Dummy Template Molecule Research Articles

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.

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.

Target recognition and preferential degradation of toxic chemical groups by innovative group-imprinted photocatalyst with footprint cavity

Target recognition and preferential degradation of toxic chemical groups remain critical challenges in photocatalytic degradation of organic contaminant. In this study, the concept of group-imprinting was first proposed, and group-imprinted copolymers of aniline and pyrrole were grafted from the surface of magnetic CuFeO2@MnO2 nanocomposites (MIP-CuFeO2@MnO2) using acrylamide as dummy templates for imprinting the amide group of tetracycline for the first attempt, and the molar ratios of dummy template molecule to functional monomer was optimized. The magnetic MIP-CuFeO2@MnO2 showed high adsorption capacity and good recognition for tetracycline. In mixture solution of tetracycline and ibuprofen, the distribution coefficient (kd) value of MIP-CuFeO2@MnO2 for tetracycline was 0.308 L/g, which is 6.86 times more than for ibuprofen (only 0.045 L/g). The selection factor (α) of MIP-CuFeO2@MnO2 is about 3.2 times that of non-imprinted counterpart, indicating that the imprinting cavities in copolymer layer which match with the amide groups of tetracycline can selectively recognize and adsorb tetracycline. More importantly, MIP-CuFeO2@MnO2 exhibited preferential degradation performance for amide groups, which was confirmed by the intermediates and degradation pathway. The E. coli growth suggests effective toxicity reduction of tetracycline due to the preferential degradation of amide groups by photocatalysis of MIP-CuFeO2@MnO2.

Development of a specific and sensitive method for the detection of glyphosate pesticide and its metabolite in tea using dummy molecularly imprinted solid-phase extraction coupled with liquid chromatography-tandem quadrupole mass spectrometry

Glyphosate, a widely used herbicide, and its primary metabolite aminomethyl phosphonic acid have been found to cause environmental and ecological issues and threaten human health. The conventional pretreatment method was insufficient for the extraction, concentration, and enrichment of trace substances, resulting in poor specificity. Thus, our objective was to develop a method for glyphosate pesticide detection using dummy molecularly imprinted solid-phase extraction (DMI-SPE) combined with liquid chromatography-tandem quadrupole mass spectrometry (DMI-SPE-LC/MS/MS). The sol-gel method was used to prepare the molecularly imprinted material, using glyphosine as the dummy template molecule, to achieve specific adsorption to glyphosate and reduce costs. The optimized polymerization conditions achieved maximum adsorption of 28.6 µg/mg glyphosate by the molecularly imprinted material. The established DMI-SPE-LC/MS/MS method was used to detect glyphosate and its metabolite (aminomethyl)phosphonic acid in tea. The concentration ranges of glyphosate and (aminomethyl)phosphonic acid (from 0.05 to 4 µg/mL) were linear with correlation coefficients of 0.999 and 0.991, respectively. The recoveries of (aminomethyl)phosphonic acid at three spiked levels ranged from 79.95% to 83.74%, with RSDs between 6.40% and 7.45%, while the recoveries of glyphosate ranged from 98.69% to 106.26%, with RSDs between 0.91% and 1.18%. Our results demonstrate that the developed DMI-SPE-LC/MS/MS method achieves high sensitivity and specific detection of glyphosate and its metabolite (aminomethyl)phosphonic acid in tea matrices.

Carbon Nanotube-Supported Dummy Template Molecularly Imprinted Polymers for Selective Adsorption of Amide Herbicides in Aquatic Products.

In this study, a carbon nanotube (CNTs)-supported dummy template molecularly imprinted polymer (DMIPs) material was synthesized and utilized for the detection of amide herbicides in aquatic products via matrix solid-phase dispersion technology (MSPD). The DMIPs material was characterized, and its adsorption kinetics and isotherm were determined, the adsorption model was established, and the selective adsorption coefficient was calculated. The extract parameters of the method were optimized and successfully employed for the separation, analysis and detection of real samples, with satisfactory detection limits and linear ranges obtained. By comparing with other methods, the CNTs@DMIPs combined with MSPD technology established in our study can effectively solve false negative problems caused by insufficient destructive force, using dummy template molecules can also address the issue of false positives caused by template molecule leakage in molecular imprinting. Overall, the method is appropriate for the separation and detection of endogenous substances from highly viscous and poorly dispersed samples and is used as a routine detection tool in the aquaculture industry.

