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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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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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FOOD CHEMISTRY · 2021 · IF 7.514

Synthesis and evaluation of mesoporous silica/mesoporous molecularly imprinted nanoparticles as adsorbents for detection and selective removal of imidacloprid in food samples

Fengqin Yin,Feng Xu,Kun Zhang,Min Yuan,Hui Cao,Tai Ye,Xiuxiu Wu,Fei Xu

The double-mesoporous-layer imprinted polymer of mesoporous silica/mesoporous molecularly imprinted nanoparticles (MIP), with high specific surface area, rich porosity, excellent mass transfer rate and selectivity, were synthesized using imidacloprid (IDP) as a template. Under the optimal conditions of pH, contact time, concentration and temperature, MIP showed high adsorption capacity of 13.86 μg·mg −1 toward IDP and the imprinting factor reached 3.5. The adsorption process model including binding isotherm and kinetics was investigated. MIP exhibited excellent regeneration and its adsorption and selectivity were outstanding among its structurally pesticide analogues. The recovery of spiked IDP for MIP in fortified real samples can reach 96.0 ± 8.5% for cabbage and 105.0 ± 9.9% for apple. The limit of detection of the enrichment method can be as low as 0.037 μg·mL- 1 with a good linear relationship (R 2  = 0.996) from 0.30 to 10.0 μg·mL −1 . The results indicated that the proposed method allowed class-specific detection of IDP in food samples.

CAS / MDL: 79-41-4
研究领域: 食品科学 · 材料科学 · 分析化学
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ANALYTICAL AND BIOANALYTICAL CHEMISTRY · 2015 ·Vol. 407 ·期 24 ·7401-7412 · IF 3.436

Effect of minimizing amount of template by addition of macromolecular crowding agent on preparation of molecularly imprinted monolith

Sun Guang-Ying,Zhong Dan-Dan,Li Xiang-Jie,Luo Yu-Qing,Ba Hang,Liu Zhao-Sheng,Aisa Haji Akber

One of the main challenges in the preparation of molecularly imprinted polymers (MIPs) is the substantial initial amount of template needed because of the requirement of high load capacities for most applications. A new strategy of macromolecular crowding was suggested to solve this problem by reducing the amount of template in the polymerization recipe. In a ternary porogenic system of polystyrene (PS) (crowding agent), tetrahydrofuran, and toluene, an imprinted monolithic column with high porosity and good permeability was synthesized using a mixture of ellagic acid (template), acrylamide, and ethylene glycol dimethacrylate. The effect of polymerization factors, including monomer–template molar ratio and the molecular weight and concentration of PS, on the imprinting effect of the resulting MIP monoliths was systematically investigated. At a high ratio of monomer–template (120:1), the greatest imprinting factor of 32.4 was obtained on the MIP monolith with the aid of macromolecular crowding agent. The PS-based imprinted monolith had imprinting even at the extremely high ratio of functional monomer to template of 1510:1. Furthermore, an off-line solid-phase extraction based on the ground MIP was conducted, and the purification recovery of ellagic acid from pomegranate-rind extract was up to 80 %. In conclusion, this approach based on macromolecular crowding is simple, and is especially valuable for those applications of MIP preparation for which a rare template is used.

CAS / MDL: 79-06-1
研究领域: 分析化学 · 材料科学
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Journal of Materials Chemistry C · 2022 ·Vol. 10 ·期 21 ·8432-8440 · IF 8.067

Molecularly imprinted CsPbBr3 quantum dot-based fluorescent sensor for trace tetracycline detection in aqueous environments

Xiao Wei,Shen Zhang,Tong Wang,Aixia Chen,Jifeng Guo,Bo Bai,Shengke Yang,Yaqian Li,Xinyi Wang,Xinni Liu

All-inorganic halide perovskite quantum dots (IPQDs) have attracted considerable attention as an emerging fluorescent material owing to their excellent optical properties. However, due to the instability of IPQDs in polar solution, IPQDs have not been used in imprinting and detection in the aqueous phase. Herein, a sensitive, selective fluorescent sensor is reported, which combines luminescent CsPbBr3 quantum dots (QDs) and molecularly imprinted polymers (MIPs) for trace tetracycline (TC) detection in aqueous environments. IPQDs@MIPs were constructed by encapsulating water-soluble CsPbBr3 QDs in pre-prepared MIPs to avoid fluorescence quenching during conventional imprinted polymerization and elution, and the porous silicon matrix protected the QDs. IPQDs@MIPs solution emitted bright green fluorescence under UV lamp irradiation, confirming that IPQDs were stable in the aqueous phase and showed excellent selectivity for TC detection. Under optimal conditions, the fluorescence intensity of the IPQDs@MIPs had a good linear correlation with TC in the concentration range of 0.2–5.0 μM, and the detection limit was 28 nM. Furthermore, the imprinting factor of the IPQDs@MIPs was 4.87, and the mechanism of fluorescence quenching was mainly the electron transfer between TC and IPQDs@MIPs. The fluorescent sensor achieved satisfactory results in the standard addition recovery experiment of an actual water sample. This work paves the way for the further development of IPQDs in the field of analytical chemistry in a practical detection environment.

