Molecular Imprinting Strategy Research Articles

An electrochemical sensor based on carbon nanofiber and molecular imprinting strategy for dasatinib recognition

Herein, we proposed a new approach to design a MIP-based electrochemical sensor with carbon nanofiber (CNF), which could improve its conductivities as well as electrode sensitivity and successful detection of dasatinib (DAS). CNFs are capable of forming high porosity with significant interconnected porous networks. The poly(2-hydroxyethyl-methacrylate-N-methacryloyl-L-tyrosine) (PHEMA-MATyr) copolymer was synthesized in the presence of both CNF and DAS by photopolymerization. After optimization of the parameters, the modified MIP-based electrochemical sensor demonstrated the ability to determine the DAS in the linear working range of 1.0 × 10−14–1.0 × 10–13 M for the standard solution and commercial serum samples with a LOD of 1.76 × 10−15 and 2.46 × 10−15, respectively. Good linearity for DAS was observed with correlation coefficients (r) of 0.996 and 0.997 for the standard solution and commercial serum samples, respectively. The recoveries of the DAS ranged from 99.45 % to 99.53 % for the tablet dosage form and commercial serum samples, with average relative standard deviations below 1.96 % in both cases. The proposed modified sensor demonstrated significant sensitivity and selectivity for the rapid determination of DAS in commercial serum samples and tablet form.

Precise selection and separation of ribavirin by nanoconfined imprinted MOFs membrane

Metal-organic frameworks (MOFs) are highly tunable materials with potential as porous media in membrane separations. However, traditional MOFs are usually not specific and selective. Here, we demonstrate a nanocomposite molecularly imprinted MOFs membrane material that can selectively adsorb and separate specific molecules. We demonstrated this adsorption-separation mechanism by introducing ribavirin molecules into multicomponent MOFs by molecular imprinting strategy and performing permeation and dynamic permeation tests. Due to the previously formed nanocages with a specific structure inside the MOFs, combined with the synergistic effect of the subsequent secondary imprinting, excellent selectivity (more than 6) and effective adsorption (46.46 mg g−1) were displayed by the obtained imprinted membrane. The stability of the membrane was measured by the process of dynamic osmosis, and the results showed that the membrane always had a large factor of separation (greater than 7). The experimental results and conclusions of this paper provide new theoretical and practical support for solving the key scientific issues of the “trade-off” effect between the permeation flux and permeation selectivity of template molecules in the traditional molecularly imprinted membranes (MIMs) osmotic separation process.

Molecular Imprinting Technology Enables Proactive Capture of Nitrogen for Boosted Ammonia Synthesis under Ambient Conditions.

Electrochemical nitrogen reduction reaction (NRR) is a burgeoning field for green and sustainable ammonia production, in which numerous potential catalysts emerge endlessly. However, satisfactory performances are still not realized under practical applications due to the limited solubility and sluggish diffusion of nitrogen at the interface. Herein, molecular imprinting technology is adopted to construct an adlayer with abundant nitrogen imprints on the electrocatalyst, which is capable of selectively recognizing and proactively aggregating high-concentrated nitrogen at the interface while hindering the access of overwhelming water simultaneously. With this favorable microenvironment, nitrogen can preferentially occupy the active surface, and the NRR equilibrium can be positively shifted to facilitate the reaction kinetics. Approximately threefold improvements in both ammonia production rate (185.7µg h-1 mg-1 ) and Faradaic efficiency (72.9%) are achieved by a metal-free catalyst compared with the bare one. It is believed that the molecular imprinting strategy should be a general method to find further applicability in numerous catalysts or even other reactions facing similar challenges.

Fabrication of an electrochemical sensor based on molecular imprinting strategy for detecting salidroside

In recent years, molecular imprinting has emerged as a promising strategy for developing highly selective and sensitive sensors for various analytes. In this study, we present the fabrication and characterization of an electrochemical sensor based on the molecular imprinting strategy for the detection of salidroside, a bioactive compound found in Rhodiola rosea. The sensor employs a modified glassy carbon electrode functionalized with multi-walled carbon nanotubes (MWCNTs) as the working electrode. The molecularly imprinted polymer (MIP) was prepared using acrylamide as the functional monomer and MWCNTs as the supporting material. The MIP-based sensor exhibited exceptional sensitivity and selectivity towards salidroside, showing a linear correlation between the logarithm of salidroside concentration and the reduced peak current in the range of 1 nM to 1 μM, with a low detection limit of 0.51 nM. The sensor demonstrated excellent reproducibility and stability, with a relative standard deviation (RSD) of 3.1 % for parallel measurements and 94.8 % retained response after a 7-day storage period. The spiked recovery experiments for Rhodiola rosea samples yielded high accuracy and precision, with recovery rates ranging from 96 % to 99 % and RSDs of 1–4 %. The developed MIP-based electrochemical sensor offers a powerful and reliable approach for the detection of salidroside, holding great potential for applications in pharmaceutical and herbal medicine industries.