Molecularly imprinted polymer on silylated cellulose matrix via dummy template for detoxification of ginkgolic acids

Ginkgo biloba extracts (GBE) is one of the most widely used natural drugs for the treatment of cardiovascular and cerebrovascular diseases, but how to remove ginkgolic acids (GAs) from extracts in a safe, efficient, and economical method is an urgent need. Combined with quantum chemistry theoretical calculations and surface molecular imprinting technology, an eco-friendly GAs molecularly imprinted polymer via dummy template molecules on silylated cellulose matrix (SCM-DMIP-GAs) has been developed to detoxify target GAs from GBE. The results of scanning electron microscope , Fourier transform infrared spectrum, X-ray diffraction, N 2 adsorption-desorption isotherm, thermogravimetry , and binding absorption experiments showed SCM-DMIP-GAs has homogeneous morphology, good selective adsorption performance, high absorption capacity and stable recyclability. Furthermore, as solid phase extraction adsorbent, SCM-DMIP-GAs displays an efficient detoxification effect (99.98 %) after once treatment. This study presents an economic, green, and efficient solution for pharmaceutical and medical fields in plant extracts detoxification. • MIP to detoxify ginkgolic acids (SCM-DMIP-GAs) was firstly prepared. • Appropriate dummy template molecule was selected by quantum chemical calculation. • SCM-DMIP-GAs with stable recyclability is green, economic, and easy to prepare. • SCM-DMIP-GAs in SPE with 99.98 % detoxification effect in once treatment.

Preparation of dummy molecularly imprinted polymers for selective extraction of aromatic amine genotoxic impurities

To ensure drug safety, the quality monitoring of genotoxic impurities (GTIs) which have very trace content in medicine is important. Therefore, it should be established an efficient sample pretreatment method to extract GTIs to achieve specific enrichment. In this work, dummy template molecular imprinting technology (DMIT) was used as dummy template molecule (DTM) to substitute for the target molecule (TM) for established the pretreatment of the sample containing aromatic amine GTIs. A novel strategy for screening out DTM by calculation of computer simulation is established, where the binding energy between the template and functional monomer has the relatively lowest value (-9.60 kcal/mol). Then dummy template molecular imprinted polymer (DMIP) was prepared by bulk polymerization according to the molar ratio of template molecule-functional monomer-crosslinker = 1:4:8, the prepared DMIP exhibited the highest adsorption (Q = 8.6 mg/g) and good blotting effect (IF = 1.3) and can simultaneously adsorb three aromatic amine GTIs. The optimal adsorption conditions were obtained by conditional optimization of solid phase extraction (SPE). The solution of pH 7 was chosen as the loading condition, and methanol/acetic acid (90:10, v/v) was chosen as the elution condition. Finally, we determined 2, 6-dichloroaniline in diclofenac sodium at a 5 ppm level and p-toluidine as the TMs in torasemide sample at 10 ppm by using DMIT-based solid phase extraction and analysis by HPLC, it satisfied the quality control of GTIs in pharmaceutics. DMIT by this strategy has great potential in the sample preparation of GTIs.

Facile Synthesis of Molecularly Imprinted Ratiometric Fluorescence Sensor for Ciguatoxin P-CTX-3C Detection in Fish

Ciguatoxin (CTX) detection methods are essential due to the serious hazard that bioaccumulation in fish and transmission along the food chain poses to human health. We report the rapid and simple development of a dual-emitting, molecularly imprinted, ratiometric fluorescence sensor (MIPs@BCDs/RCDs@SiO2) to detect ciguatoxin P-CTX-3C with high sensitivity and selectivity. The sensor was fabricated via sol–gel polymerization using monensin as the fragmentary dummy template molecule, blue carbon dots (BCDs) as the response signal, and red carbon dots (RCDs) as the reference signal. The fluorescence emission of BCDs was selectively quenched in the presence of P-CTX-3C, leading to a favorable linear correlation between the fluorescence intensity ratio (I440/I675) and the P-CTX-3C concentration in the range of 0.001–1 ng/mL with a lower detection limit of 3.3 × 10−4 ng/mL. According to LC-MS measurement results, the proposed sensor can rapidly detect ciguatoxin P-CTX-3C in coral reef fish samples with satisfactory recoveries and standard deviations. This study provides a promising strategy for rapid trace analysis of marine toxins and other macromolecular pollutants in complex matrices.

