Dummy Template Research Articles

Electrochemical molecularly imprinted polymer sensor for simple and fast analysis of tetrodotoxin in seafood

Tetrodotoxin (TTX) is a marine biotoxin whose biosynthesis is associated with the pufferfish. Its distribution is primarily focused in Asian and tropical marine areas. Currently, this group of toxins is classified as emerging in Europe, and its presence could be related to climate change. This incidence has prompted the European Union, with the European Food Safety Authority, to establish control and monitoring mechanisms for TTX in marine products in Europe. In this context, the development of analytical tools capable of ensuring the safety of food products, especially seafood and fish, is a crucial task. This study describes the development of a molecularly imprinted polymer (MIP) based electrochemical sensor for the analysis of TTX. The MIP was synthesized through the electropolymerization of a functional monomer, ortho-phenylenediamine in the presence of a dummy template, voglibose. The MIP sensor was constructed on a screen-printed gold electrode and characterized by cyclic voltammetry. Differential pulse voltammetry, using a redox probe ([Fe(CN)6]3-/4-), was used in the analysis protocol. The developed sensor exhibited a linear response between 5.0 μg mL−1 and 25.0 μg mL−1, with a limit of detection of 1.14 μg mL−1. Its high imprinting efficiency conferred outstanding selectivity towards TTX. The sensor's applicability was confirmed through recovery assays on spiked mussel samples, achieving recoveries of 81.0 %, 110.2 %, and 102.5 % for external standard addition at 30.0, 44.0, and 60.0 μg kg−1, respectively, with relative standard deviations below 15 %. These results are comparable to those obtained using Hydrophilic Interaction Liquid Chromatography coupled with Tandem Mass Spectrometry, a validated method carried out by the European Reference Laboratory for Marine Biotoxins. Thus, the MIP sensor represents a portable, simple, and fast tool with essential analytical functionalities for the sampling phase and pre-selection of laboratory samples for analysis.

Photopolymerization of Imprinted Polymer with Dummy Template for the Recognition of Hydroquinone in Aqueous Medium

This study' purposes are to synthesize molecularly imprinted polymer (MIP) with hydroxyethyl methacrylate (HEMA) and triethylene glycol dimethacrylate (TEGDMA) using p-xylene under ultraviolet curing at 405 nm for the recognition of hydroquinone (HQ) in aqueous medium. The template was extracted from the polymer with a mixture of methanol and acetic acid (9:1) by volume (v/v). The Fourier transform infrared (FTIR) spectrum of MIP (after wash) showed the absence of peak at the range of 840–860 cm−1, which represented the stretching outside the aromatic plane C–H at the para position (p-xylene). Field emission scanning electron microscope (FESEM) micrograph showed that the MIP had cavities compared to non-imprinted polymer (NIP). The MIP (MIP-Pxy) with ratio (monomer:crosslinker) 0.25 and 1.00% template gave the highest uptake of hydroquinone (HQ) in aqueous solution, which implied more specific recognition (highest KD value). The rebinding of HQ onto MIP-Pxy was best described by both isotherm (Langmuir and Freundlich) and kinetic model (pseudo-first and -second). The MIP was successfully synthesized using p-xylene, able to recognize HQ and was very selective to p-CP. Implication of the study, the synthesized MIP can be used for recognition and sensing materials for HQ and any similar molecules.

Computer simulation‐guided template selection for a molecularly imprinted polymer for selective trifluralin adsorption

