Miniaturized Solid-phase Extraction Research Articles

Solid-phase extraction coupled to automated centrifugal microfluidics SERS: Improving quantification of therapeutic drugs in human serum

Surface-enhanced Raman spectroscopy (SERS) is a powerful method in analytical chemistry, but its application in real-life medical settings has been limited due to technical challenges. In this work, we introduce an innovative approach that is meant to advance the automation of microfluidics SERS to improve reproducibility and label-free quantification of two widely used therapeutic drugs, methotrexate (MTX) and lamotrigine (LTG), in human serum. Our methodology involves a miniaturized solid-phase extraction (μ-SPE) method coupled to a centrifugal microfluidics disc with incorporated SERS substrates (CD-SERS). The CD-SERS platform enables simultaneous controlled sample wetting and accurate SERS mapping. Together with the assay we implemented a machine learning method based on Partial Least Squares Regression (PLSR) for robust data analysis and drug quantification. The results indicate that combining μ-SPE with CD-SERS (μ-SPE to CD-SERS) led to a substantial improvement in the signal-to-noise ratio compared to combining CD-SERS with ultrafiltration or protein precipitation. The PLSR model enabled us to obtain the limit of detection and quantification for MTX as 2.90 and 8.92 μM, respectively, and for LTG as 10.76 and 32.29 μM. We also validated our μ-SPE to CD-SERS method for MTX against HPLC and immunoassay (p-value <0.05), using patient samples undergoing MTX therapy. In addition, we achieved a satisfactory recovery rate (80%) for LTG when quantifying it in patient samples. Our results show the potential of this newly developed approach as a strategy for therapeutic drugs in point-of-care clinical settings and highlight the benefits of automating label-free SERS assays.

Simultaneous Determination of 23 Pyrrolizidine and Tropane Alkaloids in Infusions from Dry Edible Flowers Using Optimized μSPEed® Microextraction Prior to Their Analysis by UHPLC-IT-MS/MS.

A miniaturized solid-phase extraction of two tropane alkaloids (TAs) and twenty-one pyrrolizidine alkaloids (PAs) from infusions of dry edible flowers using optimized µSPEed® technique was developed. The optimization of the µSPEed® methodology involved testing different cartridges and comparing various volumes and numbers of loading cycles. The final conditions allowed for a rapid extraction, taking only 3.5 min. This was achieved using a C18-ODS cartridge, conditioning with 100 µL of methanol (two cycles), loading 100 µL of the infusion sample (seven cycles), and eluting the analytes with 100 µL of methanol (two cycles). Prior to their analysis by UHPLC-IT-MS/MS, the extracts were evaporated and reconstituted in 100 µL of water (0.2% formic acid)/methanol (0.2% ammonia) 95:5 (v/v), allowing for a preconcentration factor of seven times. The methodology was successfully validated obtaining recoveries ranging between 87 and 97%, RSD of less than 12%, and MQL between 0.09 and 0.2 µg/L. The validated methodology was applied to twenty samples of edible flower infusions to evaluate the safety of these products. Two infusion samples obtained from Acmella oleracea and Viola tricolor were contaminated with 0.16 and 0.2 µg/L of scopolamine (TA), respectively, while the infusion of Citrus aurantium was contaminated with intermedine and lycopsamine (PAs) below the MQL.

Mechanochemical synthesis ionic covalent organic frameworks/cotton composites for pipette tip solid-phase extraction of domoic acid in seafood

Pipette tip solid-phase extraction (PT-SPE) as a miniaturized solid-phase extraction technique have a wide range of applications in the field of sample pretreatment. In this study, ionic covalent organic frameworks@cotton (iCOF@cotton) were facilely synthesized by mechanochemical grinding method only in half an hour, and used as the adsorbents of PT-SPE. The synthesized iCOF@cotton not only had high specific surface area, suitable pore structure and cationic charge groups of iCOF that can extract polar targets quickly, but also reduced the problem of high back pressure of PT-SPE by the addition of cotton, thus accelerating extraction time. Combined with high performance liquid chromatographic tandem mass spectrometry (HPLC-MS/MS), an efficient and sensitive method was established for detection of domoic acid (DA, a toxin produced by algae). Under the optimal conditions, the proposed analysis method displayed excellent analytical performance, including broad range of linearity (10–1000 pg mL−1), low limit of detection (LOD, 5 pg mL−1), high correlation coefficient (0.9993), satisfactory precision (RSDs ≤6.4 %). In addition, the developed method was applied to the detection of DA in marine samples, and detected trace DA (18.6 pg mL−1) with satisfactory recovery (85.7%–107.2 %). The above results indicated that the prepared iCOF@cotton have great potential as the adsorbents for PT-SPE.