Dummy template based molecularly imprinted solid-phase microextraction coating for analysis of trace disinfection by-product of 2,6-dichloro-1,4-benzoquinone using high-performance liquid chromatography

Trace disinfection by-products (DBPs) produced during the disinfection of drinking water are potentially carcinogenic, teratogenic and mutagenic, which has aroused much attention recently. In this study, a molecularly imprinted (MIP) solid -phase microextraction (SPME) fiber coating was prepared by an in-situ polymerization method using a dummy template molecule for the analysis of trace 2,6-dichloroindole-1,4-benzoquinone (2,6-DCBQ), a typical DBP. The characterization results suggested that this monolithic SPME fiber under the optimized conditions had the porous structure, large surface area and good thermal stability. Due to the strong structural recognition and molecular interaction between MIP SPME coating and target molecule, it showed good extraction selectivity and capacity to trace 2,6-DCBQ with an imprinting factor of 4.7. Then, coupling with high-performance liquid chromatography (HPLC)-ultraviolet (UV) detection, a sensitive analytical method for trace 2,6-DCBQ in water samples was successfully established with a detection limit down to 2.3 ng/mL. The recoveries of the proposed method were in range of 84.4–122% with the relative standard deviations of 1.0–13% (n = 3). The results showed that this MIP SPME-HPLC-UV method possessed high analytical selectivity and sensitivity for trace 2,6-DCBQ in water, which would benefit the improvement of the practicability of DBPs monitoring and detection methodology.

Rapid determination of trace ciprofloxacin residue in milk samples using molecularly imprinted membrane extraction-high performance liquid chromatography-tandem mass spectrometry

An enrofloxacin (ENR) molecularly imprinted membrane (MIM) was prepared with a polyvinylidenedifluoride (PVDF) membrane as the carrier, ENR as the dummy template molecule, α-methacrylic acid (MAA) as the functional monomer, ethylene glycol dimethacrylate (EGDMA) as the cross-linker, and a chloroform-methanol mixture solvent as the porogen. The MIM showed excellent selectivity, high adsorption capacity, and high adsorption rate for ciprofloxacin. Additionally, a method combining molecularly imprinted membrane extraction (MIME) and high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) was developed and validated for the selective analysis of trace ciprofloxacin residue in milk samples. The sample pretreatment involved only a single step of protein precipitation. Ciprofloxacin showed good linearity in mass concentration range of 0.1-200 μg/L with a high correlation coefficient (r2>0.9996). The limit of detection (LOD, S/N=3) and limit of quantification (LOQ, S/N=10) were 0.02 μg/L and 0.1 μg/L, respectively. The relative standard deviations (RSDs) of interday and intraday precisions ranged from 3.3% to 7.9%. The ciprofloxacin recovery was in the range of 92.6%-119.1%. The results showed that the proposed method is simple and fast, with high accuracy and sensitivity, thus being suitable for the rapid detection of trace ciprofloxacin residue in milk samples.

Fe3O4/graphene molecularly imprinted composite for selective separation of catecholamine neurotransmitters and their analysis in rat brain tissues

In this study, a novel of magnetic molecularly imprinted polymers (Fe3O4/GO/DMIPs) with multi-targets recognizing function were prepared by surface molecular imprinting technique adopting isoprenaline as the dummy-template molecule and graphene oxide (GO) as the carrier. The morphology, structures and magnetic properties of nanosorbents were characterized and assessed in detail and the results indicated that the 3D recognition cavities and matching functional groups with catecholamine neurotransmitters (CNs) were successfully fabricated on Fe3O4/GO surface. Moreover, the kinetic, isothermal and selective adsorption experiments were conducted to further reveal the adsorption behavior of adsorbent toward CNs and the results showed that the Fe3O4/GO/DMIPs possessed high adsorption capacity, rapid binding rate and excellent selectivity for CNs. On this basis, the Fe3O4/GO/DMIPs were further applied as adsorbent of magnetic solid-phase extraction (MSPE) for selective recognition and separation of CNs (dopamine, epinephrine, norepinephrine) followed by UPLC-MS/MS detection. The crucial parameters affecting the extraction efficiency were systematically optimized by Box-Behnken statistical design. Under the optimum conditions, satisfactory linearity (r > 0.99) was obtained with the lower limit of quantification from 0.53 to 1.93 ng mL−1. The accuracy (RE) ranged from −7.6% to 6.4% and the intra- and inter-day precisions were not more than 8.7% and 10.2%, respectively. Hence, the strategy proposed in this study might be used for high selectivity recognition and determination of CNs in complex biological matrices, which would provide a basis and reference for its application in the fields of separation and clinical monitoring.

