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RSC Advances · 2015 ·Vol. 5 ·期 58 ·47010-47021 · IF 3.84

Template size matched film thickness for effectively in situ surface imprinting: a model study of glycoprotein imprints

Gang Wu,Jinyang Li,Xue Qu,Yuxin Zhang,Hua Hong,Changsheng Liu

Precisely controlling the material structure is a high requirement for biological target imprinting. In situ surface imprinting immobilized templates can offer thin-film molecular imprints containing site-directed binding sites on substrates, and therefore is appropriate for biological targets. However, the correlation between the required film thickness for superior imprinting effect and the bulk structure of biological template is not clearly understood. Here we use a series of glycoprotein imprinted films as a model to give a semi-quantitative description for their correlation. Glycoproteins with distinguished molecular sizes including ribonuclease B, glucose oxidase and horseradish peroxidase were used as templates. Covalently immobilizing glycoproteins was achieved by using m-aminophenylboronic acid modified SiO2 or Fe3O4 surface. Dopamine was polymerized onto this surface for glycoprotein imprinting. Varying polymerization time provided a series of thickness tunable imprinting films in nanometer-scale. The binding isotherm study for each glycoprotein imprints with different film thickness was performed. The optimal film thickness for the highest binding capacities and imprinting factors shows a positive correlation with its template size. The each optimized glycoprotein imprints can recognize their template in a simple or complex environment. These results suggest that the thickness of imprinted film should be tailored for matching the geometric size of fixed templates, and reveal the substantial influence of template structure on imprints design.

CAS / MDL: 2530-85-0
研究领域: 材料科学 · 生物技术 · 表面化学
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International Journal of Polymeric Materials and Polymeric Biomaterials · 2018 · IF 2.127

Surface molecularly imprinted material for enantiomeric resolution of ibuprofen: Preparation and study on chiral recognition and resolution property

Baojiao Gao,Yanbin Li,Lulu Chen

The surface imprinted material of one single enantiomer of ibuprofen ((S)-ibuprofen) was successfully prepared using the novel surface imprinting technique of synchronously graft/crosslinking-polymerizing and molecule imprinting. Micron sized-silica gel particles as matrix were first modified with coupling agent γ-mercaptopropyl trimethoxysilane (MPMS), obtaining MPMS-SiO2 particles, on which there was a great deal of mercapto group (‒SH). Hydroxyethyl methylacrylate (HEMA) as functional monomer and dibenzoyl peroxide (BPO) as initiator were dissolved into 1,2-dichloroethane (DCE), and HEMA molecules are automatically combined around (S)-ibuprofen molecules by right of multi-site hydrogen bonds, forming self-assembly complex. A surface-initiating system of ‒SH/BPO was constituted at the interface between MPMS-SiO2 particles and DCE solution. The free radicals produced on the surfaces of MPMS-SiO2 particles initiated HEMA molecules around (S)-ibuprofen molecules to produce graft/crosslinking-polymerization on the surfaces of SiO2 particles. At the same time, (S)-ibuprofen molecules were wrapped in the cross-linked networks so that the surface-imprinting of (S)-ibuprofen was realized, forming (S)-ibuprofen surface imprinted particles ((S)-IBU-SIP). The enantiomeric recognition and resolution properties of (S)-IBU-SIP particles were investigated. The experimental results show that (S)-IBU-SIP particles have excellent enantiodiscrimination property and enantioseparation ability. The binding capacity of (S)-IBU-SIP particles for (S)-ibuprofen gets up to 177 mg g−1, and the selectivity coefficient of (S)-IBU-SIP particles for (S)-ibuprofen relative to (R)-ibuprofen is 5.03. For the ibuprofen raceme solution, after solid phase extraction by (S)-IBU-SIP particles, the optical purity (ee value of (S)-ibuprofen) of the eluent reaches up to 82.5%, whereas the optical purity (ee value of (R)-ibuprofen) of the supernatant is 44.2%.