Carbon black-assisted miniaturized solid-phase extraction of carbamate residues from ginger by supercritical fluid chromatography combined with ion mobility quadrupole time-of-flight mass spectrometry

In this study, the qualitative and quantitative analysis of carbamate pesticide residues was achieved by a miniaturized solid phase extraction (SPE) method and supercritical fluid chromatography (SFC) combined with ion mobility quadrupole time-of-flight mass spectrometry (IM-Q-TOF/MS). The target compounds in real samples were enriched using the miniaturized SPE method, and the parameters affecting enrichment efficiency were evaluated with the optimal enrichment conditions as follows: carbon black (20 mg) and methanol used as the elution solvent with a volume of 200 µL. Meanwhile, the back temperature, back pressure and make-up solvent in SFC were investigated, and the corresponding optimal conditions were 60 °C, 140 bar and methanol with 0.1% formic acid, respectively. Subsequently, accurate mass values of nine carbamate pesticides were identified by IM-Q-TOF/MS. Through method validation and sample analysis, the results indicated that satisfactory validation parameters, such as linearity (R2 > 0.99), limit of detection (<7.01 ng/mL), limit of quantitation (<23.36 ng/mL), precision (0.21–3.91%) and reproducibility (0.08–4.76%), were obtained. Finally, this method was successfully applied to the enrichment and detection of carbamate residues in real samples of ginger.

Determination of amphetamines, opioids, cocaine metabolites and 11-nor-9-carboxy-Δ9-tetrahydrocannabinol in urine using biocompatible solid-phase microextraction and ultra-performance LC-MS/MS.

Background: Workplace drug testing primarily relies on urine analysis, targeting multiple compounds with varying physicochemical characteristics. Biocompatible solid-phase microextraction (BioSPME) is a miniaturized solid-phase extraction technique that enables the simultaneous extraction and preconcentration of analytes directly from the biological matrix. Methods: The BioSPME procedure consisted of the sequential extraction of 50-μl urine samples using LC Tips C18 in basic and acidic pH, followed by desorption with methanol and n-hexane, respectively. The extracts were analyzed by ultra-performance LC-MS/MS. Results: Intra-day precision was 1.2-8.6% and inter-day precision was 1.8-14.2%. Accuracy was 96.8-107.4%. The extraction yields were 62.8-109.4%. The matrix effects were -3.98% to 1%. Conclusion: BioSPME shows promise as an alternative method for preparing urine samples prior to drug measurement by ultra-performance LC-MS/MS.

Multivariate Simultaneous Determination of Some PAHs in Persian Gulf Oil-Contaminated Algae and Water Samples Using Miniaturized Triton X-100-Mediated Fe3O4 Nanoadsorbent and UV-Vis Detection