Application of surface-imprinted polymers supported by hydroxyapatite in the extraction of zearalenone in various cereals

Surface-imprinted polymers supported by hydroxyapatite (HAP@MIPs) were prepared using coumarin-3-carboxylic acid and naringenin as dummy template molecules of zearalenone (ZEA). HAP@MIPs were characterized by Fourier-transform infrared spectroscopy, scanning electron microscopy, particle size distribution analysis, energy-dispersive X-ray spectroscopy, and X-ray diffraction. The adsorption performance was studied. The results showed that it could reach the adsorption equilibrium within 6min. The adsorption amount could reach 6.77μgmg-1, while the concentration was 20μgmL-1. The self-made solid-phase extraction (SPE) columns were prepared with HAP@MIPs as sorbents for the separation and purification of ZEA in cereal samples. The method was established by high-performance liquid chromatography (HPLC). The recoveries were in the range of 70.09-101.88%; the relative standard deviation was 2.06-8.47%. Finally, millet, coix lachryma, and corn were placed under extreme conditions to produce ZEA. The method was used to extract and analyze ZEA in the above samples. The results showed that self-made SPE columns with HPLC could be used for the separation and enrichment of ZEA in real samples. Graphical abstract.

Dummy template surface molecularly imprinted polymers based on silica gel for removing imidacloprid and acetamiprid in tea polyphenols.

Dummy template surface molecularly imprinted polymers based on silica gel were prepared through the surface molecular imprinting technique. Nonpoisonous nicotinamide, which is a structural analogue of imidacloprid and acetamidine, was chosen as the dummy template molecule. The obtained polymers were characterized using scanning electron microscopy, Fourier transform infrared spectroscopy, and X-ray diffraction. The results showed that the polymers exhibited high adsorption capacity and selectivity for imidacloprid and acetamiprid. The maximum adsorption capacities of the polymers toward imidacloprid and acetamiprid were 42.05 and 22.99mg/g, and the adsorption could reach binding equilibrium within 150min. The polymers were successfully applied as column-filling materials to extract imidacloprid and acetamiprid from tea polyphenols with a relatively high removal rate (92.36 and 95.20%). The polymers also showed great stability and reusability during the application. The obtained polymers possessed good application prospects for removing imidacloprid and acetamiprid in tea polyphenol production processes.

The preparation and evaluation of core-shell magnetic dummy-template molecularly imprinted polymers for preliminary recognition of the low-mass polybrominated diphenyl ethers from aqueous solutions

The design, preparation process, binding abilities, morphological characteristic and prospective field of application of dummy-template magnetic molecularly imprinted polymer (DMMIP) for preliminary recognition of the selected low-mass polybrominated diphenyl ethers (PBDE-47 and PBDE-99) from aquatic environment were investigated. The surface of iron oxide (Fe3O4) nanopowder (50–100 nm particles size) was modified with tetraethoxysilane and next prepared Fe3O4@SiO2 particles were dispersed in anhydrous toluene functionalized by (3-aminopropyl)triethoxysilane. Finally, MIPs' thin film layer on the surface of Fe3O4@SiO2@NH2 was formed in acetonitrile as a solvent solution, using ethylene glycol dimethacrylate as the cross-linker, building monomer, 1,1′-Azobis(cyclohexanecarbonitrile) as the radical initiator, methacrylic acid as a functional monomer and 4,4′-Dihydroxydiphenyl ether as the dummy template molecule as a structural analogue of low-mass PBDEs. To characterize the chemical structure of prepared DMMIPs, the Fourier transform infrared spectroscopy analysis was performed. The specific surface area of the developed sorbent was estimated using Brauner-Emmet-Teller nitrogen adsorption/desorption analysis. To assess the average pore sizes, pore diameters and pore volumes of the prepared sorbent, the Barret-Joyner-Halenda technique was applied. The average values of imprinting factor for PBDE-47 and PBDE-99 were 11.3 ± 1.6 and 13.7 ± 1.2, respectively. The average value of recovery of PBDE-47 and PBDE-99 for developed DMMIPs from modelling water: methanol solution were 85.4 ± 6.7% and 86.4 ± 9.4%, respectively. In a case of spiked distilled water, tap water as well as local river water the calculated recovery values ranged from 65%% up to 82% and from 33% up to 76% for PBDE-47 and PBDE-99, respectively. Following the preliminary research on selected water samples, the proposed combination of imprinting technology and core–shell materials with magnetic properties might be considered as a promising sorption tool used for targeted recognition of low-mass PBDEs in aquatic solutions.

