Search Results (31)

The application of microsphere molecularly imprinted materials for the targeted extraction and purification of flavonoids derived from agricultural waste has emerged as a prominent area of investigation. An innovative boronate affinity imprinted microsphere (MC-CD@BA-MIP) was successfully synthesized using the Pickering emulsion interfacial assembly strategy for the selective separation of naringin (NRG). The double-bond functionalized covalent organic framework (COF)-based microspheres were synthesized through Schiff–base reaction and secondary interfacial emulsion polymerization. Then, the synthetic mono-(6-mercapto-6-deoxy)-β-cyclodextrin (SH-β-CD) was grafted onto the surface of the microspheres (MC) using click chemistry. The 1-allylpyridine-3-boronic acid (APBA) as a functional monomer was grafted onto the initiator (ABIB) through atom transfer radical polymerization (ATRP). Ultimately, the synthesized boronic acid-imprinted ABIB-BA-MIPs were immobilized onto the COFs microsphere surface through host–guest interactions. As expected, under neutral conditions, the MC-CD@BA-MIPs still exhibited a significant adsorption capacity (38.78 μmol g⁻¹ at 308 K) for NRG. The regenerated MC-CD@BA-MIPs maintained 92.56% of their initial adsorption capacity through six consecutive cycles. Full article

The development of fluorescent sensors with high sensitivity and fast response times is attracting the interest of more and more researchers. Herein, dual-emission ratiometric molecularly imprinted fluorescent encoded microspheres were fabricated and applied for the fast detection of norfloxacin. Core–shell-structured imprinted polymers with ZIF-8 as the supporting core were obtained first and two quantum dots with green and red emission provided the fluorescent signal. The introduction of the optical encoding technique greatly simplified the preparation process. After the addition of NOR, the green intensity at 525 nm remained constant and the fluorescent intensity at 625 nm decreased significantly because of the inner filter effect. Under the optimum detection conditions, a good linear correlation ranged from 5 μg L⁻¹ to 500 μg L⁻¹, and the spiked recoveries of the method were 89.76%–106.94%. The detection limit for chicken, pork, fish, and milk samples was established at 2 μg L⁻¹. More importantly, the established sensor provided a faster mass transfer rate, and the detection process took only 15 min, indicating great potential as an alternative for the fast detection of NOR in food samples. Full article

Molecularly Imprinted Microspheres (MIMs) or Microsphere Molecularly Imprinted Polymers represent an innovative design for the selective extraction of active compounds from natural products, showcasing effectiveness and cost-efficiency. MIMs, crosslinked polymers with specific binding sites for template molecules, overcome irregularities observed in traditional Molecularly Imprinted Polymers (MIPs). Their adaptability to the shape and size of target molecules allows for the capture of compounds from complex mixtures. This review article delves into exploring the potential practical applications of MIMs, particularly in the extraction of active compounds from natural products. Additionally, it provides insights into the broader development of MIM technology for the purification of active compounds. The synthesis of MIMs encompasses various methods, including precipitation polymerization, suspension polymerization, Pickering emulsion polymerization, and Controlled/Living Radical Precipitation Polymerization. These methods enable the formation of MIPs with controlled particle sizes suitable for diverse analytical applications. Control over the template-to-monomer ratio, solvent type, reaction temperature, and polymerization time is crucial to ensure the successful synthesis of MIPs effective in isolating active compounds from natural products. MIMs have been utilized to isolate various active compounds from natural products, such as aristolochic acids from Aristolochia manshuriensis and flavonoids from Rhododendron species, among others. Based on the review, suspension polymerization deposition, which is one of the techniques used in creating MIPs, can be classified under the MIM method. This is due to its ability to produce polymers that are more homogeneous and exhibit better selectivity compared to traditional MIP techniques. Additionally, this method can achieve recovery rates ranging from 94.91% to 113.53% and purities between 86.3% and 122%. The suspension polymerization process is relatively straightforward, allowing for the effective control of viscosity and temperature. Moreover, it is cost-effective as it utilizes water as the solvent. Full article