This research shows the development of a miniaturized solid-phase extraction method with UV-Vis detection for simultaneous determination of dibenzofuran, fluoranthene and phenanthrene using chemometrics approaches. After synthesis of Fe3O4 nanoparticles (Fe3O4 NPs), the surface of the nanoparticles was modified by Triton X100 coating. The influence of extraction solvent and volume, concentration of Triton X100, extraction time, and sample pH were studied and optimized. Due to high spectral overlapping, resolving ternary mixtures for simultaneous determination of targets with classical analytical methods is impossible. Therefore, the recorded UV-Vis spectra were transformed using continuous wavelet transform and then subjected to artificial neural networks (ANNs). The Db4 mother wavelet was used as the better mother wavelet. For simultaneous detection of analytes, a comparison of feed-forward back-propagation and radial basis function networks was accomplished. The calibration graphs showed linearity in the ranges of 2.4–250 ng mL−1, 50–3750 ng mL−1, and 48–5000 ng mL−1 with a limit of detection of 0.58, 9.5 ng mL−1, and 12.5 ng mL−1 under optimal conditions for phenanthrene, fluoranthene, and dibenzofuran, respectively. The limit of quantitation was achieved at 3.52 ng mL−1, 16.35 ng mL−1, and 31.3 ng mL−1 for phenanthrene, fluoranthene and dibenzofuran, respectively. The method involving TX-100-coated Fe3O4 NPs in a liquid sample phase for analyte extraction, followed by ethanol desorption and UV-Vis detection, was successfully applied for the determination of polycyclic aromatic hydrocarbons in oil-field water and algae samples.

Bioactive Compounds and Antioxidant Activity from Spent Coffee Grounds as a Powerful Approach for Its Valorization.

Coffee is one of the world's most popular beverages, and its consumption generates copious amounts of waste. The most relevant by-product of the coffee industry is the spent coffee grounds, with 6 million tons being produced worldwide per year. Although generally treated as waste, spent coffee grounds are a rich source of several bioactive compounds with applications in diverse industrial fields. The present work aimed at the analysis of spent coffee grounds from different geographical origins (Guatemala, Colombia, Brazil, Timor, and Ethiopia) for the identification of bioactive compounds with industrial interest. For this purpose, the identification and quantification of the bioactive compounds responsible for the antioxidant activity attributed to the spent coffee grounds were attempted using miniaturized solid-phase extraction (µ-SPEed), combined with ultrahigh-performance liquid chromatography with photodiode array detection (UHPLC-PDA). After validation of the µ-SPEed/UHPLC-PDA method, this allowed us to conclude that caffeine and 5-caffeoylquinic acid (5-CQA) are the most abundant bioactive compounds in all samples studied. The total phenolic content (TPC) and antioxidant activity are highest in Brazilian samples. The results obtained show that spent coffee grounds are a rich source of bioactive compounds, supporting its bioprospection based on the circular economy concept closing the loop of the coffee value chain, toward the valorization of coffee by-products.

Application of pipette-tip solid-phase extraction technique for fast determination of levofloxacin from wastewater sample using cobalt metal-organic framework

In this research, a miniaturized solid-phase extraction method based on pipette tip solid-phase extraction (PT-SPE) was employed for the determination of levofloxacin. Cobalt metal-organic framework (CoMOF) was used as an adsorbent. Levofloxacin was determined using high-performance liquid chromatography and UV detection (HPLC-UV). Important parameters that influence the extraction efficiency (i.e. pH, amount of adsorbent, extraction time, volumes of sample, and eluting solvent) were tested and optimized. Results indicated that the proposed method was validated over the range of 0.70 - 150.0 µg L-1. The relative standard deviation (RSD%) was below 2.75% for the levofloxacin. The limit of detection (LOD) of this method is 0.041 µg L-1. The preconcentration factor (PF) was obtained at 200 and the analysis time was around 10 min that confirming the reliability and accuracy of this method for extraction of levofloxacin. The PT-SPE procedure based on CoMOF adsorbent was efficiently extracted for levofloxacin more than 95%. In a static system, the adsorption capacity of CoMOF adsorbent for levofloxacin was obtained at 156.7 mg g-1 (n=10). The validation of results was successfully obtained for levofloxacin values based on the spiking real samples before determination by the HPLC technique.

Application of a novel nylon needle filter-based solid-phase extraction device to determination of 1-hydroxypyrene in urine.

