Search Results (34)

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

Doce de leite is a caramel-like confection, mainly produced in several Latin American countries, with increasing popularity worldwide. This overview outlines nine distinct industrial technologies for the production of doce de leite: (1) total batch manufacturing process; (2) batch manufacturing system with fractionated mix addition; (3) manufacturing with pre-concentration in a vacuum evaporator and finishing in an open pan; (4) manufacturing with pre-concentration in a vacuum evaporator, finishing in an open pan, and lactose micro-crystallization; (5) continuous flow manufacturing with total concentration in a vacuum evaporator and a viscosity control holding tank (hot well); (6) manufacturing with total concentration in a vacuum evaporator and sterilization in an autoclave system; (7) manufacturing with sucrose pre-caramelization and a total batch system; (8) manufacturing in colloidal mill without an evaporation process; and (9) manufacturing based of doce de leite bars with a sucrose crystallization stage. We conducted a literature review to gather data on the discussed processes and their principal characteristics, which may be pertinent to doce de leite manufacturers. The choice of a specific process will depend on the desired doce de leite characteristics, the type of doce de leite to be produced, and the manufacturing company’s requirements. When properly integrated, these technologies contribute to efficient and profitable production, yielding high-quality products with appropriate chemical, microbiological, and sensory characteristics at an industrial scale. Full article

A method to determine aceclofenac, ketorolac, and sulindac in human urine samples using microemulsion electrokinetic chromatography (MEEKC) has been developed in this study. The optimization of MEEKC conditions was carried out by changing the microemulsion compositions including the buffer pH, borate salt concentration, surfactant concentration, co-surfactant concentration, organic modifier concentration, and oil droplet concentration. The optimum separation of selected drugs was obtained with a composition of microemulsion containing 10 mM borate buffer pH 9, 0.5% sodium dodecyl sulphate (SDS), 6.6% n-butanol, 6.0% acetonitrile, and 0.8% ethyl acetate. Excellent linearity was obtained in the range concentration of 25 to 200 ppm with r² > 0.999. Limits of detection (LOD, S/N = 3) and limits of quantification (LOQ, S/N = 10) were 2.72 to 4.75 and 9.08 to 15.85 ppm, respectively. The solid-phase extraction (SPE) method using C-18 as an adsorbent and the solid phase micro-tip extraction (SPMTE) method using multiwalled carbon nanotubes (MWCNTs) as an adsorbent were used to clean-up and pre-concentrate the urine samples prior to the MEEKC analysis. The best recoveries of the selected drugs in the spiked urine sample were 91 to 103% with RSD of 1.26 to 4.03% (n = 3) using the SPE-MEEKC method. Full article

This study aims to apply the ionic liquid-based solidified floating organic drop micro-extraction (IL-SFODME) technique to improve the preconcentration of trace mercury levels, serving as a preparatory step for analysis via graphite furnace atomic absorption spectrometry (GFAAS) without using chelating agents. The process involves separating and preconcentrating mercury ions using IL-SFODME, followed by GFAAS analysis. This study systematically examined several factors affecting micro-extraction efficiency, including pH, the amount of ionic liquid 1-Hexyl-3-methylimidazolium hexafluorophosphate (HMIMPF6), extraction time, stirring rate, and temperature, to determine the optimal conditions. Under these optimized conditions, an enhancement factor of 171 was achieved for a 75 mL sample solution. The calibration curve was linear within the 0.5–10 µg/L range, with a detection limit (3σ) of 0.12 µg/L and a quantification limit (10σ) of 0.40 µg/L. The relative standard deviation (RSD) for 7 replicate measurements of 1 µg/L mercury was ±2.78%. The combination of the ionic liquid and SFODME methods without using a chelating agent is used for the first time for metal extraction. The method was successfully applied to extract and determine mercury in reference water samples and various real water samples, demonstrating notably satisfactory extraction efficiency. Full article

MicroRNAs (miRNAs) are short non-coding RNAs that are found in various cellular compartments and play an important role in regulating gene expression. Extracellular miRNAs, such as those found within extracellular vesicles such as exosomes are involved in cell-to-cell communication. The intercellular transfer of miRNAs has been implicated in various diseases’ pathogenesis including cancer and has been studied extensively as potential cancer biomarkers. However, the extraction of miRNA from exosomes is still a challenging task. The current nucleic acid extraction assays are expensive and labor-intensive. In this study, we demonstrated a microfluidic device for aptamer-based magnetic separation of the exosomes and subsequent detection of the miRNA using a fluorescence switching assay, which was enabled by carbon nanomaterials coated on magnetic beads. In the OFF state, the fluorophore-labelled cDNA is quenched using carbon nanomaterials. However, when the target miRNA210 is introduced, the cDNA detaches from the bead’s surface, which leads to an increase in the fluorescence intensity (ON state). This increment was found to be proportional to miRNA concentration within the dynamic range of 0–100 nM with a detection limit of 5 pM. The assay was validated with spiked miRNA using the standard RT-PCR method. No notable cross-reactivity with other closely related miRNAs was observed. The developed method can be utilized for the minimally invasive detection of cancer biomarkers. 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