Preparation of dummy molecularly imprinted polymers based on dextran-modified magnetic nanoparticles Fe3O4 for the selective detection of acrylamide in potato chips

Novel dummy magnetic molecularly imprinted polymers (dex-MMIPs) were prepared for highly selective recognition and fast enrichment of acrylamide (AA) in potato chips. Propionamide (PA) was used as dummy template molecule and the Fe3O4 nanoparticles modified with carboxymethyl dextran were developed as supports. Methacrylic acid (MAA) and ethyleneglycoldimethacrylate (EGDMA) were chosen as the functional monomer and cross-linker, respectively. Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), and transmission electron microscopy (TEM) were used to characterize the synthesized dex-MMIPs. The adsorption of dex-MMIPs reached equilibrium within 20 min, and the maximum adsorption quantity (Qm) was 19.28 mg/g with the dissociation constant (Kd) of 35.7 mg/L. Moreover excellent recognition toward acrylamide was achieved compared to analogs, such as N, N′-methylenebisacrylamide (MBA) and nicotinamide (VPP). The satisfactory recoveries of 83.9–96.8% were achieved for selective separation and enrichment of AA in spiked potato chips by dex-MMIPs.

Research progress of dummy template molecularly imprinted polymers in separation of natural products

The dummy template molecularly imprinted polymers not only has such characteristics of normal imprinted polymers as rapid identification, easy preparation, stable structure and multiple reuse, but also can imprint the compounds in natural products that are not suitable as direct template. Therefore, it has drawn more and more attention in the field of the study of natural products. This paper summarizes the methods for the selection of dummy template molecules by investigating the relevant literatures in the past ten years, analyzes the advantages and disadvantages of dummy template molecules in the practical application, and based on the types of natural products active ingredients, this paper is the first to review of the latest progress in extraction and separation of dummy template molecularly imprinted polymers. We believed that this paper could provide references for better applications of the dummy template molecularly imprinted polymers to extract and separate natural products.

Separation and determination of alkylamides from prickly ash powder using molecularly imprinting technique

In this work, a molecularly imprinted polymer solid phase extraction method was developed to extract Zanthoxylum alkylamides from prickly ash. Surface molecularly imprinted polymers (SMIP) were prepared using the molecular structural analogs of sanshool as a dummy template molecule and acylated silica as backbone. The structural characteristics of the polymers were determined by Fourier-transform infrared spectroscopy and scanning electron microscopy. Dynamic adsorption and isothermal adsorption were investigated. SMIP was used to prepare a molecularly imprinted solid-phase extraction column (SPEC) for the extraction of Zanthoxylum alkylamides from prickly ash powder, followed by high performance liquid chromatography (HPLC) determination. Through separation by SMIP-SPEC, the purity of alkylamides in prickly ash extracts increased from 27.26%–93.58 %. Good linearity for alkylamides standard solution was obtained in the range of 1.0–800.0 μg/mL, and low detection and quantification limits were 0.044 and 0.147 μg/mL, respectively. The method recoveries at four concentration levels of alkylamides were found within 90.3−97.1 % with relative standard deviations (RSDs) of 2.5%–5.9%. These indicate the good recognition ability and affinity to Zanthoxylum alkylamides of SMIP and the novelty of the method for the extraction of alkylamides. The method described could be used for the enrichment of alkylamides and rapid detection.

