Search Results (29)

Multimetric indices play a pivotal role in assessing river ecological quality, aligning with the European Water Framework Directive (EU WFD) requirements. However, indices developed specifically for large rivers are uncommon. Our objective was to develop a fish-based tool specifically tailored to assess the ecological quality in Portuguese large rivers. Data were collected from seven sites in each of three Portuguese large rivers (Minho, Guadiana, and Tagus). Each site was classified using an environmental disturbance score, combining different pressure types, such as water chemistry, land use, and hydromorphological alterations. The Fish-based Multimetric Index for Portuguese Large Rivers (F-MMIP-LR) comprises four metrics: % native lithophilic individuals; % alien individuals; % migrant individuals; and % freshwater native individuals, representing compositional, reproductive, and migratory guilds. The index showed good performance in separating least- and most-disturbed sites. Least-disturbed sites were rated ‘high’ or ‘good’ by F-MMIP-LR, contrasting with no such classification for most-disturbed sites, highlighting index robustness. The three rivers presented a wide range of F-MMIP-LR values across the gradient of ‘bad’ to ‘high’, indicating that, on a large spatial extent, the biological condition was substantially altered. The F-MMIP-LR provides vital information for managers and decision-makers, guiding restoration efforts and strengthening conservation initiatives in line with the WFD. Full article

Molecularly imprinted polymers (MIPs), as magnetic extraction adsorbents, are used for the selective, rapid determination and extraction of dexamethasone and hydrocortisone in skincare products. Therefore, in this paper, magnetic molecularly imprinted polymers (MMIPs) and magnetic non-molecularly imprinted polymers (MNIPs) were utilized as adsorbents to describe the adsorption phenomena of dexamethasone and hydrocortisone. This interpretation, based on a statistical physics theory, applies the multilayer model with saturation to comprehend the adsorption of the drugs. Results obtained via numerical simulation revealed that dexamethasone and hydrocortisone adsorption happens via a non-parallel orientation on the surfaces of MMIPs and MNIPs, and they also showed that the adsorption amount of the MMIPs for the template molecule was notably greater than that of the MNIPs at the same initial concentration. The adsorption energy values retrieved from the data analysis ranged between 7.65 and 15.77 kJ/mol, indicating that the extraction and determination of dexamethasone and hydrocortisone is a physisorption process. Moreover, the distribution of a site’s energy was calculated to confirm the physical nature of the interactions between adsorbate/adsorbent and the heterogeneity of the surfaces of the MMIPs and MNIPs. Finally, the thermodynamic interpretation confirmed the exothermicity and spontaneous nature of the adsorption of these drugs on the tested adsorbents. Full article

Magnetic molecularly imprinted polymers (MMIPs) have fused molecular imprinting technology with magnetic separation technology, emerging as an innovative material capable of recognizing specific molecules and efficiently separating target substances. Their application to the extraction and purification of mycotoxins has great potential, due to the toxicity and economic impact of these contaminants. In this work, MMIP has been proposed as a sample treatment for the determination of main four aflatoxins (B₁, B₂, G₁ and G₂) in pig feed. The MMIP was formed through the integration of magnetic material (Fe₃O₄) with commercial molecularly imprinted polymers, avoiding the synthesis step and, therefore, simplifying the process. The analyses were carried out by high-performance liquid chromatography with fluorescence detection and the method was validated and limits of quantification (LOQs) between 0.09 and 0.47 ng/g were obtained, below the allowed or recommended levels by the European Union. Repeatability and intermediate precision showed relative standard deviations lower than 10% in all cases and trueness ranged from 92 to 111%. Finally, the proposed method was applied to 31 real pig feed samples, detecting aflatoxins with concentrations between 0.2 and 3.2 ng/g. Full article