The residues of progestins in milk are significant risk factors for teenage acne and may cause hormone-dependent cancers in consumers, so the determination of these residues in milk is very important. However, an immunoassay or immunoassay-like method capable of determining multiple progestins in milk has not been reported so far. The present study, for the first time, synthesized a type of magnetic molecularly imprinted microsphere that was capable of simultaneously recognizing five progestins. At the same time, an enzyme labeled conjugate was synthesized by coupling progesterone 3-(o-carboxymethyl)oxime with streptavidinated horseradish peroxidase. The above two reagents were used to develop a semi-homogeneous method for the simultaneous detection of the residues of the five progestins in milk. During the experiments, biotinylated horseradish peroxidase was used to amplify the signal, so the sensitivity to the five drugs (limits of detection 0.04–0.1 pg/mL) was increased 44–75-fold. In addition, the magnetic molecularly imprinted microsphere could be regenerated four times by using simple elution. Through general comparison of its detection spectrum, sensitivity, simplicity, and reusability, the present method exhibited better performance than the previous immunoassays for the detection of progestins, and so it could be used as a routine tool for the screening of progestins residues in milk. Full article

Quercetin is a kind of flavonoid compound, which has antioxidative, anti-aging and anti-cancer effects, so it is of great importance to study the efficient extraction and highly sensitive detection of quercetin. Molecular imprinting technology has remarkable selectivity and resistance to complex matrix interference, which is often used for extracting quercetin. The methods of molecular imprinted solid phase extraction, molecularly imprinted microsphere extraction, molecularly imprinted electrochemical sensor recognition and molecularly imprinted composite material extraction of quercetin from plant samples were discussed in detail. This review provides valuable information on efficient and sensitive methods for separating and purifying quercetin in plants. It also provides a technical reference for further investigation of the separation and analysis of active ingredients in natural products. Full article

The detection of human serum albumin (HSA) is of significant clinical importance in disease diagnoses. In this work, polymer-based synthetic receptors are designed by incorporating Ag-ZnS microspheres in molecularly imprinted poly(methacrylic acid-co-ethylene glycol dimethacrylate) (MIPs) for the gravimetric detection of HSA. Among different compositions of Ag-ZnS@MIPs, MIPs having methacrylic acid and ethylene glycol dimethacrylate volume ratio of 3:2 exhibit enhanced HSA sensitivity in the concentration range of 5–200 ng/mL. A remarkably low threshold limit of detection (LOD = 0.364 ng/mL) is achieved with quartz crystal microbalance (QCM) based gravimetric sensors. Furthermore, the Ag-ZnS@MIPs/QCM sensors show high selectivity for HSA compared to other proteins, e.g., bovine serum albumin (BSA), glycoprotein, ribonuclease, and lysozyme. Hence, the gravimetric quantification of HSA realizes a highly sensitive, selective, and label-free detection mechanism with a limit of quantification down to 1.1 ng/mL. Full article

The choice of carrier material is critical in the study of natural drug release preparations and glycosylated magnetic molecularly imprinted materials. The stiffness and softness of the carrier material affect the efficiency of drug release and the specificity of recognition. The dual adjustable aperture-ligand in molecularly imprinted polymers (MIPs) provides the possibility of individualized design for sustained release studies. In this study, a combination of paramagnetic Fe₃O₄ and carboxymethyl chitosan (CC) was used to enhance the imprinting effect and improve drug delivery. A combination of tetrahydrofuran and ethylene glycol was used as a binary porogen to prepare MIP-doped Fe₃O₄-grafted CC (SMCMIP). Salidroside serves as the template, methacrylic acid acts as the functional monomer, and ethylene glycol dimethacrylate (EGDMA) serves as the crosslinker. Scanning and transmission electron microscopy were used to observe the micromorphology of the microspheres. The structural and morphological parameters of the SMCMIP composites were measured, including the surface area and pore diameter distribution. In an in vitro study, we found that the SMCMIP composite had a sustained release property of 50% after 6 h of release time in comparison to the control SMCNIP. The total amounts of SMCMIP released at 25 °C and 37 °C were 77% and 86%, respectively. In vitro results showed that the release of SMCMIP followed Fickian kinetics, meaning that the rate of release is dependent on the concentration gradient, with diffusion coefficients ranging from 3.07 × 10⁻² cm²/s to 5.66 × 10⁻³ cm²/s. The results of cytotoxicity experiments showed that the SMCMIP composite did not have any harmful effects on cell growth. The survival rates of intestinal epithelial cells (IPEC-J2) were found to be above 98%. By using the SMCMIP composite, drugs may be delivered in a sustained manner, potentially leading to improved therapeutic outcomes and reduced side effects. Full article