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

For years, researchers have focused on the determination of metal ions at trace levels in environmental and food samples using analytical methods that employ techniques with low cost acquisition and maintenance and without microwave-assisted acid digestion procedures or aggressive reagents. Therefore, the present study deals with the synthesis and application of a novel, restricted-access poly(protoporphyrin-co-vinyl pyridine) adsorbent to preconcentrate copper in water samples and bovine milk that have only been subjected to pH adjusting (pH 6.0) and filtration using posterior on-line determination by FAAS. Regarding macromolecules, the restricted-access property of the adsorbent was achieved using the hydrophilic compound 2-hydroxyethyl methacrylate (HEMA). This method is based on the preconcentration of Cu²⁺ ions using a flow-injection system which is buffered with 0.05 mol L⁻¹ of Britton–Robinson (BR) at a pH of 6.0 and has a flow rate of 14.0 mL min⁻¹ through a mini-column packed with 50.0 mg of adsorbent. The elution was carried out using 0.40 mol L⁻¹ of HCl toward the FAAS detector. The developed method provided a preconcentration factor of 44.7-fold, low limits of detection (LOD) (0.90 µg L⁻¹) and quantification (LOQ) (2.90 µg L⁻¹), tolerance to interfering ions (95.0 and 103.0%), and intra-day and inter-day precision assessed as the RSD (percentage of relative standard deviation), which ranged from 3.08 to 4.80%. The restricted-access poly(protoporphyrin-co-vinyl pyridine) adsorbent demonstrated outstanding features to exclude macromolecules, bovine serum albumin (BSA), and humic acid (HA) from an aqueous medium. Lake water and bovine milk samples were analyzed by the proposed preconcentration method with minimal sample pretreatment (which was based mainly on pH adjusting and filtration using an analytical curve with external calibration), yielding recovery values from addition and recovery tests ranging from 91.7 to 101.9%. The developed method shows great advantages over previously published methods, avoiding the time-consuming use of concentrated acids in a microwave-assisted acid digestion procedure. Full article

Due to its important environmental role, the analysis of trace metals in natural waters is attracting increasing attention; consequently, faster and more accurate analytical methods are now needed to reach even lower limits of detection. In this work, we propose the use of electro-membrane extraction (EME) to improve analytical methods based on hollow fiber liquid phase micro-extraction (HFLPME). Specifically, an EME-based method for the determination of trace Ni in seawater has been developed, using an HFLPME system with di-2-ethylhexyl phosphoric acid (DEHPA) in kerosene as a chemical carrier, followed by instrumental determination by graphite furnace atomic absorption spectroscopy (GFAAS). Under optimum conditions, Ni was pre-concentrated 180 ± 17 times after 15 min, using sample pH = 5.5, the concentration of DEHPA 0.9 M in the liquid membranes, and 1.9 M HNO₃ in the acceptor solution, as well as an electric potential of 25 V with the sample being stirred at 500 rpm. When compared with other HFLPME systems for pre-concentration of trace Ni in seawater in the absence of electric potential, the enrichment factor was improved 2.2 times, while the time of extraction was reduced an 89%. The limit of detection of the new method was 23.3 ng L⁻¹, and both its applicability and accuracy were successfully evaluated by analyzing Ni concentration in a seawater-certified reference material (BCR-403), showing the reliability of EME for sample preparation in the determination of trace metals in marine water samples. Full article

In this paper, we propose the combined procedure of noble metal (NM) determination, including fire assay, acid digestion, and reversible dynamic sorptive preconcentration, followed by flow-injection ICP-MS. Reversible preconcentration of all NMs was carried out using micro-column packed new PVBC-VP sorbent and elution with a mixture of thiourea, potassium thiocyanate, and HCl, which recovers Pd, Ir, Pt, and Au by 95% and Ru, and Rh by 90%. The proposed procedure was approved using certified reference materials. Full article

This work studied the feasibility of using a novel microreactor based on torus geometry to carry out a sample pretreatment before its analysis by graphite furnace atomic absorption. The miniaturized retention of total arsenic was performed on the surface of a magnetic sorbent material consisting of 6 mg of magnetite (Fe₃O₄) confined in a very small space inside (20.1 µL) a polyacrylate device filling an internal lumen (inside space). Using this geometric design, a simulation theoretical study demonstrated a notable improvement in the analyte adsorption process on the solid extractant surface. Compared to single-layer geometries, the torus microreactor geometry brought on flow turbulence within the liquid along the curvatures inside the device channels, improving the efficiency of analyte–extractant contact and therefore leading to a high preconcentration factor. According to this design, the magnetic solid phase was held internally as a surface bed with the use of an 8 mm-diameter cylindric neodymium magnet, allowing the pass of a fixed volume of an arsenic aqueous standard solution. A preconcentration factor of up to 60 was found to reduce the typical “characteristic mass” (as sensitivity parameter) determined by direct measurement from 53.66 pg to 0.88 pg, showing an essential improvement in the arsenic signal sensitivity by absorption atomic spectrometry. This methodology emulates a miniaturized micro-solid-phase extraction system for flow-through water pretreatment samples in chemical analysis before coupling to techniques that employ reduced sample volumes, such as graphite furnace atomic absorption spectroscopy. Full article