Novel core–shell magnetic molecularly imprinted polymers (MMIPs) were synthesized using the sol–gel method for the adsorption of cefixime (CFX). Fe₃O₄@SiO₂ is the core, and molecularly imprinted polymers (MIPs) are the shell, which can selectively interact with CFX. The preparation conditions, adsorption kinetics, adsorption isotherms, selective adsorption ability, and reutilization performance of the MMIPs were investigated. The adsorption capacity of MMIPs for CFX was 111.38 mg/g, which was about 3.5 times that of MNIPs. The adsorption equilibrium time was 180 min. The dynamic adsorption experiments showed that the adsorption process of MMIPs to CFX conformed to the pseudo-second-order model. Through static adsorption study, the Scatchard analysis showed that MMIPs had two types of binding sites—the high-affinity binding sites and the low-affinity binding sites—while the Langmuir model fit the adsorption isotherms well (R² = 0.9962). Cefepime and ceftiofur were selected as the structural analogs of CFX for selective adsorption studies; the adsorption of CFX by MMIPs was higher than that of other structural analogs; and the imprinting factors of CFX, cefepime, and ceftiofur were 3.5, 1.7, and 1.4, respectively. Furthermore, the MMIPs also showed excellent reusable performance. Full article

Hybrid magnetic molecularly imprinted polymers (MMIPs) have the advantages of the technology of molecularly imprinted material and magnetic nanoparticles. The magnetic properties of MMIPs allow easy magnetic separation of various pollutants and analytes. A convenient and simple approach has been developed for the preparation of MMIPs based on polyamide (nylon-6) and magnetic nanoparticles. The polymer matrix was formed during the transition of nylon-6 from a dissolved state to a solid state in the presence of template molecules and Fe₃O₄ nanoparticles in the initial solution. Methylene blue (MB) was used as a model imprinted template molecule. The MMIPs exhibited a maximum adsorption amount of MB reached 110 µmol/g. The selectivity coefficients toward MB structural analogs were estimated to be 6.1 ± 0.6 and 2.1 ± 0.3 for 15 μM hydroxyethylphenazine and toluidine blue, which shows high MMIP selectivity. To prove the MMIPs’ specificity in MB recognition, magnetic nonimprinted polymers (MNIPs) were synthesized without the presence of a template molecule. MMIPs exhibited much higher specificity in comparison to MNIPs. To show the remarkable reusability of the MMIP sorbent, more than four MB absorption and release cycles were carried out, demonstrating almost the same extraction capacity step by step. We believe that the proposed molecular imprinting technology, shown in the MB magnetic separation example, will bring new advances in the area of MMIPs for various applications. Full article

Magnetic molecularly imprinted polymers (MMIPs) contain the predesigned specialized recognition capability that can be chosen to build credible functional materials, that are easy to handle and have a good degree of specificity. Hence, the given piece of work is intended to design a novel electrochemical sensor incorporating magnetite-based molecularly imprinted polymers. The building materials consisted of a cross-linker (EGDMA), reaction-initiator (AIBN), monomer (methylene succinic acid-MSA), and template molecule (Sunset Yellow-SY dye). MMIPs exhibited a diameter of 57 nm with an irregular shape due to the presence of cavities based on SEM analysis. XRD patterns exhibited crystallinity, as well as amorphous peaks that are attributed to polymeric and non-polymeric frameworks of MMIPs. The crystallite size of the MMIPs from XRD analysis was found to be 16.28 nm based on the Debye-Scherrer’s equation. Meanwhile, the FTIR bands showed the synthesis of MMIPs using monomer and methylene succinic acid. The sorption data at the optimized operating conditions (pH 2, sorbent dosage 3 mg, time 18 min) showed the highest sorption capacity of 40 mg/g. The obtained data best fitted to the Langmuir sorption isotherm and followed the pseudo-second-order kinetics. The magneto-sensors were applied for ultrasensitive, rapid, and simple sensing of SY dye. The electrochemical experiments were run at the operating condition range of (scan rate 10–50 mV/s, tads 0–120 s, pH 5–9, potential range 1–1.5 V for CV and 1–1.3 V for SWAdASV). The linear range of detection was set to 1.51 × 10⁻⁶ M to 1.51 × 10⁻⁶ M posing LOD and LOQ values of 8.6242 × 10⁻⁵ M and 0.0002874 M, respectively. The regression analysis value for the calibration was found to be 0.950. Additionally, high adsorption efficiency, selectivity, reusability, and strong structural stability of the magneto-sensors showed potential use for SY detection in real samples. These characteristics make MMIPs a viable electrochemical substrate for the detection of chemical contaminants in the environment and in health-related products. Full article