Construction of Highly Active and Selective Molecular Imprinting Catalyst for Hydrogenation.

Surface molecular imprinting (MI) is one of the most efficient techniques to improve selectivity in a catalytic reaction. Heretofore, a prerequisite to fabricating selective catalysts by MI strategies is to sacrifice the number of surface-active sites, leading to a remarkable decrease of activity. Thus, it is highly desirable to design molecular imprinting catalysts (MICs) in which both the catalytic activity and selectivity are significantly enhanced. Herein, a series of MICs are prepared by sequentially adsorbing imprinting molecules (nitro compounds, N) and imprinting ligand (1,10-phenanthroline, L) over the copper surface of Cu/Al2O3. The resulting Cu/Al2O3-N-L MICs not only offer promoted catalytic selectivity but also enhance catalytic activity for nitro compounds hydrogenation by an creating imprinting cavity derived from the presorption of N and forming new active Cu-N sites at the interface of the copper sites and L. Characterizations by means of various experimental investigations and DFT calculations disclose that the molecular imprinting effect (promoted activity and selectivity) originates from the formation of new active Cu-N sites and precise imprinting cavities, endowing promoted catalytic selectivity and activity on the hydrogenation of nitro compounds.

Epitope Imprinting of Phospholipids by Oriented Assembly at the Oil/Water Interface for the Selective Recognition of Plasma Membranes

AbstractPhospholipids, as fundamental building blocks of the cell membrane, play important roles for molecule transportation, cell recognition, etc. However, due to the structural diversity and amphipathic nature, there are few methods for the specific recognition of lipids as compared to other biomolecules such as proteins and glycans. Herein, we developed a molecular imprinting strategy for controllable imprinting toward the polar head of phospholipid exposed on the surface of cellular membranes for recognition. Phosphatidylserine, as unique lipid on the outer membrane leaflet of exosome and also hallmark for cell apoptosis, was imprinted with the developed method. The phosphatidylserine imprinted materials showed high efficiency and specific targeting capability not only for apoptotic cell imaging but also for the isolation of exosomes. Collectively, the synthesized molecularly imprinted materials have great potential for selective plasma membrane recognition for targeted drug delivery and biomarker discovery.

Epitope Imprinting of Phospholipids by Oriented Assembly at the Oil/Water Interface for the Selective Recognition of Plasma Membranes.

Phospholipids, as fundamental building blocks of the cell membrane, play important roles for molecule transportation, cell recognition, etc. However, due to the structural diversity and amphipathic nature, there are few methods for the specific recognition of lipids as compared to other biomolecules such as proteins and glycans. Herein, we developed a molecular imprinting strategy for controllable imprinting toward the polar head of phospholipid exposed on the surface of cellular membranes for recognition. Phosphatidylserine, as unique lipid on the outer membrane leaflet of exosome and also hallmark for cell apoptosis, was imprinted with the developed method. The phosphatidylserine imprinted materials showed high efficiency and specific targeting capability not only for apoptotic cell imaging but also for the isolation of exosomes. Collectively, the synthesized molecularly imprinted materials have great potential for selective plasma membrane recognition for targeted drug delivery and biomarker discovery.

Mesoporous molecularly imprinted nanoparticles with peptide mimics for the detection of phenolic compounds

Immobilized enzymes outperform free enzymes in many properties and are widely used in environmental monitoring, engineering applications, food and medical fields. Based on the developed immobilization techniques, the search for immobilization with wider applicability, lower cost and more stable enzyme properties is of significant importance. In this study, we reported a molecular imprinting strategy for immobilizing peptide mimics of DhHP-6 on mesoporous materials. The DhHP-6 molecularly imprinted polymer (MIP) showed much higher adsorption capacity than raw mesoporous silica toward DhHP-6. The DhHP-6 peptide mimics was immobilized on the surface of mesoporous silica for the fast detection of phenolic compounds, a widely spread pollutant with highly toxic and difficult in degradation. Immobilized enzyme of DhHP-6-MIP exhibited higher peroxidase activity, better stability, and recyclability than free peptide. Notably, DhHP-6-MIP showed excellent linearity for the detection of the two phenols with detection limits of 0.28 μM and 0.25 μM, respectively. In combination with the spectral analysis and PCA method, DhHP-6-MIP provided better discrimination between the six phenolic compounds (phenol, catechol, resorcinol, hydroquinone, 2-chlorophenol, 2, 4-dichlorophenol). Our study showed that immobilization of peptide mimics by the molecular imprinting strategy using mesoporous silica as carriers was a simple and effective approach. The DhHP-6-MIP has great potentiality for the monitoring and degradation of environmental pollutants.