AbstractTo meet selective adsorption toward trifluralin, a novel molecularly imprinted polymer (MIP) was fabricated by the dummy template molecular imprinting technology. First, computational simulation was performed to select a suitable dummy template, 3,5‐dinitro‐4‐methylbenzoic acid (T1), based on the maximum basis set superposition error (BSSE)‐corrected binding interaction energy (ΔE) of the monomer N‐vinylpyrrolidone (NVP)‐T1 complex and its structural overlap with trifluralin. Then, the MIP was prepared via the bulk polymerization. The adsorption experiments showed the MIP exhibited a trifluralin adsorption capacity of 5.1 mg g−1, an imprinting factor (IF) of 2.2, and short adsorption equilibrium time of 5 min. The adsorption of trifluralin conformed to the Freundlich adsorption (R2 = 0.985) and pseudo‐second‐order model (R2 = 0.999). In addition, the MIP exhibited selectivity to trifluralin over other adsorbents, including structural analogs (pendimethalin and oryzalin), pesticide (carbendazim), and nitrocompounds (nitrofurantoin, furazolidone, and furaltadone), with the selectivity factor (β) in the range of 1.2–3.0, respectively. In trifluralin/oryzalin mixture, the IF toward oryzalin was still as high as 1.9. The removal rate of the MIP to trifluralin in environmental water samples ranged from 90.08% to 99.04%. This study provides theoretical and experimental insights for the preparation of MIP using dummy templates.

Dual-template magnetic molecularly imprinted polymers for selective extraction and sensitive detection of aflatoxin B1 and benzo(α)pyrene in environmental water and edible oil

The coexistence of multiple contaminates in the environment and food is of growing concern due to their extremely hazard as a well-known class I carcinogen, like aflatoxin B1 (AFB1) and benzo(α)pyrene (BaP). AFB1 and BaP are susceptible to coexistence in environmental water and edible oil, posing a significant potential risk to environmental monitoring and food safety. The remaining challenges in detecting multiple contaminates include unsatisfied sensitivity, insufficient targets selectivity, and interferences in complex matrices. Here, we developed dual-template magnetic molecularly imprinted polymers (DMMIPs) for selective extraction of dual targets in complex matrices from the environment and food. The DMMIPs were fabricated by surface imprinting with vinyl-functionalized Fe3O4 as carrier, 5,7-dimethoxycoumarin and pyrene as dummy templates, and methacrylamide as functional monomer. The DMMIPs showed excellent adsorption ability (12.73–15.80 mg/g), imprinting factors (2.01–2.58), and reusability of three adsorption-desorption cycles for AFB1 and BaP. The adsorption mechanism including hydrogen bond, electrostatic interaction and van der Waals force was confirmed by physical characterization and DFT calculation. Applying DMMIPs in magnetic solid phase extraction (MSPE) followed by high-performance liquid chromatography (HPLC) analysis enabled detection limits of 0.134 μg/L for AFB1 and 0.107 μg/L for BaP. Recovery rates for water and edible oil samples were recorded as 86.2%–110.3% with RSDs of 4.1%–11.9%. This approach demonstrates potential for simultaneous identification and extraction of multiple contaminants in environmental and food.

Preparation and optimization of dummy molecularly imprinted polymer-based solid-phase extraction system for selective enrichment of p-toluene sulfonate esters genotoxic impurities

Sulfonate esters, one class of genotoxic impurities (GTIs), have gained significant attention in recent years due to their potential to cause genetic mutations and cancer. In the current study, we employed the dummy template molecular imprinting technology with a dummy template molecule replacing the target molecule to establish a pretreatment method for samples containing p-toluene sulfonate esters. Through computer simulation and ultraviolet–visible spectroscopy analysis, the optimal functional monomer acrylamide and polymerization solvent chloroform were selected. Subsequently, a dummy template molecularly imprinted polymer (DMIP) was prepared by the precipitation polymerization method, and the polymer was characterized in morphology, particle size, and composition. The results of the adsorption and enrichment study demonstrated that the DMIP has high adsorption capability (Q = 7.88 mg/g) and favorable imprinting effects (IF = 1.37); Further, it could simultaneously adsorb three p-toluene sulfonate esters. The optimal adsorption conditions were obtained by conditional optimization of solid-phase extraction (SPE). A pH 7 solution was selected as the loading condition, the methanol/1 % phosphoric acid solution (20:80, v/v) was selected as the washing solution, and acetonitrile containing 10 % acetic acid in 6 mL was selected as the elution solvent. Finally, we determined methyl p-toluene sulfonate alkyl esters, ethyl p-toluene sulfonate alkyl esters, and isopropyl p-toluene sulfonate alkyl esters in tosufloxacin toluene sulfonate and capecitabine at the 10 ppm level (relative to 1 mg/mL active pharmaceutical ingredient (API) samples) by using DMIP-based SPE coupled with HPLC. This approach facilitated the selective enrichment of p-toluene sulfonate esters GTIs from complex API samples.