Tolfenpyrad, a pyrazolamide insecticide, can be effectively used against pests resistant to carbamate and organophosphate insecticides. In this study, a molecular imprinted polymer using tolfenpyrad as a template molecule was synthesized. The type of functional monomer and the ratio of functional monomer to template were predicted by density function theory. Magnetic molecularly imprinted polymers (MMIPs) were synthesized using 2-vinylpyridine as a functional monomer in the presence of ethylene magnetite nanoparticles at a monomer/tolfenpyrad ratio of 7:1. The successful synthesis of MMIPs is confirmed by the results of the characterization analysis by scanning electron microscopy, nitrogen adsorption–desorption isotherms, Fourier transform infrared spectroscopy, X-ray diffractometer, thermogravimetric analyzer, and vibrational sample magnetometers. A pseudo-second-order kinetic model fit the adsorption of tolfenpyrad, and the kinetic data are in good agreement with the Freundlich isothermal model. The adsorption capacity of the polymer to the target analyte was 7.20 mg/g, indicating an excellent selective extraction capability. In addition, the adsorption capacity of the MMIPs is not significantly lost after several reuses. The MMIPs showed great analytical performance in tolfenpyrad-spiked lettuce samples, with acceptable accuracy (intra- and inter-day recoveries of 90.5–98.8%) and precision (intra- and inter-day relative standard deviations of 1.4–5.2%). Full article

Broad-spectrum antibiotics from the fluoroquinolone family have emerged as prominent water contaminants, among other pharmaceutical pollutants. In the present study, an antibacterial magnetic molecularly imprinted polymer (MMIP) composite was successfully fabricated using carboxy methyl dextrin grafted to poly(aniline-co-meta-phenylenediamine) in the presence of Fe₃O₄/CuO nanoparticles and ciprofloxacin antibiotic. The characteristics of obtained materials were investigated using FTIR, XRD, VSM, TGA, EDX, FE-SEM, zeta potential, and BETanalyses. Afterward, the MMIP’s antibacterial activity and adsorption effectiveness for removing ciprofloxacin from aqueous solutions were explored. The results of the antibacterial tests showed that MMIP had an antibacterial effect against Escherichia coli, a Gram-negative pathogen (16 mm), and Staphylococcus aureus, a Gram-positive pathogen (22 mm). Adsorption efficacy was evaluated under a variety of experimental conditions, including solution pH, adsorbent dosage, contact time, and initial concentration. The maximum adsorption capacity (Q_max) of the MMIP for ciprofloxacin was determined to be 1111.1 mg/g using 3 mg of MMIP, with an initial concentration of 400 mg/L of ciprofloxacin at pH 7, within 15 min, and agitated at 25 °C, and the experimental adsorption results were well-described by the Freundlich isotherm model. The adsorption kinetic data were well represented by the pseudo-second-order model. Electrostatic interaction, cation exchange, π-π interactions, and hydrogen bonding were mostly able to adsorb the majority of the ciprofloxacin onto the MMIP. Adsorption–desorption experiments revealed that the MMIP could be retrieved and reused with no noticeable reduction in adsorption efficacy after three consecutive cycles. Full article

Long-term use of norfloxacin (NOR) will cause NOR residues in foods and harm human bodies. The determination of NOR residues is important for guaranteeing food safety. In this study, a simple, selective, and label-free colorimetric chemosensor for in situ NOR detection was developed based on Fe₃O₄ magnetic molecularly imprinted nanoparticles (Fe₃O₄ MMIP NPs). The Fe₃O₄ MMIP NPs showed good peroxidase-like catalytic activity to 3,3′,5,5′-tetramethylbenzidine (TMB) and selective adsorption ability to NOR. The colorimetric chemosensor was constructed based on the Fe₃O₄ MMIP NPs-H₂O₂-TMB reaction system. The absorbance differences were proportional to the concentrations of NOR in the range of 10–300 ng/mL with a limit of detection at 9 ng/mL. The colorimetric chemosensor was successfully applied to detect NOR residue in milk. The recovery range was 78.2–95.81%, with a relative standard deviation of 2.1–9.88%. Together, the proposed colorimetric chemosensor provides a reliable strategy for the detection of NOR residues in foods. Full article