CAS / MDL: 97-90-5
研究领域: 药物化学 · 分析化学
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MICROCHIMICA ACTA · 2015 ·Vol. 182 ·期 7 ·1527-1534 · IF 3.741

Specific recognition and fluorescent determination of aspirin by using core-shell CdTe quantum dot-imprinted polymers

Wei Xiao,Zhou Zhiping,Hao Tongfan,Xu Yeqing,Li Hongji,Lu Kai,Dai Jiangdong,Zheng Xudong,Gao Lin,Wang Jixiang,Yan Yongsheng,Zhu Yanzhuo

A molecularly imprinted polymer (MIP) was deposited on the surface of CdTe quantum dots (QDs) to act as a recognition element for aspirin. The MIP was synthesized from 3-aminopropyltriethoxysilane as the functional monomer, aspirin as the template, and tetraethoxysilane as the cross-linker via a sol–gel process that leads to surface imprinting. It is shown that the fraction of QDs and the polymerization process affect size and morphology of the MIP-coated QDs. The optical stability, effects of pH, detection time and selective determination of aspirin were optimized. The fluorescence intensity of the particles (photoexcited at 400 nm and measured at 628 nm) decreases linearly with increasing concentration of aspirin in the 2.0–50 μmol L −1 range. The limit of detection (at an S/N of 3) is 0.25 μmol L −1 . The method was successfully applied to the determination of aspirin in human urine and saliva. CdTe quantum dots, APTES (the functional monomer), aspirin (the template) and TEOS (the cross-linker) were copolymerized to form a surface-imprinted polymeric network around the template. After extraction of the template, the imprint-coated quantum dots are capable of specifically recognizing aspirin.

研究领域: 分析化学 · 材料科学 · 药物分析
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SEPARATION SCIENCE AND TECHNOLOGY · 2015 · IF 1.171

Preparation of Nicotine-Imprinted Monolith by in-situ Surface Imprinting onto Internal Hole Surface of Macroporous Silica for Selective Enrichment and Separation of Nicotine in Environmental Water Sample

Cuimei Lu,Hui Li,Miaomiao Xu,Susu Wang,Gui Li,Wei Zhong,Siyin Qin

A novel surface imprinting technique combined with in-situ polymerization was developed to prepare nicotine-imprinted monolith (MIPM) in a stainless column by grafting molecularly imprinted polymers (MIPs) onto the internal hole surface of macroporous silica. Binding capacity of this MIPM was evaluated by frontal chromatographic technique and the MIPM solid phase extraction researched. Then, the applicability for this MIPM to selectively gather nicotine in environmental water sample was evaluated. Results indicated that the pH value of mobile phase greatly influenced binding capacity of the MIPM. When the mobile phase was at pH 5.0, adsorption capacity was the highest, with a value of 6.4 mg/L. Furthermore, when a pH 9.0 phosphate buffer was used as elution solvent during solid phase extraction, the target compound could be selectively desorbed from the MIPM, with a recovery of 99.6%. In addition, no great loss in recovery emerged when this MIP monolith was repeatedly used for solid phase extraction of nicotine in environmental water sample, revealing a good repeatability.

CAS / MDL: 97-90-5 1185-55-3
研究领域: 分析化学 · 环境科学
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JOURNAL OF APPLIED POLYMER SCIENCE · 2014 ·Vol. 132 ·期 15 · IF 1.64

Optimal design of an imprinted preassembled system by quantum chemical calculations and preparation of a surface-imprinted material for the selective removal of quinoline

Wenming Yang,Pengfei Ma,Ting Fan,Zhiping Zhou,Hong Liu,Wanzhen Xu

In this study, we examined the rational preparation of molecularly imprinted polymers (MIPs) for the selective removal of quinoline from octane. Before the preparation, density functional theory, as one of the methods of quantum chemical calculation, was used for the simulation of a quinoline-imprinted preassembly system. Methacrylic acid turned out to be the more suitable monomer for quinoline compared with acrylamide, and different template–monomer ratios, including 1:1, 1:2, and 1:3, were studied and are discussed. On the basis of the result of molecular simulation, quinoline-imprinted polymers were prepared with a combination of surface imprinting and living polymerization. The prepared quinoline–MIPs were characterized and used as selective adsorbents for batch-mode binding experiments. The fitting result of the adsorption data indicates that the adsorption kinetics and adsorption isotherms of the quinoline-imprinted polymers fit well a pseudo-second-order kinetics model and the Freundlich model, respectively. A selective recognition ability was demonstrated by equilibrium binding analysis. This study will provide needful guidance and a theoretical basis for the preparation of imprinted materials in the field of industrial denitrification. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132 , 41730.