Synthesis of Boronate Affinity-Based Oriented Dummy Template-Imprinted Magnetic Nanomaterials for Rapid and Efficient Solid-Phase Extraction of Ellagic Acid from Food.

Ellagic acid (EA) is a natural polyphenol and possesses excellent in vivo bioactivity and antioxidant behaviors, which play an important role in the treatment of oxidative stress-related diseases, such as cancer. Additionally, EA is also known as a skin-whitening ingredient. The content of EA would determine its efficacy. Therefore, the accurate analysis of EA content can provide more information for the scientific consumption of EA-rich foods and cosmetics. Nevertheless, the analysis of EA in these samples is challenging due to the low concentration level and the presence of interfering components with high abundance. Molecularly imprinted polymers are highly efficient pretreatment materials in achieving specific recognition of target molecules. However, the traditional template molecule (EA) could not be absolutely removed. Hence, template leakage continues to occur during the sample preparation process, leading to a lack of accuracy in the quantification of EA in actual samples, particularly for trace analytes. In addition, another drawback of EA as an imprinting template is that EA possesses poor solubility and a high price. Gallic acid (GA), called dummy templates, was employed for the synthesis of MIPs as a solution to these challenges. The approach used in this study was boronate affinity-based oriented surface imprinting. The prepared dummy-imprinted nanoparticles exhibited several significant advantages, such as good specificity, high binding affinity ((4.89 ± 0.46) × 10-5 M), high binding capacity (6.56 ± 0.35 mg/g), fast kinetics (6 min), and low binding pH (pH 5.0) toward EA. The reproducibility of the dummy-imprinted nanoparticles was satisfactory. The dummy-imprinted nanoparticles could still be reused even after six adsorption-desorption cycles. In addition, the recoveries of the proposed method for EA at three spiked levels of analysis in strawberry and pineapple were 91.0-106.8% and 93.8-104.0%, respectively, which indicated the successful application to real samples.

Novel dummy molecularly imprinted polymer for simultaneous solid-phase extraction of stanozolol metabolites from urine

Stanozolol, a synthetic derivative of testosterone, is one of the common doping drugs among athletes and bodybuilders. It is metabolized to a large extent and metabolites are detected in urine for a longer duration than the parent compound. In this study, a novel dummy molecularly imprinted polymer (DMIP) is developed as a sorbent for solid-phase extraction of stanozolol metabolites from spiked human urine samples. The optimized DMIP is composed of stanozolol as the dummy template, methacrylic acid as the functional monomer, and ethylene glycol dimethacrylate as the cross-linker in a ratio of 1:10:80. The extracted analytes were quantitively determined using a newly developed and validated ultrahigh-performance liquid chromatography tandem mass spectrometry method, where the limits of detection and quantitation were 0.91 and 1.81 ng mL−1, respectively, fulfilling the minimum required performance limit decided on by the World Anti-Doping Agency. The mean percentage extraction recoveries for 3’-hydroxystanozolol, 4β-hydroxystanozolol, and 16β-hydroxystanozolol are 97.80% ± 13.80, 83.16% ± 7.50, and 69.98% ± 2.02, respectively. As such, the developed DMISPE can serve as an efficient cost-effective tool for doping and regulatory agencies for simultaneous clean-up of the stanozolol metabolites prior to their quantification.Graphical abstract

Fabrication of molecularly imprinted carbon nanotubes integrating ionic liquids for efficient detection of perfluoroalkyl carboxylic acid in environmental water