In view of the great threat of chloramphenicol (CAP) to human health and the fact that a few producers have illegally used CAP in the food production process to seek economic benefits in disregard of laws and regulations and consumer health, we urgently need a detection method with convenient operation, rapid response, and high sensitivity capabilities to detect CAP in food to ensure people’s health. Herein, a molecularly imprinted polymer (MIP) electrochemical sensor based on a dual-signal strategy was designed for the highly sensitive analysis of CAP in milk. The NiFe Prussian blue analog (NiFe-PBA) and SnS₂ nanoflowers were modified successively on the electrode surface to obtain dual signals from [Fe(CN)₆]^3−/4− at 0.2 V and NiFe-PBA at 0.5 V. SiO₂-COOH@MIPs that could specifically recognize CAP were synthesized via thermal polymerization using carboxylated silica microspheres (SiO₂-COOH) as carriers. When the CAP was adsorbed by SiO₂-COOH@MIPs, the above two oxidation peak currents decreased at the same time, allowing the double-signal analysis. The SiO₂-COOH@MIPs/SnS₂/NiFe-PBA/GCE sensor used for determining CAP was successfully prepared. The sensor utilized the interactions of various nanomaterials to achieve high-sensitivity dual-signal detection, which had certain innovative significance. At the same time, the MIPs were synthesized using a surface molecular imprinting technology, which could omit the time of polymerization and elution and met the requirements for rapid detection. After optimizing the experimental conditions, the detection range of the sensor was 10⁻⁸ g/L–10⁻² g/L and the limit of detection reached 3.3 × 10⁻⁹ g/L (S/N = 3). The sensor had satisfactory specificity, reproducibility, and stability, and was successfully applied to the detection of real milk samples. Full article

The development of complex biological sample-compatible fluorescent molecularly imprinted polymers (MIPs) with improved performances is highly important for their real-world bioanalytical and biomedical applications. Herein, we report on the first hydrophilic “turn-on”-type fluorescent hollow MIP microparticles capable of directly, highly selectively, and rapidly optosensing hippuric acid (HA) in the undiluted human urine samples. These fluorescent hollow MIP microparticles were readily obtained through first the synthesis of core-shell-corona-structured nitrobenzoxadiazole (NBD)-labeled hydrophilic fluorescent MIP microspheres by performing one-pot surface-initiated atom transfer radical polymerization on the preformed “living” silica particles and subsequent removal of their silica core via hydrofluoric acid etching. They showed “turn-on” fluorescence and high optosensing selectivity and sensitivity toward HA in the artificial urine (the limit of detection = 0.097 μM) as well as outstanding photostability and reusability. Particularly, they exhibited much more stable aqueous dispersion ability, significantly faster optosensing kinetics, and higher optosensing sensitivity than their solid counterparts. They were also directly used for quantifying HA in the undiluted human urine with good recoveries (96.0%–102.0%) and high accuracy (RSD ≤ 4.0%), even in the presence of several analogues of HA. Such fluorescent hollow MIP microparticles hold much promise for rapid and accurate HA detection in the clinical diagnostic field. Full article