研究领域: 材料科学 · 化学工程 · 环境科学
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JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY · 2017 · IF 4.421

Ion/molecule imprinted polymers with double binding sites via twice imprinting strategy for selective and simultaneous removal of λ-cyhalothrin and Cu(II)

Hengjia Zhu,Jianming Pan,Jun Cao,Yue Ma,Fengxian Qiu,Wenli Zhang,Yongsheng Yan

Herein we reported a facile method to prepare porous ion/molecule imprinted polymers (I-MIPs) via twice imprinting strategy for the simultaneous uptake of copper ions (Cu(II)) and λ-cyhalothrin (LC). Firstly, N -(β-aminoethyl)-γ-aminopropytrimethoxysilane (DAMO) was grafted on silica particles surface to synthesis Cu(II)-imprinted polymers to introduce iron imprinted sites. They were then utilized as stabilizers to prepare a stable W/O Pickering HIPEs template (LC as the imprinting molecule), which was then polymerized with dual imprinting sites including Cu(II) and LC. The adsorption equilibrium, kinetic results and selective recognition experiments were exhibited their prospected dual selectivity and simultaneous removal of LC and Cu(II).

研究领域: 环境科学 · 材料科学
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Materials Today Communications · 2020 · IF 2.678

Preparation and adsorption properties of rosin-based bisphenol A molecularly imprinted microspheres

Caili Yu,Jianhang Shan,Yong Chen,Jintao Shao,Faai Zhang

Rosin-based bisphenol A (BPA) molecular imprinted polymer (P-MIP) microspheres were prepared by suspension polymerization using rosin-based isophorone diisocyanate polyurethane as the primary monomer, methacrylic acid as the functional monomer, and BPA as the template molecule. The structure, morphology, particle size and adsorption properties of the microspheres were characterized and analyzed by means of infrared spectroscopy, scanning electron microscopy, laser particle size analysis and ultraviolet-visible spectrophotometry. The results showed that the imprinted microspheres exhibited a spherical shape with an average particle size of 123 μm. The adsorption behavior of BPA on the P-MIP microspheres followed a pseudo-first-order kinetic model, corresponding to physical adsorption. The isothermal adsorption model conformed to the Freundlich model, indicating that the binding sites were non-uniform. The imprinting factors ( σ ) of the P-MIP microspheres for BPA, para-tert-butyl phenol, hydroquinone and phenol were 2.69, 1.53, 1.26 and 1.10, respectively, indicating that the P-MIP microspheres had specific adsorption properties for BPA. After the imprinted microspheres were repeatedly used for five times, the adsorption rate was 96 %, indicating good repeatability.

研究领域: 材料科学 · 环境科学
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Desalination and Water Treatment · 2016 · IF 1.272

Enhanced adsorption of norfloxacin on modified TiO2 particles prepared via surface molecular imprinting technique

Song Li,Lei Fang,Miaomiao Ye,Yan Zhang

For norfloxacin removal in aquatic environment, TiO2 particles (P25) were modified via surface molecular imprinting technique to improve the adsorption property and sustainable use by photocatalytic regeneration. Orthogonal experiment was adopted to quantify the significance of preparation factors and determine the optimum preparation conditions. The adsorption of norfloxacin on the molecular imprinted particles (MIPs), the non-imprinted particles (NIPs), and P25 fitted the second-order adsorption model and Langmuir model well. The MIPs showed a higher adsorption capacity toward norfloxacin than the NIPs and P25. The adsorption rate constant, maximum adsorption capacity, and Langmuir constant of the MIPs toward norfloxacin were 0.49 g mg−1 min−1, 2.99 mg g−1, and 2.4 L mg−1, respectively. Removal efficiencies for norfloxacin, ciprofloxacin, carbamazepine, and phenol by the MIPs were 76.99, 78.81, 7.87, and 2.68%, respectively, which indicated that the MIPs had higher affinity toward norfloxacin and fluoroquinolones with similar structures. Moreover, the MIPs exhibited the photocatalytic property and could be regenerated by UV irradiation with stable removal efficiency for norfloxacin in five adsorption–regeneration cycles.