It is extremely significant while challenging to accurately detect low-levels of perfluoroalkyl carboxylic acid compounds (PFCAs) in environmental water. Herein, adopting perfluorotetradecanoic acid as the dummy template, selective molecularly imprinted composites (CNTs@ILs@MIPs) grafted carbon nanotubes integrating hydrophilic ionic liquids were successfully prepared via surface imprinting and dummy-template imprinting techniques. The obtained CNTs@ILs@MIPs were applied as selective extraction adsorbent for specifically extract PFCAs in environmental water coupled with gas chromatography-mass spectrometry quantification. Detailed studies were conducted on the main preparation parameters and extraction conditions. The CNTs@ILs@MIPs displayed excellent adsorptivity, and the established method exhibited low LODs (0.60–1.64 ng L−1), wide linearity with R2 above 0.9994, and satisfactory adsorption recoveries (80.5–112.5%) for seven PFCAs. This proposed method provides a new applicable approach for the detection of targeted pollutants in environmental water by utilizing the high affinity and recognition ability of molecularly imprinted carbon nanotube functional materials modified with ionic liquids.

Molecular imprinting-based triple-emission ratiometric fluorescence sensor with aggregation-induced emission effect for visual detection of doxycycline

The development of high-performance sensors for doxycycline (DOX) detection is necessary because its residue accumulation will cause serious harm to human health and the environment. Here, a novel tri-emission ratiometric fluorescence sensor was proposed by using “post-mixing” strategy of different emissions fluorescence molecularly imprinted polymers with salicylamide as dummy template (DMIPs). BSA was chosen as assistant functional monomer, and also acted as sensitizers for the aggregation-induced emission (AIE) effect of DOX. The blue-emitting carbon dots and the red-emitting CdTe quantum dots were separately introduced into DMIPs as the response signals. Upon DOX recognition within 2 min, blue and red fluorescence of the tri-emission DMIPs sensor were quenched while green fluorescence of DOX was enhanced, resulting in a wide range of color variations observed over bluish violet-rosered-light pink-orange-yellow-green with a detection limit of 0.061 μM. The sensor possessed highly selective recognition and was successfully applied to detect DOX in complicated real samples. Moreover, with the fluorescent color collection and data processing, the smartphone-assisted visual detection of the sensors showed satisfied sensitivity with low detection limit. This work provides great potential applications for rapid and visual detection of antibiotics in complex substrates.

Development of a selective electrochemical microsensor based on molecularly imprinted polydopamine/ZIF-67/laser-induced graphene for point-of-care determination of 3-nitrotyrosine

3-nitrotyrosine (3-NT) is a biomarker closely associated with the early diagnosis of oxidative stress-related disorders. The development of an accurate, cost-effective, point-of-care 3-NT sensor holds significant importance for self-monitoring and clinical treatment. In this study, a selective, sensitive, and portable molecularly imprinted electrochemical sensor was developed. ZIF-67 with strong adsorption capacity was facilely modified on an electrochemically active laser-induced graphene (LIG) substrate (formed ZIF-67/LIG). Subsequently, biocompatible dopamine was chosen as the functional monomer, and interference-free ʟ-tyrosine was used as the dummy template to create molecularly imprinted polydopamine (MIPDA) on the ZIF-67/LIG, endowing the sensor with selectivity. The morphologies, electrochemical properties, and detection performance of the sensor were comprehensively investigated using scanning electron microscopy, cyclic voltammetry, electrochemical impedance spectroscopy, and differential pulse voltammetry. To achieve the best performance, several parameters were optimized, including the number of polymerization cycles (15), elution time (60 min), incubation time (7 min), and pH of the buffer solution (6). The turnaround time for this sensor is 10 min. Benefiting from the alliance of MIPDA, ZIF-67, and LIG, the sensor exhibited excellent sensitivity with a detection limit of 6.71 nM, and distinguished selectivity against 11 interfering substances. To enable convenient clinical diagnosis, a customized electrochemical microsensor with MIPDA/ZIF-67/LIG was designed, showcasing excellent reliability and convenience in detecting biological samples without pretreatment. The proposed microsensor will not only facilitate clinical diagnosis and improve patient care, but also provide inspiration for the development of other portable and accurate electrochemical biosensors.