Photothermal Therapy of Neuroblastoma via Polysialic Acid‐Targeting Nanomissiles (Small 46/2022)

Neuroblastoma Therapy In article number 2201671, Zhen Liu and co-workers construct polysialic acid-targeting nano-missiles via a molecular imprinting strategy using oligosialic acid containing 4-7 units digested from polySia as the template. Effective targeted photothermal therapy of neuroblastoma is achieved using nano-missiles loaded with the near-infrared fluorescent reactive dye indocyanine green.

DFT-assisted design inspired by loofah-derived biomass carbon decorated CoFe-CoFe2O4 conjugated molecular imprinting strategy for hazardous thiamphenicol analysis in spiked food

Inspired by the porous microstructure of biomass carbon (BC) and the high adsorption properties of magnetic nanomaterials. A novel electrochemical sensor was developed for the selective assay of thiamphenicol (TAP) in fresh milk, honey, and meat samples by the preconcentration with magnetic molecularly imprinted polymer (MIP) based on differential pulse voltammetry (DPV). The magnetic MIP sensor (MIP/BC/CoFe-CoFe2O4/GCE) was fabricated by coupling CoFe-CoFe2O4 particles embedded loofah sponges derived BC with MIP film-decorated glassy carbon electrode (GCE). Theoretical simulation and quantum calculations based on density functional theory (DFT) accelerate the prediction and selection of rational functional monomers, as well as the ratio of template molecules to monomers. The surface structure, elemental composition, and electrochemical behavior were characterized by XRD, XPS, SEM, TEM, CV, and EIS, respectively. Various factors such as the amount of BC/CoFe-CoFe2O4, monomer/template ratio, polymerization cycles, pH value, elution time, and incubation time have been optimized to enhance the performance of the sensor. Under the optimal conditions, the current response intensities have three segments of good linear relationships with the TAP concentrations in the range of 0.01–2.0 µM (R2 =0.9930) and 2–400 µM (R2 =0.9955) as well as 400–5000 µM (R2 =0.9900) with an ultralow detection limit (LOD, S/N = 3) of 0.003 µM. Besides, the magneto-actuated electrochemical sensor exhibited outstanding analytical performance, i.e., excellent reproducibility and repeatability, ideal stability, and superior anti-interference ability. Moreover, the reliable recoveries (95.11%−105.00%) and the ideal relative standard deviations (RSDs) (1.2%−4.9%) for TAP determination in husbandry samples demonstrated that our developed sensor has good potential in the application.

Bio-inspired design on EGCG-selective membrane: An anchoring/imprinting strategy based on bi-interactions

In recent years, molecularly imprinted membrane (MIM) has exhibited superiority in industrial separation, drug purification, solid-phase extraction and even medical detection owing to its remarkable selectivity. For catechins, however, the reactivity with free radicals limits the traditional construction of MIM towards such molecules. Here in this work, we have developed a bio-inspired MIM towards Epigallocatechin gallate (EGCG, a representative catechin) by the anchoring/imprinting strategy. The covalent interactions based on boronate-affinity supplied an oriented anchoring effect, while the non-covalent interactions from l-cysteine promoted the formation of imprinted sites that are highly matched with template. Mild and efficient imprinting was carried out by self-polymerization of dopamine to avoid the destruction of templates. As a result, remarkable selectivity coefficients (2.70 and 4.58), permselectivity coefficients (more than 3.19 and 3.41) and separation factors (5.18 and 7.00) were achieved on the EGCG-imprinted membrane (EIM), accompanied by the impressive imprinting factor (10.14) and superior regeneration performance (only 4.4% of the decline in five cycles). For deep insight into selective recognition and separation, microscopic and visualized mechanisms of site formation and specific rebinding was proposed by molecular dynamics simulations. Approaches with such an anchoring/imprinting strategy will enrich the avant-garde molecular imprinting strategies, and also expand membrane-based applications.