研究领域: 环境科学 · 材料科学
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Journal of Materials Chemistry A · 2014 ·Vol. 3 ·期 3 ·1287-1297 · IF 0

Synthesis of hydrophilic surface ion-imprinted polymer based on graphene oxide for removal of strontium from aqueous solution

Yan Liu,Xiangguo Meng,Min Luo,Minjia Meng,Liang Ni,Jian Qiu,Zhaoyong Hu,Fangfang Liu,Guoxing Zhong,Zhanchao Liu,Yongsheng Yan

A novel hydrophilic ion-imprinted polymer based on graphene oxide has been synthesized by reversible addition–fragmentation chain transfer (RAFT) polymerization with surface imprinting technique. Methylacrylic acid is used as a hydrophilic functional monomer. The resultant adsorbent is verified by UV-vis scanning spectrophotometer, Fourier transmission infrared spectrometry, scanning electron microscopy, transmission electron microscopy, atomic force microscopy, X-ray diffraction, water contact angle measurements, and thermogravimetric analysis. The results suggest that the surface imprinted polymer synthesized by RAFT is a homogeneous thin layer. Owing to the intrinsic advantages of controlling/living polymerization and surface imprinting technology, the obtained RAFT surface ion-imprinted polymer (RAFT-IIP) exhibits excellent imprinting efficiency and adsorption capacity in comparison to the ion-imprinted polymer prepared by traditional radical polymerization. Furthermore, the adsorption isotherm and recognizing ability towards Sr(II) onto RAFT-IIP and non-imprinted polymer (NIP) are compared in batch experiments. The equilibrium data are well fitted by Langmuir model and RAFT-IIP has higher selectivity and nearly four times larger Langmuir calculated maximum adsorption capacity (145.77 mg g−1) than that of NIP at 25 °C. Meanwhile, RAFT-IIP is regenerated and found to be suitable for reuse in successive adsorption–desorption cycles five times without significant loss in adsorption capacity.

研究领域: 材料科学 · 环境科学
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NEW JOURNAL OF CHEMISTRY · 2015 ·Vol. 40 ·期 1 ·564-570 · IF 3.086

Surface protein imprinted magnetic nanoparticles for specific recognition of bovine hemoglobin

Weiming Li,Miaomiao Chen,Huayu Xiong,Wei Wen,Hanping He,Xiuhua Zhang,Shengfu Wang

Molecular imprinting for the detection of protein has gained great interest in recent years. For this purpose, we prepared magnetic molecularly imprinted polymers (MIPs) for the recognition of bovine hemoglobin (BHb) through the surface imprinting technique with two-stage core–sell sol–gel polymerization on the surface of silica modified Fe3O4 nanospheres. 3-Aminopropyltriethoxylsilane and octyltrimethoxysilane were chosen as monomers to construct the MIP layer. The morphology and structure property of prepared nanoparticles were characterized by TEM, X-ray diffraction, Fourier transform infrared spectrometry, and the vibrating sample magnetometer. The obtained magnetic MIPs with high saturation magnetization (60 emu g−1) made it easy to separate the target protein from solution by an external magnetic field. The adsorption and recognition performance of this magnetic MIPs was discussed through adsorption kinetics, adsorption isotherms, special selectivity, reusability and reproducibility tests. It turned out that the magnetic MIPs showed a relatively high adsorption capacity of 124.86 mg g−1 and excellent selectivity towards BHb with a separation factor of 1.99. Moreover, the adsorption capacity of magnetic MIPs was not significantly reduced after three continuous adsorption and elution processes, which indicated their good reusability for at least three repeated cycles.