Molecularly imprinted metal-organic frameworks assisted cloth and paper hybrid microfluidic devices for visual detection of gonyautoxin

Marine algal toxin contamination is a major threat to human health. Thus, it is crucial to develop rapid and on-site techniques for detecting algal toxins. In this work, we developed colorimetric cloth and paper hybrid microfluidic devices (μCPADs) for rapid detection of gonyautoxin (GTX1/4) combined with molecularly imprinted polymers. In addition, the metal-organic frameworks (MOFs) composites were applied for this approach by their unique features. Guanosine serves as a dummy template for surface imprinting and has certain structural advantages in recognizing gonyautoxin. MOF@MIPs composites were able to perform a catalytic color reaction using hydrogen peroxide-tetramethylbenzidine for the detection of GTX1/4. The cloth-based sensing substrates were assembled on origami μPADs to form user-friendly, miniaturized colorimetric μCPADs. Combined with a smartphone, the proposed colorimetric μCPADs successfully achieved a low limit of detection of 0.65 μg/L within the range of 1–200 μg/L for rapid visual detection of GTX1/4. Moreover, the GTX1/4 of real shellfish and seawater samples were satisfactorily detected to indicate the application prospect of the μCPADs. The proposed method shows good potential in the low-cost, stable establishment of assays for the rapid detection of environmental biotoxins.

Highly selective colorimetric determination of glutathione based on sandwich-structured nanoenzymes composed of gold nanoparticle-coated molecular imprinted metal-organic frameworks.

Asandwich-structured composite nanoenzyme (NH2-MIL-101(Fe)@Au@MIP) was prepared using molecularly imprinted polymers, metal-organic frameworks, and gold nanoparticles and a highly selective glutathione (GSH) colorimetric sensor was constructed. The inner part of the composite nanoenzymes is a metal-organic framework loaded with gold nanoparticles (AuNPs), NH2-MIL-101(Fe)@Au, which has superior peroxidase-like activity compared with NH2-MIL-101(Fe). This is due to the surface plasmon resonance effect of AuNPs. GSH can form strong Au-S bonds with AuNPs, which can significantly reduce the enzymatic activity of NH2-MIL-101(Fe)@Au, thereby changing the absorbance at 450nm of the sensing system. The degree of change in absorbance is correlated with the concentration of GSH. In the outer part, the molecularly imprinted polymer with oxidized glutathione (GSSG) as a dummy template provided specific pores, which significantly improved the selectivity of the sensing system. The sensor showed good GSH sensing performance in the range 1 ~ 50μM with a lower limit of detection (LOD) of 0.231μM and good sensing performance in fetal bovine serum, indicating its highpotential for clinical diagnostic applications.

Development of antibody-engineered molecularly imprinted polymers for selective capture of aflatoxin B1 from starchy food and medicinal materials

Molecularly imprinted polymers(MIPs) have been widely used as selective recognition materials for analysis and detection of mycotoxins, such as aflatoxin B1(AFB1). However, little attention was given to investigate key factors that affecting selectivity and specificity of MIPs, such as functional monomers and imprinted cavity compatibility. Inspired by the recognition of antibody to antigen, we designed and employed amino acids as functional monomers with multiple interaction sites via hydrogen bonding and aromatic π-π stacking, meanwhile, synthesized structurally matched alternative template, 5,7-dimethoxycyclopentenone [2,3-c]coumarin(DMPC) to prepare MIPs via silica surface grafting. The adsorption of antibody-engineered MIPs was enhanced significantly compared to that of MIPs prepared by conventional functional monomers and dummy templates for selective capture of AFB1. And the specific recognition sites of MIPs left by DMPC conferred the most remarkable selectivity toward AFB1 among aflatoxins. The mechanism and contribution of functional groups and imprinted cavities for selective adsorption of AFB1 were elucidated, providing a different approach to improving functional monomers and templates in MIPs. The solid phase extraction cartridges packed DMPC-ATry-MIPs@SiO2 were used for enrichment of AFB1 in Lotus seeds and Coix seeds. The recoveries were 94.48–112.90 % and 83.32–116.04 % respectively, even after being used five times repeatedly. The cartridges could replace expensive and low-reusability immunoaffinity columns in the analysis and detection of AFB1 in real samples, providing a kind of promising sample pretreatment materials for trace analysis in food and drugs.