Synthesis of highly selective molecularly imprinted nanoparticles by a solid-phase imprinting strategy for fluorescence turn-on recognition of phospholipid

Molecularly imprinted polymers (MIPs) are artificial receptors with template tailored recognition sites complementary to the targets. The versatility of this molecular imprinting technique has been hampered by the lack of practical synthetic procedures to prepare highly selective MIP nanoparticles targeting phospholipids, which are challenging to be imprinted due to their amphiphilic structure. Here, a novel sedimentation-based solid-phase imprinting strategy is introduced relying on polymerization in the presence of template-modified silica nanospheres (SNs). To demonstrate this concept, the sphingosine-1-phosphate receptor agonist fingolimod phosphate (FP) was coupled to SNs which were dispersed in the prepolymerization medium consisting of the fluorescent functional monomer 1,8-bis(N-vinylimidazol-N′-methyl)anthracene bromide and the crosslinking monomer ethyleneglycol dimethacrylate. High dilution polymerization of the dispersion under agitation followed by simple sedimentation-based separation of the SN template resulted in the isolation of surface imprinted fluorescent MIP nanoparticles (FMIP NPs) in a high yield (17 %). The FMIP NPs displayed fluorescence enhancement in response to the template with a high imprinting factor (IF=9) under the experimental conditions and good specificity, and could recognize FP in human serum with recoveries of 68–74 %. Moreover, the template-modified SNs could be recycled for reuse. Such molecular imprinting strategy opens a new approach to produce highly selective artificial receptors targeting phospholipids.

Amino acids imprinted ZIF-8s for the highly efficient and selective adsorption of antioxidant peptides from silkworm pupa protein

Antioxidant peptides from edible protein sources have attracted great attention due to their high activity, easy adsorption and low toxicity. The purpose of this study was to develop a new MOF material with specific recognition and capture ability to achieve the aim of highly efficient and selective antioxidant peptides from silkworm pupa protein hydrolysate-N (SPPH-N). Firstly, Histidine (His) widely presented in antioxidant peptides was used to in-suit construct the modified ZIF-8 material (ZIF-His) with imprinted defective mesopores, based on “molecular imprinting strategy”. Then, it was applied to extract antioxidant peptides from SPPH-N. ZIF-His exhibited high adsorption uptake for antioxidant peptides and especially presented specific adsorption property for peptides contained His, tryptophan, phenylalanine and tyrosine. Three peptides with the highest antioxidant activity (FKVPNMY, AVNMVPFPR and VNMVPFPR) from ZIF-His eluent were identified by Nano-LC-MS/MS. These peptides were synthesized and presented the excellent free radicals scavenging activity and the Ferric reducing power.

Advances in application of molecularly imprinted polymers to the detection of polar pesticide residues

极性农药包括杀菌剂、除草剂、杀虫剂等,种类丰富,成本低廉,在农业中应用广泛,其滥用易导致水资源和土壤等环境污染,人类通过间接接触动植物源性食品和环境中的极性农药残留也增加了农药暴露风险。极性农药的物理化学性质差异大,通常痕量存在于食品和环境样品等复杂基质中,这对其准确检测分析带来了挑战。分子印迹聚合物(MIPs)作为一种人工制备的选择性吸附剂,具有与模板分子在空间结构、大小尺寸和功能基团上互补的特定识别位点,且易于制备,成本低,稳定性好,重复利用率高,已被广泛用于极性农药残留的样品前处理和分析检测中。MIPs可以作为固相萃取(SPE)、固相微萃取(SPME)、磁性固相萃取(MSPE)、搅拌棒固相萃取(SBSE)等前处理方法的吸附剂,还可用于制备光、电、化学传感器,作为质谱检测的离子源基底和拉曼光谱的增强基底。目前针对极性农药残留的检测,已有许多研究报道了多种分子印迹材料用于高效分离分析各种复杂基质中的极性农药残留,但未见此方面的综述报道。该文首先介绍了MIPs的印迹策略、聚合策略,并针对传统MIPs制备和应用中存在的问题,简要概括了一些新型的分子印迹策略和制备技术;然后从极性农药残留分析的角度出发,总结归纳了分子印迹材料近年来特别是近5年来在各种极性农药残留(包括新烟碱类、有机磷类、三嗪类、唑类、脲类等)检测中的应用,并针对现存问题展望了其未来的发展方向和趋势。

Selective and Sensitive Electrochemical Sensor Based on Molecular Imprinting Strategy for Recognition and Quantification of Sofosbuvir in Real Samples

Selective and Sensitive Electrochemical Sensor Based on Molecular Imprinting Strategy for Recognition and Quantification of Sofosbuvir in Real Samples

Facile fabrication of snowman-like magnetic molecularly imprinted polymer microspheres for bisphenol A via one-step Pickering emulsion polymerization