研究领域: 生物化学 · 纳米材料科学 · 分析化学
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CHEMICAL ENGINEERING JOURNAL · 2022 · IF 16.744

Templating precise multiple binding sites: Promising molecularly imprinted membrane orchestrated by sequential surface imprinting strategy

Jia Gao,Qingyan Guo,Yan Yan,Chao Yu,Muning Chen,Wendong Xing,Li Yan,Yongsheng Yan,Yilin Wu

Olive mill wastewater (OMW) is a hazardous environmental effluent due to its high phenolic compounds (PCs) content. Novel strategies affording molecular precision and functional versatility are needed to recover PCs and reduce ecotoxicity. Luteolin (LTL) was selected as a typical PC in the OMW. In this study, we outlined a molecularly imprinted membrane (MPL@CSMIMs) orchestrated by a sequential surface imprinting strategy to selectively separate LTL . Dopamine (DA), as a multifunctional monomer, could self-polymerize in an alkaline solution to form the first LTL-imprinting procedure. A polydopamine (PDA) modulated bottom-up approach was regarded as a molecular linker to enhance the hydrophilicity and binding activity, as well as established a strong and stable adhesion platform for integrated structure. The second imprinting procedure was formed by atom transfer radical polymerization (ATRP). The covalent and non-covalent functional monomers (boronic acid and amino groups) were introduced to create the tailor-made second-imprinted sites. Adsorption isotherm and dynamics, permeation selectivity, and stability were investigated, possessing desirable rebinding ability (49.63 mg g −1 ) and permselectivity factors ( β AGN/LTL  = 5.80, β CTC/LTL  = 12.82), respectively. In-situ diffuse reflection infrared Fourier transform spectroscopy (In-situ ATR-FTIR) analysis, molecular simulation, and X-ray photoelectron spectroscopy (XPS) analysis revealed that the templating precise adsorption property for LTL was mainly realized by the shape of LTL-imprinted sites and synergistic covalent and non-covalent interactions. Compared to one-step or one-pot imprinting approaches, the proposed sequential surface imprinting strategy offered a more flexible and precise combination to improve the selectivity of MIMs significantly. The efficiency of the sequential imprinting approach made it a competitive and appealing method to develop MIMs.

研究领域: 环境科学 · 材料科学 · 生物化学
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FOOD CHEMISTRY · 2024 · IF 8.5

Computational simulation-assisted template selection of magnetic MOFs molecularly imprinted materials applying the adsorption and detection of multiple fluoroquinolones

Mingfei Pan,Xuan Liu,Jingming Sun,Dan Zhang,Yixin Wang,Xiaochun Hu,Shuo Wang

This study utilized computational simulation and surface molecular imprinting technology to develop a magnetic metal-organic framework molecularly imprinted polymer (Fe 3 O 4 @ZIF-8@SMIP) capable of selectively recognizing and detecting multiple fluoroquinolones (FQs). The Fe 3 O 4 @ZIF-8@SMIP material was synthesized using the “common” template-ofloxacin, identified by computational simulation, demonstrating notable adsorption capacity (88.61–212.93 mg g −1 ) and rapid mass-transfer features (equilibration time: 2–3 min) for all tested FQs, consistent with Langmuir adsorption model. Subsequently, this material was employed as a magnetic solid-phase-extraction adsorbent for adsorption and detection of multiple FQs by combining with high performance liquid chromatography. The developed method exhibited good linearity for various FQs within the concentration range of 0.1–500 μg L −1 , with low limit of detection (0.0605–0.1529 μg L −1 ) and limit of quantitation (0.2017–0.5097 μg L −1 ). Satisfactory recoveries (88.38–103.44%) were obtained when applied to spiked food samples, demonstrating the substantial potential of this Fe 3 O 4 @ZIF-8@SMIP material for rapid enrichment and identification for multiple FQs residues.

研究领域: 分析化学 · 材料科学 · 食品科学
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