Evaluation of the hydrophobic/hydrophilic interaction individually between the sorbent and target compounds in sample pretreatment is a big challenge. Herein, a smart titanium substrate with switchable surface wettability was fabricated and selected as the sorbent for the solution. The titanium wires and meshes were fabricated by simple hydrothermal etching and chemical modification so as to construct the superhydrophilic and superhydrophobic surfaces. The micro/nano hierarchical structures of the formed TiO₂ nanoparticles in situ on the surface of Ti substrates exhibited the switchable surface wettability. After UV irradiation for about 15.5 h, the superhydrophobic substrates became superhydrophilic. The morphologies and element composition of the wires were observed by SEM, EDS, and XRD, and their surface wettabilities were measured using the Ti mesh by contact angle goniometer. The pristine hydrophilic wire, the resulting superhydrophilic wire, superhydrophobic wire, and the UV-irradiated superhydrophilic wire were filled into a stainless tube as the sorbent instead of the sample loop of a six-port valve for on-line in-tube solid-phase microextraction. When employed in conjunction with HPLC, four kinds of wires were comparatively applied to extract six estrogens in water samples. The optimal conditions for the preconcentration and separation of target compounds were obtained with a sample volume of 60 mL, an injection rate of 2 mL/min, a desorption time of 2 min, and a mobile phase of acetonile/water (47/53, v/v). The results showed that both the superhydrophilic wire and UV-irradiated wire had the highest extraction efficiency for the polar compounds of estrogens with the enrichment factors in the range of 20–177, while the superhydrophobic wire exhibited the highest extraction efficiency for the non-polar compounds of five polycyclic aromatic hydrocarbons (PAHs). They demonstrated that extraction efficiency was mainly dependent on the surface wettability of the sorbent and the polarity of the target compounds, which was in accordance with the molecular theory of like dissolves like. Full article

The detection of chemicals is a fundamental issue of modern civilisation, however existing methods do not always achieve the desired sensitivity. Preconcentrators, which are devices that allow increasing the concentration of the intended analyte via e.g., adsorption/desorption, are one of the solutions for increasing the sensitivity of chemical detection. The increased detection sensitivity granted by preconcentration can be used to miniaturise detection instruments, granting them portability. The primary goal of this review is to report on and briefly explain the most relevant recent developments related to the design and applications of preconcentrators. The key design elements of preconcentrators and the emerging area of liquid-phase preconcentrators are briefly discussed, with the most significant applications of these devices being highlighted. Full article

In environments polluted by mercury vapors that are potentially harmful to human health, there is a need to perform rapid surveys in order to promptly identify the sources of emission. With this aim, in this work, a low cost, pocket-sized portable mercury measurement system, with a fast response signal is presented. It consists of a preconcentrator, able to adsorb and subsequently release the mercury vapour detected by a quartz crystal microbalance (QCM) sensor. The preconcentrator is based on an adsorbing layer of titania/gold nanoparticles (TiO₂NP/AuNPs), deposited on a micro-heater that acts as mercury thermal desorption. For the detection of the released mercury vapour, gold electrodes QCM (20 MHz) have been used. The experimental results, performed in simulated polluted mercury-vapour environments, showed a detection capability with a prompt response. In particular, frequency shifts (−118 Hz ± 2 Hz and −30 Hz ± 2 Hz) were detected at concentrations of 65 µg/m³ Hg⁰ and 30 µg/m³ Hg⁰, with sampling times of 60 min and 30 min, respectively. A system limit of detection (LOD) of 5 µg/m³ was evaluated for the 30 min sampling time. Full article

We report on the hyphenation of the modern flow techniques Lab-In-Syringe and Lab-On-Valve for automated sample preparation coupled online with high-performance liquid chromatography. Adopting the bead injection concept on the Lab-On-Valve platform, the on-demand, renewable, solid-phase extraction of five nonsteroidal anti-inflammatory drugs, namely ketoprofen, naproxen, flurbiprofen, diclofenac, and ibuprofen, was carried out as a proof-of-concept. In-syringe mixing of the sample with buffer and standards allowed straightforward pre-load sample modification for the preconcentration of large sample volumes. Packing of ca. 4.4 mg microSPE columns from Oasis HLB^® sorbent slurry was performed for each sample analysis using a simple microcolumn adapted to the Lab-On-Valve manifold to achieve low backpressure during loading. Eluted analytes were injected into online coupled HPLC with subsequent separation on a Symmetry C18 column in isocratic mode. The optimized method was highly reproducible, with RSD values of 3.2% to 7.6% on 20 µg L⁻¹ level. Linearity was confirmed up to 200 µg L⁻¹ and LOD values were between 0.06 and 1.98 µg L⁻¹. Recovery factors between 91 and 109% were obtained in the analysis of spiked surface water samples. Full article