In this work, a simple and miniaturized solid-phase extraction device was constructed by connecting a commercial nylon needle filter to a syringe, which was applied for extracting 1-hydroxypyrene from a urine sample via hydrophobic and hydrogen bond interactions. The nylon membrane in the needle filter acted as the solid-phase extraction adsorbent, meanwhile, it filtered the particles in the urine sample. To obtain high extraction efficiency, key parameters influencing extraction recovery were investigated. The entire pretreatment process was accomplished within 5min under the optimal conditions. By coupling high-performance liquid chromatography-ultraviolet, a rapid, low-cost, and convenient nylon needle filter-based method was established for the analysis of 1-hydroxypyrene in a complex urine matrix. Within the linearity range of 0.2-1000 μg/L, the method exhibited a satisfactory correlation coefficient (R=0.9999). The limit of detection was 0.06 μg/L, and the recoveries from urine sample spiked with three concentrations (5, 20, and 100 μg/L) ranged from 105.8% to 113.1% with the relative standard deviations less than 6.7% (intra-day, n=6) and 8.9% (inter-day, n=4). Finally, the proposed method was successfully applied for detecting 1-hydroxypyrene in urine samples from college students, smokers, gas station workers, and chip factory workers. The detected concentration in actual urine samples ranged from 0.46 to 5.26 μg/L. Taken together, this simple and cost-effective nylon needle filter-based solid-phase extraction device showed an excellent application potential for pretreating hydrophobic analytes from aqueous samples.

Development of a magnetic MOF-based M-D-μSPE methodology combined with LC-MS/MS for the determination of fluorotelomer alcohols and its metabolites in animal derived foods

In this study, a novel modified metal organic framework (MOF) was prepared and used as adsorbent of miniaturized solid-phase extraction (M-D-μSPE) for analyzing 8–2 FTOH and its metabolites in edible tissues by LC-MS/MS. This synthesized adsorbent, named as Fe3O4@Fe-MIL 101-NH2 (magnetic Fe-MOF), was characterized. Moreover, the effects factors on the adsorption behavior of the adsorbents for the analytes were investigated and optimized in detail, such as solution pH, adsorbent amount, extraction time, desorption condition. The adsorbtion mechanism of magnetic Fe-MOF might be electrostatic interaction, CF-π hydrophobic and Lewis acid base. Compared with conventional adsorbents (such as PSA, C18), magnetic Fe-MOF reduced matrix effect. The limits of quantification ranged 0.10–1.5 µg/kg. The recoveries of analytes ranged 78.0% − 90.3% in spiked samples, with relative standard deviations less than 12.0%. The developed method was successfully utilized to analyze incurred samples, which proves that it is a rapid, efficient, and sensitive method.

Polypyrrole monolithic extraction phase: From conventional to miniaturized sample preparation techniques

Monolithic polymers are described as continuous and highly porous materials. They have been gaining popularity as an effective extracting phase for some sample preparation methods, due to their variety of functionalities, such as wide pH range tolerance, good permeability, and its ability to allow changes into their surface. Polypyrrole represents an interesting alternative for the modification in extraction phases due to its well related ability to perform multiple interactions, such as acid-base, π - π, ion exchange, interactions with hydrophobic affinities or polar functional groups. Among the different sample preparation techniques, solid-phase extraction (SPE) is one of the most popular and used; a miniaturized version of SPE is the disposable pipette extraction (DPX). DPX is a recent miniaturized extraction technique that usually employing silica-based sorbents inside a pipette tip (5 or 1 mL). The present study proposes the development of a monolithic extraction phase composed by styrene divinylbenzene (1:1) modified with polypyrrole for SPE and DPX techniques. The efficiency of the material was evaluated in face of the extraction of different samples and analytes, triazine herbicides in water and dexamethasone in synthetic synovial liquid by conventional and miniaturized solid-phase extraction techniques. The extractions performed by SPE and DPX presented absolute recovery values ranging from 74.8 to 105.0%, inter-day precision ranging from 0.6 to 14.0%, and limit of quantification of 0.5 and 5.0 ng.mL−1, respectively. The DPX miniaturized method exhibited results equivalent to the methods reported in the literature for extraction of dexamethasone in synovial fluid samples. Moreover, this technique proved to be quicker and cheaper than SPE, and produced fewer residual volumes, supporting the preference for green chemistry. Monolithic polymers modified with polypyrrole presented to be a feasible alternative extraction phase for miniaturized sample preparation techniques.