The possibility of generating organically modified hollow TiO₂ microspheres via a simple sol-gel synthesis was demonstrated for the first time in this work. A mixture of titania precursors, including an organically modified precursor, was used to obtain methyl-modified hollow TiO₂ microspheres selective for bilirubin by the molecular imprinting technique (Methyl-HTM-MIM). Methyl-HTM-MIM were prepared by a sol-gel method using titanium (IV) isopropoxide (TTIP), and methyltitanium triisopropoxide (MTTIP) as precursors. Two ratios of titania precursors were tested (1/6 and 1/30 mol_MTTIP/mol_TTIP). With the characterization results obtained by the SEM and ATR-FTIR techniques, it was possible to establish that only the 1/30 mol_MTTIP/mol_TTIP ratio allowed for the preparation of hollow spheres with a reasonably homogeneous methylated-TiO₂ shell. It was possible to obtain a certain degree of organization of the hybrid network, which increased with calcination temperatures. By adjusting isothermal adsorption models, imprinting parameters were determined, indicating that the new methylated microspheres presented greater selectivity for bilirubin than the totally inorganic hollow TiO₂ microspheres. The effectiveness of the molecular imprinting technique was proven for the first time in an organically modified titania material, with imprinting factor values greater than 1.4, corresponding to a significant increase in the maximum adsorption capacity of the template represented by the molecularly imprinted microspheres. In summary, the results obtained with the new methyl-HTM-MIM open the possibility of exploring the application of these microspheres for selective sorption (separation or sensing, for example) or perhaps even for selective photocatalysis, particularly for the degradation of organic compounds. Full article

Hollow mesoporous silica nanoparticles have been widely applied as a carrier material in the molecular imprinting process because of their excellent properties, with high specific surface area and well-defined active centers. However, these kinds of materials face the inevitable problem that they have low mass transfer efficiency and cannot be conveniently recycled. In order to solve this problem, this work has developed a composite hydrogel microsphere (MMHSG) encapsulated with hollow mesoporous imprinted nanoparticles for the selective extraction of 2’-deoxyadenosine (dA). Subsequently, the hollow mesoporous imprinted polymers using dA as template molecule and synthesized 5-(2-carbomethoxyvinyl)-2′-deoxyuridine (AcrU) as functional monomer were encapsulated in hydrogel. MMHSG displayed good performance in specifically recognizing and quickly separating dA, whereas no imprinting effect was observed among 2′-deoxyguanosine (dG), deoxycytidine (dC), or 5′-monophosphate disodium salt (AMP). Moreover, the adsorption of dA by MMHSG followed chemisorption and could reach adsorption equilibrium within 60 min; the saturation adsorption capacity was 20.22 μmol·g⁻¹. The introduction of AcrU could improve selectivity through base complementary pairing to greatly increase the imprinting factor to 3.79. Therefore, this was a successful attempt to combine a hydrogel with hollow mesoporous silica nanoparticles and molecularly imprinted material. Full article

An electrochemical sensor based on a molecularly imprinted polymer membrane (MIP) was developed. The electrochemical sensor was prepared by electropolymerization of o-phenylenediamine (O-PD) on the surface of glassy carbon electrode (GCE), modified by AuNPs@covalent organic framework (COF) microspheres with ascorbic acid (AA) as template molecule. First, ultrasmall polyvinylpyrrolidone (PVP)-coated AuNPs were prepared by a chemical reduction method. Then, 1,3,5-tri(p-formylphenyl)benzene (TFPB) and N-boc-1,4-phenylene diamine (NBPDA) underwent an ammonaldehyde condensation reaction on PVP-coated AuNPs to form AuNPs@COF_TFPB-NBPDA microspheres. The porous spherical structure of AuNPs@ COF_TFPB-NBPDA could accelerate the mass transfer, enlarge the specific surface area, and enhance the catalytic activity of PVP-coated AuNPs. The electrochemical sensors, based on AuNPs@ COF_TFPB-NBPDA/GCE and nMIPs/AuNPs@COF_TFPB-NBPDA/GCE, were applied for the detection of AA, with a detection limit of 1.69 and 2.57 μM, as well as linear ranges of 5.07 to 60 mM and 7.81 to 60 mM. The nMIPs/AuNPs@COF_TFPB-NBPDA sensor had satisfactory stability, selectivity, and reproducibility for AA detection. Full article