Magnetic nanocomposites (MNCs) combine the features of magnetic nanoparticles and a second material, which provide distinct physical, chemical, and biological properties. The magnetic core for nanocomposite synthesis is extensively used due to its high saturation magnetization, chemical stability, large surface area, and easy functionalization. Moreover, magnetic nanoparticles (MNPs) have great potential for magnetic resonance imaging (MRI), magnetic particle imaging (MPI), hyperthermia, and targeted drug and gene delivery by an external magnetic field. Numerous composing units exist, which leads to the outstanding application of composites. This review focuses on nucleic acid-based bioapplications of MNCs with polymeric, organic, inorganic, biomolecules, and bioinspared surface coating. In addition, different forms, such as core–shell, doping, multilayer, yolk–shell, and Janus-shaped hybrids, are discussed, and their unique properties are highlighted. The unique types of nanocomposites as magnetic molecularly imprinted polymer (MMIP) properties are presented. This review presents only the synthesis of MNCs using ready-made magnetic cores. These restrictions are associated with many materials, the quantitative and qualitative magnetic core composition, and synthesis procedures. This review aims to discuss the features of nucleic acid-based MNC information available to researchers in this field and guide them through some problems in the area, structure variation, and surface functionalization possibilities. The most recent advancements of MNCs and imprinted polymers in nucleic acid-based therapy, diagnostics, theranostics, magnetic separation, biocatalytic, and biosensing are introduced. Full article

In this paper, magnetic molecularly imprinted polymers (MMIPs) were fabricated on the surface of Fe₃O₄ by surface molecular imprinting technology, which can selectively adsorb 17β-estradiol (E2). The optimized experiments demonstrated that MMIPs possessed the best adsorption capacity when methanol was used as the solvent and MAA was used as the crosslinking agent, with a molar ratio of E2: MMA: EGDMA as 1:4:50. SEM, FTIR, and XRD were employed to investigate the morphologies of MMIPs and the results demonstrated that the MMIPs that can selectively adsorb E2 were successfully prepared on Fe₃O₄ particles. The adsorption experiments showed that 92.1% of E2 was adsorbed by the MMIPs, which is higher than the magnetic non-molecularly imprinted polymers (MNIPs). The Freundlich isotherm model was more suitable to describe the adsorption process of E2 by MMIPs. Meanwhile, MMIPs had a better recognition ability for E2 and its structural analogs such as estrone and estriol. The MMIPs still had good adsorption performance after methanol regeneration five times. The prepared MMIPs had the advantages of efficient adsorption ability and high reusability, so they can be applied for selective recognition and removal of E2. Full article

The present study reports the development and application of a novel, sensitive, and selective voltammetric sensor for the quantitation of folate or vitamin B₉ in foodstuffs. The sensor was made from magnetic molecularly imprinted polymers (MMIPs), which were synthesized by the core–shell method using magnetite nanoparticles obtained by the polyol method. The MMIP-based sensor was used for the selective and specific detection of folate in different food samples. The MMIP material was constructed using magnetic water-dispersible nanomaterial, which was prepared by immersing iron (III) acetylacetonate in tri-ethylene-glycol (TEG) solvent. The magnetic water-dispersible nanomaterial was then subjected to polymerization using allyl alcohol as a functional monomer, ethylene-glycol-dimethacrylate (EGDMA) as a cross-linking agent, and 2,2-Azobisisobutyronitrile (AIBN) as a radical initiator. The proposed magnetic materials were characterized by Brunauer–Emmett–Teller (BET), field emission gun scanning electron microscopy (FEG-SEM), thermogravimetric analysis (TGA), and vibrating sample magnetometer (VSM) analysis. The quantification of folate was performed by square wave voltammetry under optimized conditions using 15 mg of MMIPs and 85 mg of carbon paste. The modified electrode presented a linear dynamic range (LDR) of 2.0–12 µmol L⁻¹ and a limit of detection (LOD) of 1.0 × 10⁻⁷ mol L⁻¹ in 0.1 mol L⁻¹ acetate buffer solution (pH 4.0). The proposed sensor was successfully applied for folate detection in different food samples, where recovery percentages ranging from 93 to 103% were obtained. Finally, the results obtained from the analysis of selectivity showed that the modified biomimetic sensor is highly efficient for folate determination in real food samples. Adsorption tests were used to evaluate and compare the efficiency of the MMIPs and magnetic non-molecularly imprinted polymer (MNIPs)—used as control material, through the application of HPLC as a standard method. Full article