RAFT Method for Preparation of Molecularly Imprinted Polymer–SBA15 Nanocomposite as a Pipette Tip Solid-Phase Microextraction Adsorbent

Methoxyfenozide-selective surface molecularly imprinted polymer (MIP) sorbent was synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization based on support matrix of SBA-15. The size, morphology, composition, and properties of the prepared nanocomposite have also been characterized and determined using scanning electron microscopy (SEM) and Fourier-transform- infrared (FT-IR) spectroscopy. A miniaturized solid-phase extraction procedure has been developed for ultra-trace determination of methoxyfenozide adsorbed on polymethacrylic acid-functionalized Santa Barbara Amorphous type material (SBA-15), which is packed into a pipette- tip (PT). The PT-SPE was assembled by packing 2.0 mg of nanocomposite of MIP as sorbent into a 100 μL pipette tip. The method was optimized for several important extraction parameters such as sample volume, pH, amount of sorbent, and eluent solvent. The results determine that the prepared adsorbent has a high extraction power. High sensitivity, non-use of organic solvent, high selectivity, and low detection limits are the unique advantages of the proposed method.

Miniaturized solid-phase extraction using a mesoporous molecular sieve SBA-15 as sorbent for the determination of triterpenoid saponins from Pulsatilla chinensis by ultrahigh-performance liquid chromatography-charged aerosol detection

A simple, sensitive and efficient solid-phase extraction method, combined with ultrahigh-performance liquid chromatography-charged aerosol detection, was applied to the pre-concentration and determination of four triterpenoid saponins from Pulsatilla chinensis (P. chinensis) ultrasound extract samples. Mesoporous molecular sieve Santa Barbara Amorphous 15 (SBA-15) displayed higher selectivity compared to Mobil Composition of Matter 41 (MCM-41), NH2-SBA-15 and mesoporous carbon when it comes to being used in pretreatment methods. It was applied as an effective sorbent in the SPE for the enrichment of the target analytes. Additionally, several key experimental parameters including the kinds of sorbents, the amount of SBA-15, the elute pH and types of elution solvent were investigated in detail. Under the optimized conditions, the satisfactory linearity (r2 ≥ 0.9940) was acquired and the limits of detection reached 0.461−0.976 μg/mL for the target analytes. The recoveries ranged from 95.1%–103.2%. The experimental results showed that SBA-15 was a candidate material for the purification and concentration of target triterpenoid saponins from complex P. chinensis samples. The study provided theoretical support for the application of mesoporous materials in the field of drug separation and provided references for the extraction and determination of trace compounds in the complex systems of traditional Chinese medicine.

Oxidized carbon nanotubes as sorbent for miniaturized solid-phase extraction of progestins from environmental water samples prior to their determination by HPLC-UV.

A solid-phase extraction method is presented for micro-extraction of three progestins (levonorgestrel, 19-norethisterone acetate and medroxyprogesterone acetate) from water samples. A mini-column was packed with 60mg of oxidized multiwalled carbon nanotubes and coupled to a flow injection assembly. The extraction parameters, such as washing solution, eluent type, eluent volume, flow rate and sample volume, were optimized. Separation and determination were performed by HPLC with UV detection. The method has a good linear range (0.90-9.0μgL-1), acceptable limits of detection (0.05-0.14μgL-1) and low RSDs (0.8-4.6%). Attractive features of the method include low consumption of organic solvents and preconcentration factors of up to 100. The method was applied to analyze stream, underground and effluent water samples, and recoveries between 74 and 121% were obtained. Graphical abstractSchematic representation of the flow injection assembly couples to an ox-MWCNTs extraction column used to perform the solid phase extraction procedure of progestins in environmental water samples.

