future prospects for improving molecularly imprinted (micro)solid phase extraction (MIMSPE) are also appraised. Full article