Evaluation of deep eutectic solvents in the synthesis of molecularly imprinted fibers for the solid-phase microextraction of triazines in soil samples.

Nowadays, molecularly imprinted polymers (MIPs) are well established and are considered excellent materials for performing selective extractions. However, with the progressive implementation of the principles of green chemistry, it is necessary to find greener alternatives for both the synthesis and further use of MIPs in sample preparation. Accordingly, in the present work, different deep eutectic solvents (DES, both hydrophilic and hydrophobic), as an alternative to conventional organic solvents (i.e., toluene), were evaluated as porogens for the synthesis of imprinted fibers (monoliths), using fused silica capillaries as molds, for solid-phase microextraction (SPME). From this study, the polymer prepared with propazine (dummy template), methacrylic acid (monomer), ethylene glycol dimethacrylate (cross-linker), and a formic acid:L-menthol (1:1) DES (porogen) showed the best performance for selective rebinding of triazines. After optimization of the different variables involved in SPME, the new imprinted fibers were successfully applied to the extraction of target analytes (desisopropylatrazine, desethylatrazine, simazine, and atrazine) from soil sample extracts, providing relative recoveries ranging from 75.7 to 120.1%, reaching limits of detection within the range of 6.2-15.7ngg-1, depending upon the analyte.

Development of a microfluidic device to enrich and detect zearalenone in food using quantum dot-embedded molecularly imprinted polymers.

Mycotoxins are secondary metabolites of certain moulds, prevalent in 60-80% of food crops and many processed products but challenging to eliminate. Consuming mycotoxin-contaminated food and feed can lead to various adverse effects on humans and livestock. Therefore, testing mycotoxin residue levels is critical to ensure food safety. Gold standard analytical methods rely on liquid chromatography coupled with optical detectors or mass spectrometers, which are high-cost with limited capacity. This study reported the successful development of a microfluidic "lab-on-a-chip" device to enrich and detect zearalenone in food samples based on the fluorescence quenching effect of quantum dots and selective affinity of molecularly imprinted polymers (MIPs). The dummy template and functional polymer were synthesized and characterized, and the detailed microfluidic chip design and optimization of the flow conditions in the enrichment module were discussed. The device achieved an enrichment factor of 9.6 (±0.5) in 10 min to quantify zearalenone spiked in food with high recoveries (91-105%) at 1-10 mg kg-1, covering the concerned residue levels in the regulations. Each sample-to-answer test took only 20 min, involving 3 min of manual operation and no advanced equipment. This microfluidic device was mostly reusable, with a replaceable detection module compatible with fluorescence measurement using a handheld fluorometer. To our best knowledge, the reported device was the first application of an MIP-based microfluidic sensor for detecting mycotoxin in real food samples, providing a novel, rapid, portable, and cost-effective tool for monitoring mycotoxin contamination for food safety and security.