Core-shell microparticles formed by the metal-organic framework CIM-80(Al) (Silica@CIM-80(Al)) as sorbent material in miniaturized dispersive solid-phase extraction

Core-shell SiO2@CIM-80(Al) microspheres were synthesized, characterized, and used as novel sorbent in a dispersive miniaturized solid-phase extraction (D-μSPE) method for the determination of fourteen polycyclic aromatic hydrocarbons (PAHs) in wastewaters by ultra-high performance liquid chromatography coupled to a fluorescence detector (UHPLC-FD). A Doehlert experimental design permitted to optimize the main parameters affecting the microextraction procedure, intending the obtaining of a simple approach. Optimized extraction conditions include 13 mg of SiO2@CIM-80(Al) microparticles (~2 mg CIM-80(Al)), 2.5 min of extraction time, 0.125 mL of acetonitrile (ACN) as desorption solvent and 0.5 min of desorption time. The entire method showed adequate analytical performance with limits of detection down to 5 ng L−1, and inter-day precision lower than 14.1% for a concentration level of 0.5 μg L−1. The extraction capability of SiO2@CIM-80(Al) microspheres was compared to that obtained with commercially available silica microspheres and the neat MOF CIM-80(Al), demonstrating the advantages of the use of MOF core-shell sorbents in D-μSPE.

Mixed Functionalization of Organic Ligands in UiO-66: A Tool to Design Metal-Organic Frameworks for Tailored Microextraction.

The mixed-ligand strategy was selected as an approach to tailor a metal–organic framework (MOF) with microextraction purposes. The strategy led to the synthesis of up to twelve UiO-66-based MOFs with different amounts of functionalized terephthalate ligands (H-bdc), including nitro (-NO2) and amino (-NH2) groups (NO2-bdc and NH2-bdc, respectively). Increases of 25% in ligands were used in each case, and different pore environments were thus obtained in the resulting crystals. Characterization of MOFs includes powder X-ray diffraction, infrared spectroscopy, and elemental analysis. The obtained MOFs with different degrees and natures of functionalization were tested as sorbents in a dispersive miniaturized solid-phase extraction (D-µSPE) method in combination with high-performance liquid chromatography (HPLC) and diode array detection (DAD), to evaluate the influence of mixed functionalization of the MOF on the analytical performance of the entire microextraction method. Eight organic pollutants of different natures were studied, using a concentration level of 5 µg· L−1 to mimic contaminated waters. Target pollutants included carbamazepine, 4-cumylphenol, benzophenone-3, 4-tert-octylphenol, 4-octylphenol, chrysene, indeno(1,2,3-cd)pyrene, and triclosan, as representatives of drugs, phenols, polycyclic aromatic hydrocarbons, and disinfectants. Structurally, they differ in size and some of them present polar groups able to form H-bond interactions, either as donors (-NH2) or acceptors (-NO2), permitting us to evaluate possible interactions between MOF pore functionalities and analytes’ groups. As a result, extraction efficiencies can reach values of up to 60%, despite employing a microextraction approach, with four main trends of behavior being observed, depending on the analyte and the MOF.

Metal–Organic Frameworks in Solid-Phase Extraction Procedures for Environmental and Food Analyses

Environmental and food analysis usually require the use of sample preparation steps, with significant utilization of solid-phase extraction techniques. This review article covers recent trends in the use of metal–organic frameworks (MOFs) as novel sorbents, with particular emphasize on miniaturized methods to follow green analytical chemistry principles. Thus, the use of MOFs in miniaturized solid-phase extraction (µSPE), performed in static off-line and on-line modes, and solid-phase microextraction (SPME), including the on-line procedures of in-tube and on-disk approaches, will be described with particular emphasis on the specific applications.

Application of a Pillared-Layer Zn-Triazolate Metal-Organic Framework in the Dispersive Miniaturized Solid-Phase Extraction of Personal Care Products from Wastewater Samples.