In this work, novel selective recognition materials, namely magnetic molecularly imprinted polymers (MMIPs), were prepared. The recognition materials were used as pretreatment materials for magnetic molecularly imprinted solid-phase extraction (MSPE) to achieve the efficient adsorption, selective recognition, and rapid magnetic separation of methotrexate (MTX) in the patients’ plasma. This method was combined with high-performance liquid chromatography–ultraviolet detection (HPLC–UV) to achieve accurate and rapid detection of the plasma MTX concentration, providing a new method for the clinical detection and monitoring of the MTX concentration. The MMIPs for the selective adsorption of MTX were prepared by the sol–gel method. The materials were characterized by transmission electron microscopy, Fourier transform-infrared spectrometry, X-ray diffractometry, and X-ray photoelectron spectrometry. The MTX adsorption properties of the MMIPs were evaluated using static, dynamic, and selective adsorption experiments. On this basis, the extraction conditions were optimized systematically. The adsorption capacity of MMIPs for MTX was 39.56 mgg⁻¹, the imprinting factor was 9.40, and the adsorption equilibrium time was 60 min. The optimal extraction conditions were as follows: the amount of MMIP was 100 mg, the loading time was 120 min, the leachate was 8:2 (v/v) water–methanol, the eluent was 4:1 (v/v) methanol–acetic acid, and the elution time was 60 min. MTX was linear in the range of 0.00005–0.25 mg mL⁻¹, and the detection limit was 12.51 ng mL⁻¹. The accuracy of the MSPE–HPLC–UV method for MTX detection was excellent, and the result was consistent with that of a drug concentration analyzer. Full article

Several degenerative disorders of the central nervous system, including Parkinson’s disease (PD), are related to the pathological aggregation of proteins. Antibodies against toxic disease proteins, such as α-synuclein (SNCA), are therefore being developed as possible therapeutics. In this work, one peptide (YVGSKTKEGVVHGVA) from SNCA was used as the epitope to construct magnetic molecularly imprinted composite nanoparticles (MMIPs). These composite nanoparticles were characterized by dynamic light scattering (DLS), high-performance liquid chromatography (HPLC), isothermal titration calorimetry (ITC), Brunauer–Emmett–Teller (BET) analysis, and superconducting quantum interference device (SQUID) analysis. Finally, the viability of brain endothelial cells that were treated with MMIPs was measured, and the extraction of SNCA from CRISPR/dCas9a-activated HEK293T cells from the in vitro model system was demonstrated for the therapeutic application of MMIPs. Full article

During the last few years, separation techniques using molecular imprinting polymers (MIPs) have been developed, making certain improvements using magnetic properties. Compared to MIP, Magnetic molecularly imprinted polymers (MMIPs) have high selectivity in sample pre-treatment and allow for fast and easy isolation of the target analyte. Its magnetic properties and good extraction performance depend on the MMIP synthesis step, which consists of 4 steps, namely magnetite manufacture, magnetic coating using modified components, polymerization and template desorption. This review discusses the factors that will affect the performance of MMIP as a selective sorbent at each stage. MMIP, using Fe₃O₄ as a magnetite core, showed strong superparamagnetism; it was prepared using the co-precipitation method using FeCl₃·6H₂O and FeCl₂·H₂O to obtain high magnetic properties, using NH₄OH solution added for higher crystallinity. In magnetite synthesis, the use of a higher temperature and reaction time will result in a larger nanoparticle size and high magnetization saturation, while a higher pH value will result in a smaller particle size. In the modification step, the use of high amounts of oleic acid results in smaller nanoparticles; furthermore, determining the correct molar ratio between FeCl₃ and the shielding agent will also result in smaller particles. The next factor is that the proper ratio of functional monomer, cross-linker and solvent will improve printing efficiency. Thus, it will produce MMIP with high selectivity in sample pre-treatment. Full article