Molecularly imprinted solid-phase extraction to treat biological samples has attracted considerable attention. Herein, molecularly imprinted polymer (MIP) microspheres with porous structures were prepared by a combined suspension-iniferter polymerization method using capecitabine (CAP) as a template molecule. This material was subsequently used as a solid-phase extraction agent to separate and enrich drug molecules in urine samples. UV analysis revealed that methacrylate (MAA) was an ideal functional monomer, and 1H Nuclear Magnetic Resonance (¹H NMR), Ultraviolet (UV), and Fourier transform-infrared (FT-IR) spectroscopic analyses were used to study the interaction forces between MAA and CAP, demonstrating that hydrogen bonding was the primary interaction force. MIPs with outstanding selectivity were successfully prepared, and the analysis of their surface morphology and chemical structure revealed a spherical morphology with small holes distributed across a rough surface. This surface morphology significantly reduced the mass transfer resistance of template molecules, providing an ideal template recognition effect. Using the molecularly imprinted solid-phase extraction method, CAP and the structural analog cytidine (CYT) were pretreated in urine samples and quantified by HPLC. The results showed that CAP and CYT recoveries reached 97.2% and 39.8%, respectively, with a limit of detection of 10.0–50.0 µg·mL⁻¹. This study provides a novel approach to drug molecule pretreatment that can be applied in drug separation and functional materials science fields. Full article

Imprinted materials possess designed cavities capable of forming selective interactions with molecules used in the imprinting process. In this work, we report the synthesis of 5-fluorouracil (5-FU)-imprinted microparticles and their application in prolonged drug delivery. The materials were synthesized using either ethylene glycol dimethacrylate (EGDMA) or trimethylolpropane trimethacrylate (TRIM) cross-linkers. For both types of polymers, methacrylic acid was used as a functional monomer, whereas 2-hydroxyethyl methacrylate was applied to increase the final materials’ hydrophilicity. Adsorption isotherms and adsorption kinetics were investigated to characterize the interactions that occur between the materials and 5-FU. The microparticles synthesized using the TRIM cross-linker showed higher adsorption properties towards 5-FU than those with EGDMA. The release kinetics was highly dependent upon the cross-linker and pH of the release medium. The highest cumulative release was obtained for TRIM-based microparticles at pH 7.4. The IC₅₀ values proved that 5-FU-loaded TRIM-based microparticles possess cytotoxic activity against HeLa cell lines similar to pure 5-FU, whereas their toxicity towards normal HDF cell lines was ca. three times lower than for 5-FU. Full article

Adsorption of urea from dialysate is essential for wearable artificial kidneys (WRK). Molecularly imprinted microspheres with nanoporous and multilayered structures are prepared based on liquid–liquid phase separation (LLPS), which can selectively adsorb urea. In addition, we combine the microspheres with a designed polydimethylsiloxane (PDMS) chip to propose an efficient urea adsorption platform. In this work, we propose a formulation of LLPS including Tripropylene glycol diacrylate (TPGDA), ethanol, and acrylic acid (30% v/v), to prepare urea molecularly imprinted microspheres in a simple and highly controllable method. These microspheres have urea molecular imprinting sites on the surface and inside, allowing selective adsorption of urea and preservation of other essential constituents. Previous static studies on urea adsorption have not considered the combination between urea adsorbent and WRK. Therefore, we design the platform embedded with urea molecular imprinted microspheres, which can disturb the fluid motion and improve the efficiency of urea adsorption. These advantages enable the urea absorption platform to be highly promising for dialysate regeneration in WRK. Full article