In this paper, the magnetic molecularly imprinted polymers (M-MIPs) for bisphenol A were synthesized via facile one-step Pickering emulsion polymerization using Fe3O4 nanoparticles as the only stabilizer. The synthesis was based on non-covalent molecular imprinting strategy and performed by thermally initiated radical polymerization. The morphology of M-MIPs microspheres was examined by the field emission scanning electron microscope. The result indicated that most of prepared M-MIPs microspheres appeared snowman-like shape instead of the regular spherical form. The binding performance of M-MIPs microspheres was researched through a batch of binding tests including binding kinetics and binding isotherm. M-MIPs could reach binding equilibrium within 60 min. The binding capacity of M-MIPs (16.20 μmol g−1) was higher than that of magnetic non-imprinted polymers (M-NIPs), whose binding capacity was 9.44 μmol g−1. The specific binding was also carried out with BPA and its structurally similar compounds. The result showed that the M-MIPs possessed high selectivity towards BPA with the imprinting factor of 1.69. The M-MIPs may be useful in the environmental and analytic fields.

Molecular Imprinting Strategies for Tissue Engineering Applications: A Review.

Tissue Engineering (TE) represents a promising solution to fabricate engineered constructs able to restore tissue damage after implantation. In the classic TE approach, biomaterials are used alongside growth factors to create a scaffolding structure that supports cells during the construct maturation. A current challenge in TE is the creation of engineered constructs able to mimic the complex microenvironment found in the natural tissue, so as to promote and guide cell migration, proliferation, and differentiation. In this context, the introduction inside the scaffold of molecularly imprinted polymers (MIPs)—synthetic receptors able to reversibly bind to biomolecules—holds great promise to enhance the scaffold-cell interaction. In this review, we analyze the main strategies that have been used for MIP design and fabrication with a particular focus on biomedical research. Furthermore, to highlight the potential of MIPs for scaffold-based TE, we present recent examples on how MIPs have been used in TE to introduce biophysical cues as well as for drug delivery and sequestering.

Reaction: Goal-Oriented PAF Design for Uranium Extraction from Seawater

Guangshan Zhu received his BSc (1993) and PhD (1998) degrees in chemistry from Jilin University. He is now a full professor at Northeast Normal University. Driven by the demands in sustainable energy and environments, his current research interest focuses on the design and synthesis of porous aromatic frameworks for gas adsorption, separation, and uranium capture.

Application of Molecular Imprinting Technology in Post-translational Modified Protein Enrichment

Post-translational modification of proteins plays an important regulatory role in the process of cell life, enabling proteins to have biological activities and perform corresponding functions. The content of post-translational modification proteins in the organism is very low, which makes it commit to a mighty challenge to accurately identify the post-translational modification proteins. The molecular imprinted cavity, which perfectly matches the size, shape, and functional groups of the target molecules, has shown great potential in the separation field. In this paper, the types and characteristics of post-translational modified proteins and molecular imprinting methods were summarized. On this basis, the application of molecular imprinted polymers to the enrichment of post-translational modified proteins was reviewed, and the prospect of its development was prospected. At present, commonly used molecular imprinting techniques are bulk imprinting, surface imprinting, and epitope imprinting. New molecular imprinting strategies have been developed, such as boronate affinity molecular imprinting, nano-framework surface imprinting, and post-imprinting modification. These molecularly imprinted techniques have shown great potential in the separation of glycosylated, phosphorylated, acetylated and sulfated proteins.

Molecularly Imprinted Nanogels Possessing Dansylamide Interaction Sites for Controlling Protein Corona In Situ by Cloaking Intrinsic Human Serum Albumin.

Nanomaterials have become increasingly promising for biomedical applications owing to their specific biological characteristics. As drug delivery vehicles, nanomaterials have to circulate in the bloodstream to deliver the encapsulated components to the target tissues. Protein corona regulation is one of the promising approaches that gives stealth capability to avoid immune response. The aim of this study was to develop molecularly imprinted polymer nanogels (MIP-NGs) capable of protein corona regulation, using intrinsic human serum albumin (HSA) and with a functional monomer, dansylamide ethyl acrylamide (DAEAm), the dansylamide group serving as a ligand for HSA. The recognition capability of HSA for MIP-NGs was investigated by isothermal titration calorimetry (ITC). The affinity of the MIP-NGs prepared with DAEAm was then compared to that of the reference MIP-NGs prepared with pyrrolidyl acrylate developed in our previous study. Furthermore, we demonstrated that the concurrent use of these two different functional monomers for molecular imprinting was further effective to construct high-affinity recognition nanocavities for HSA and to form HSA-rich protein corona in the human plasma owing to the different interaction modes of the monomers. We believe that the molecular imprinting strategy developed through the use of ligand-based functional monomer is an effective strategy to create artificial molecular recognition materials.