Dispersive solid phase extraction using a hydrophilic molecularly imprinted polymer for the selective extraction of patulin in apple juice samples

A molecularly imprinted polymer with a specific selectivity for patulin was successfully synthesized. The molecularly imprinted material was prepared using the two functional monomers dopamine and melamine and formaldehyde as the cross-linker. The resulting material possessed a large number of hydrophilic groups, such as hydroxyls, imino groups, and ether linkages. For the first time, uric acid was used as a dummy template for its structural similarity to patulin. Comprehensive characterization and detailed studies of the adsorption process were carried out via adsorption isotherms, while the rate-limiting steps were investigated using adsorption kinetics. Separation, determination, and quantification of patulin were achieved by ultra-high performance liquid chromatography coupled with both photodiode array detection and tandem mass spectrometry. The latter was applied to patulin confirmation in the analysis of real samples. The methodology was validated in 20 apple juice samples. The results showed that the developed hydrophilic molecularly imprinted polymer had high selectivity and specific adsorption towards patulin, with mean recoveries ranging between 85 and 90% and a relative standard deviation lower than 15%. The developed molecularly imprinted polymer exhibited good linearity in the range 1–100 ng mL−1 with coefficient of determination (R2) > 0.99. The limit of detection was 0.5 ng mL−1, and the limit of quantification was 1 ng g−1. The developed method showed a good purification capacity for apple juices due to its hydrophilic nature and the polar interactions established with the target analyte.Graphical abstract

Dummy molecularly imprinted polymer-based solid-phase extraction method for the determination of some phthalate monoesters in urine by gas chromatography–mass spectrometry analysis

A dummy molecularly imprinted polymer-based solid-phase extraction (SPE) sorbent was used for the selective extraction of some phthalate monoesters, monoethyl phthalate (MEP), monobutyl phthalate (MnBP) and mono-(2-ethylhexyl) phthalate (MEHP) in urine prior to gas-chromatography-mass spectrometry (GC-MS) analysis. Diethyl phthalate (DEP), a phthalate ester, was successfully used as a dummy template to prepare selective sorbent for MEP, MnBP, and MEHP extraction. DEP-imprinted poly(ethylene glycol dimethacrylate N-methacryloyl-l-tryptophan methyl ester) (DPEMT) microbeads were synthesized by suspension polymerization and characterized by Fourier Transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and Brunauer Emmet Teller (BET) analysis. The critical parameters (i.e., pH, sorbent amount, ionic strength, sample volume, elution solvent) affecting the extraction performance of the DPEMT-SPE sorbent were optimized. Under optimum conditions, good linearities were obtained in the concentration range of 4 to 60 ng/mL with determination coefficients (R2) of greater than 0.9959. The developed SPE method provided low limits of detection (LOD) of 0.05–1.20 ng/mL and limits of quantification (LOQ) of 0.18–4.01 ng/mL with relative standard deviations (RSDs) of less than 8.95 % for intra- and inter-day analyses. The proposed SPE method was used to analyze phthalate monoesters in spiked urine samples, and recoveries of 97.45–109.26 % were obtained. DPEMT-SPE sorbent was reused for 15 times without any losses of performance. Consequently, a highly selective and sensitive SPE method based on a dummy molecularly imprinted polymer combined with GC-MS was successfully developed to monitor human phthalate exposure via urine samples.

The construction of highly selective surface molecularly imprinted polymers based on Cu(II) coordination for the detection of bisphenol A

Herein, we designed and constructed a highly selective MIPs for bisphenol A (BPA) named Cu-MIPs@CS based on Cu(II) coordination. The synthesis of Cu-MIPs@CS employed a dummy template strategy and surface imprinting technology, with chitosan (CS) as the substrate linked to imprinted layers via Cu2+ bridging. 4-vinylpyridine acted as the functional monomer, capable of forming a complex with the template ketoprofen, while ethylene glycol dimethacrylate served as the cross linker. Cu-MIPs@CS exhibited a significantly enhanced imprinting factor of 14.78 for BPA, which was approximately 6.6 times higher than that of imprinted materials without Cu2+ (MIPs@CS). Cu-MIPs@CS exhibited a selective factor of 12.74 towards resorcinol, which possessed identical functional groups but a smaller size than BPA, representing an enhancement of selectivity by 12.25-fold compared to MIPs@CS. More importantly, Cu-MIPs@CS exhibited a superior discrimination ability between BPA and its structural analogue, diphenolic acid, with an excellent selective factor of 2.93, highlighting its significance in distinguish the structural analogue of BPA. In contrast, MIPs@CS lack sufficient selectivity to differentiate between them. Through exploration of adsorption mechanism of Cu-MIPs@CS, it was demonstrated that the incorporation of Cu2+ significantly reduced nonspecific adsorption, but also facilitated the creation of more selective imprinted cavities by introducing metal coordination, thereby notably enhancing the selectivity of Cu-MIPs@CS. Finally, the developed Cu-MIPs@CS were applied as the solid phase extraction adsorbent and combined with HPLC-DAD detection to establish an analytical method towards BPA in drinking water samples. The limit of detection of the method was 0.14 μg L−1 and recoveries ranged from 95.6 % to 101 %. This work provided broad prospects for construction of highly selective MIPs and accurate quantification of trace amounts of BPA.