The determination of patulin from food samples using dual-dummy molecularly imprinted solid-phase extraction coupled with LC-MS/MS

A molecularly imprinted polymer (MIP) with specific adsorption for patulin was successfully polymerized by precipitation polymerization using 2-oxindole (2-oxin) and 6-hydroxynicotinic acid (6-HNA) as dummy template molecules, methylacrylic acid (MAA) as a functional monomer, trimethylolpropane trimethacrylate (TRIM) as a crosslinker, 2,2-azobis-(2-methylpropionitrile) (AIBN) as a initiator, and methanol as a porogen solvent. The molecularly imprinted solid phase extraction (MI-SPE) column was prepared using the polymer as a sorbent and applied for the selective extraction of patulin from real samples. The results showed that the MI-SPE method had high selectivity and specific adsorption towards patulin with mean recoveries ranged between 81.3% and 106.3% and a relative standard deviation (RSD) < 4.5%. Additionally, the developed MI-SPE method coupled with liquid chromatography-tandem mass spectrometry (LC-MS/MS) exhibited good linearity in the range of 1–100 ng mL−1 with correlation coefficients (R2) >0.998. The limits of detection (LODs, S/N = 3) were 0.05–0.2 ng g−1, and the limits of quantification (LOQs, S/N = 10) were 0.2–0.5 ng g−1. The developed method showed a better purification and higher patulin recovery for real samples than the quick, easy, cheap, effective, rugged, safe “QuEChERS” method.

Trace analysis of estrogens in milk samples by molecularly imprinted solid phase extraction with genistein as a dummy template molecule and high-performance liquid chromatography–tandem mass spectrometry

Dummy molecularly imprinted polymer microspheres (DMIPMS) towards estrogens were synthesized by Pickering emulsion polymerization employing genistein (GEN) as a dummy template molecule. The FTIR analysis indicated the successful preparation of the imprinted polymers, and the characterization results of scanning electron microscopy and nitrogen adsorption desorption measurement indicated that the obtained DMIPMS are in possess of regular spherical shapes, porous structures and narrow diameter distribution, a BET surface area of 402.74 m2 g−1, a total pore volume of 0.568 cm3 g−1 and a pore diameter of 3.62 nm. The binding capacity and selectivity of DMIPMS were investigated in equilibrium binding experiments and chromatographic evaluation experiments through scatchard analysis and molecular imprinting factor (IF) analysis, respectively. The MIPs showed high binding capacity and excellent selectivity towards seven selected natural and synthetic estrogens, which are Estrone (E1), 17β-estradiol (βE2), estriol (E3), ethinylestradiol (EE2), dienestrol(DS), diethylstilbestrol (DES), and hexestrol (HEX). A method for selective determination of seven estrogens in milk samples via dummy molecularly imprinted solid phase extraction coupled with HPLC-MS/MS was developed, which showed good linearity from 2 to 500 µg L−1 with a correlation coefficient (R2) of more than 0.999. The detection limits were within the range of 0.10–0.35 µg L−1 and the recoveries of the seven estrogens at three spiking levels (10,100,250 µg L−1) ranged from 88.9% to 102.3% with relative standard deviation (RSD, n = 5) for intra-day and inter-day assays varied from 0.8% to 4.5%. The developed method is thus proven to be efficient and reliable for regular monitoring of trace estrogens in complex matrices such as milk samples.

Aflatoxins screening in non-dairy beverages by Mn-doped ZnS quantum dots – Molecularly imprinted polymer fluorescent probe

Synthesized molecularly imprinted polymer (MIP) materials have been anchored on the surface of PEG-Mn-doped ZnS quantum dots (QDs) to develop a fluorescence probe for aflatoxins (AFs) recognition/determination in non-dairy beverages. MIP synthesis used 5,7-dimethoxycoumarin (DMC) as a dummy template molecule, and methacrylic acid (MAA) as a functional monomer. Under optimized conditions (1.25 mL of 5 mg L−1 MIP-PEG-ZnS QDs solution, pH 5.0, and 12 min delay time before scanning), the prepared MIP-QDs composite was found to offer high affinity and selectivity for AFs (AFB1, AFB2, AFG1 and AFG2). A fast fluorimetric screening method (total AFs assessment) was therefore feasible. The limits of detection (LOD) and quantification (LOQ) were 0.016 and 0.053 mg L−1, respectively. Analytical recoveries (inter- and intra-day assays) were from 99 ± 4% to 107 ± 5%, with RSD (intra-day assay) lower than 13, and RSD (inter-day) lower than 7%. The optimized method was applied for total AFs assessment in several non-dairy beverage samples.