The pillared-layer Zn-triazolate metal-organic framework (CIM-81) was synthesized, characterized, and used for the first time as a sorbent in a dispersive micro-solid phase extraction method. The method involves the determination of a variety of personal care products in wastewaters, including four preservatives, four UV-filters, and one disinfectant, in combination with ultra-high performance liquid chromatography and UV detection. The CIM-81 MOF, constructed with an interesting mixed-ligand synthetic strategy, demonstrated a better extraction performance than other widely used MOFs in D-µSPE such as UiO-66, HKUST-1, and MIL-53(Al). The optimization of the method included a screening design followed by a Doehlert design. Optimum conditions required 10 mg of CIM-81 MOF in 10 mL of the aqueous sample at a pH of 5, 1 min of agitation by vortex and 3 min of centrifugation in the extraction step; and 1.2 mL of methanol and 4 min of vortex in the desorption step, followed by filtration, evaporation and reconstitution with 100 µL of the initial chromatographic mobile phase. The entire D-µSPE-UHPLC-UV method presented limits of detection down to 0.5 ng·mL−1; intra-day and inter-day precision values for the lowest concentration level (15 ng·mL−1)-as a relative standard deviation (in %)-lower than 8.7 and 13%, respectively; average relative recovery values of 115%; and enrichment factors ranging from ~3.6 to ~34. The reuse of the CIM-81 material was assessed not only in terms of maintaining the analytical performance but also in terms of its crystalline stability.

Nanostructured polyaniline based pipette tip solid phase extraction coupled with high-performance liquid chromatography for the selective determination of trace levels of three sulfonamides in honey and milk samples with the aid of experimental design methodology

In this study, a miniaturized solid-phase extraction based on 2-(hexyloxy) naphthalene-sulfate doped polyaniline polymer as a new nanostructured sorbent packed into a 200 μL pipette tip (PT-SPE) as a rapid and efficient method was developed for the simultaneous and selective extraction of three sulfonamide (SAs) antibiotics in aqueous solution. The resultant polymer was well characterized by FT-IR, UV–Vis., FESEM, EDX and XRD. In this strategy, the pipette tip containing the sorbent was matched to a syringe and the sample solution was loaded onto the sorbent using a microsyringe pump. The eluate was analyzed with high performance liquid chromatography using UV–Vis. spectrometry detection (HPLC/UV–Vis). In preliminary experiments, sample pH, sorbent dosage, sample volume and eluent volume were identified as critical variables affecting the solid phase micro-extraction of SAs by the developed sorbent. The response surface methodology (RSM) based on a rotatable central composite design (CCD) was employed for modeling the chromatographic peak areas of SAs as responses and optimized the effective extraction variables. This method is cost-effective because only 7.4 mg sorbent amount and 0.6 mL methanol as eluent were required for the extraction of analytes. The multiple response criteria were used to optimize simultaneous responses of the analytes using the desirability function. Under the optimal conditions, a good linear relationship between the peak areas and concentrations of the SAs was found in the range of 50–50,000 ng mL−1 with correlation coefficients above 0.999. The developed method was successfully applied to the analysis of SAs in milk, and honey samples.

A miniaturized solid-phase extraction adsorbent of calix[4]arene-functionalized graphene oxide/polydopamine-coated cellulose acetate for the analysis of aflatoxins in corn.

A calix[4]arene-functionalized graphene oxide/polydopamine-coated cellulose acetate adsorbent was fabricated for the pre-concentration of aflatoxins. The highly porous developed adsorbent does not produce the high backpressure that normally occurs in particle-packed cartridges and its large surface area helps to improve adsorption. The highly efficient adsorption of aflatoxins by the hybrid adsorbent is facilitated via hydrogen bonding and hydrophobic and π-π interactions. Polymerization time, amount of calix[4]arene-functionalized graphene oxide, type and volume of desorption solvent, sample pH, sample volume, and sample flow rate were optimized. The linearity of aflatoxin B1 was in the range of 0.01-10.0 μg/kg, aflatoxin B2 was in the range of 0.02-10.0μg/kg and aflatoxin G1 and aflatoxin G2 were in the range of 0.050-10.0μg/kg. The limits of detection were 0.01μg/kg for aflatoxin B1, 0.02μg/kg for aflatoxin B2and 0.05μg/kg for aflatoxin G1 and aflatoxin G2. The developed calix[4]arene-functionalized graphene oxide/polydopamine-coated cellulose acetate adsorbent was successfully utilized for the analysis of aflatoxins from corn samples and the extraction efficiency was satisfactory with obtained recoveries from 83.0 to 106.7%. Moreover, fabricated adsorbent is easy to prepare, inexpensive, and can be reused.