Development of a Screening Method for Fluoroquinolones in Meat Samples Using Molecularly Imprinted Carbon Dots.

An accurate and simple screening method has been developed for the determination of fluoroquinolone antibiotics. Carbon dots were synthesized by simple hydrothermal treatment as highly fluorescent nano-sensors. They were subsequently used in the synthesis of organic-based molecularly imprinted polymers to develop fluorescence-based polymeric composites using enoxacin as a representative dummy template molecule of fluoroquinolones. The method was optimized concerning the pH of the medium and composite concentration. The normalized fluorescence intensity showed efficient quenching under optimized conditions upon successive addition of the template, with an excellent correlation coefficient. The proposed method was applied to eight other fluoroquinolones, exhibiting, in all cases, good correlation coefficients (0.65-0.992) within the same linearity range (0.03-2.60 mg mL-1). Excellent detection and quantification limits were been obtained for the target analytes down to 0.062 and 0.186 mg L-1, respectively. All studied analytes showed no interference with enrofloxacin, the most commonly used veterinary fluoroquinolone, with a percentage of cross-reactivity varying from 89.00 to 540.00%. This method was applied successfully for the determination of enrofloxacin in three different types of meat samples: beef, pork, and chicken, with good recoveries varying from 70 to 100% at three levels. This new procedure is an easy analytical method that can be useful as a screening method for monitoring the environmental hazard of fluoroquinolones in quality control laboratories.

Three-Dimensional Porous PVDF Foam Imprinted Membranes with High Flux and Selectivity toward Artemisinin/Artemether.

In this study, a new 3D porous PVDF-foam-imprinted membrane (PPIM) for the selective separation of artemisinin (ART) was first prepared via the dopamine adhesion of pre-synthesized MIPs into the interior of the PPIM. In the PPIM, the pre-synthesized molecularly imprinted polymers (MIPs) with artesunate (ARU) as a dummy template were uniformly loaded on the interior of the membrane, avoiding the defects of recognition site encapsulation found in the conventional membrane. This membrane also exhibited excellent flux, which is beneficial in practical separation applications. The PPIM was systematically characterized via FT-IR, SEM, pore-size distribution analysis, water contact angle test, membrane flux, and mechanical performance analysis, respectively. In the static adsorption experiment, the pseudo-second-order kinetic model better fitted the rebinding data of ART. Under dynamic conditions, the ART adsorption capacity of the PPIM could be further remarkably improved by tailoring the flow rate to 3 mL min-1. In the selective separation experiment, with artemether (ARE) as the competition substrate, the selective separation ability (α) of the PPIM towards ART/artemether (ARE) reached its peak value (3.16) within only 10 min at this flow rate, which is higher than that of porous PVDF foam non-imprinted membranes (PPNM) (ca. 1.5), showing great separation efficiency in a short time. Moreover, the PPIM can be reused five times without a significant decrease in its adsorption capacities, showing good regeneration performance. This work highlights a simple strategy for constructing new MIMs with high flux and great mechanical strength to achieve the efficient selective separation of ART and ARE in practical applications.