研究领域: 分析化学 · 材料科学 · 环境科学
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SEPARATION AND PURIFICATION TECHNOLOGY · 2024 · IF 8.1

Recyclable and selective PVDF-based multifunctional molecular imprinted membranes for the removal of Bisphenol A

Jinyue Chai,Junlei Zheng,Haiting Yu,Fang Chai,Miaomiao Tian

Bisphenol A (BPA) has been widely detected in environmental and human products and has significant health and environmental impacts. Consequently, an innovative molecularly imprinted membrane was fabricated for the selective adsorption of BPA within water environment. Tannic acid (TA), abundant in plants, was employed to effectuate the reduction of AgNO 3 in an environmentally friendly, and gentle manner, imbuing the membrane with antibacterial properties. A functional hydrophilic layer was created utilizing TA and polyimide (PEI), and mild and efficient imprinting was accomplished through dopamine (DA) self-polymerization. Compared with the blank membrane, the contact angle of the molecularly imprinted membranes (PVDF@Ag@P@MIMs) was reduced to 67.62°, and the optimal adsorption capacity was 33.41 mg g −1 . The imprinting factor of the PVDF@Ag@P@MIMs membrane was 2.90, indicating that the membrane could effectively separate BPA. After 6 cycles of utilization, the adsorption loss was only 4.55 %. In addition, the synthesis of PVDF@Ag@P@MIMs is simple and free of pollutants. The experimental results and green synthesis process of the molecularly imprinted membranes indicate that these materials have potential applications in environmental protection, selective separation, chemical industry, and other fields.

CAS / MDL: 9002-18-0
研究领域: 环境科学 · 材料科学 · 化学工程 · 纳米技术
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NEW JOURNAL OF CHEMISTRY · 2016 ·Vol. 41 ·期 3 ·1129-1136 · IF 3.277

Simultaneous selective extraction of nitramine explosives using molecularly imprinted polymer hollow spheres from post blast samples

Jian Wang,Zihui Meng,Min Xue,Lili Qiu,Xiao Dong,Zhibin Xu,Xuan He,Xueyong Liu,Jinshan Li

Molecularly imprinted polymer hollow spheres (MIHSs) were produced by using hexanitrohexaazaisowurtzitane (HNIW or CL-20) as a template, silica nanospheres as a sacrificial matrix, acrylamide as a functional monomer, ethylene glycol dimethacrylate as a cross-linker and acetonitrile as a porogen at 4 °C under UV irradiation. This sorbent was applied to the selective solid-phase extraction (SPE) of several explosives simultaneously by using a newly-developed SPE procedure. For the first time, 2,4,6-trinitrotoluene (TNT), 1,3,5-trinitro-1,3,5-triazacyclohexane (RDX), 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane (HMX) and CL-20 were selectively extracted and determined simultaneously from simulated post-blast samples prepared from motor oil and vacuum pump oil. The matrix effects were successfully eliminated and accurate quantization was achieved. When the loading amounts of HMX, RDX, TNT and CL-20 were, respectively, below 10, 2, 5 and 20 nmol for 100 mg of MIHS, these explosives were almost retrieved completely (above 98%). For the MIHSs and non-imprinted polymer hollow spheres (NIHSs), in acetonitrile and methanol, the imprinting factors (IFs) of CL-20 and tetraacetyldibenzylhexaazaisowurtzitane (TADB, a structural analogue of CL-20) changed dramatically, from 7.75 to 1.57 and 0.88 to 2.39, respectively. It highlighted the significant effect of solvents on imprinted sites.

CAS / MDL: 2530-85-0 78-10-4
研究领域: 分析化学 · 材料科学 · 环境科学
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ACS Applied Materials & Interfaces · 2016 · IF 7.145

Fluorescence Probe Based on Hybrid Mesoporous Silica/Quantum Dot/Molecularly Imprinted Polymer for Detection of Tetracycline

Liang Zhang,Ligang Chen

A newly designed fluorescence probe made from a hybrid quantum dot/mesoporous silica/molecularly imprinted polymer (QD/MS/MIP) was successfully created, and the probe was used for the detection of tetracycline (TC) in serum sample. QD/MS/MIP was characterized by transmission electron microscope, Fourier transform infrared spectroscopy, UV spectroscopy, X-ray powder diffraction, nitrogen adsorption–desorption experiment and fluorescence spectroscopy. Tetracycline, which is a type of broad-spectrum antibiotic, was selected as the template. The monomer and the template were combined by covalent bonds. After the template was removed to form a binding site, a hydrogen bonding interaction formed between the hole and the target molecule. Moreover, when rebinding TC, a new complex was produced between the amino group of QD/MS/MIP and the hydroxyl group of TC. After that, the energy of the QDs could transfer to the complex, which explains the fluorescence quenching phenomenon. The fluorescent intensity of QD/MS/MIP decreased in 10 min, and an excellent linearity from 50 to 1000 ng mL–1 was correspondingly obtained. This composite material has a high selectivity with an imprinting factor of 6.71. In addition, the confirmed probe strategy was successfully applied to serum sample analyses, and the recoveries were 90.2%–97.2% with relative standard deviations of 2.2%–5.7%. This current work offers a novel and suitable method to synthesize QD/MS/MIP with a highly selective recognition ability. This composite material will be valuable for use in fluorescence probe applications.

研究领域: 分析化学 · 纳米技术 · 材料科学 · 药物分析
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ACS Applied Materials & Interfaces · 2015 · IF 6.723

Fabrication of Surface Protein-Imprinted Nanoparticles Using a Metal Chelating Monomer via Aqueous Precipitation Polymerization

Wei Li,Yan Sun,Chongchong Yang,Xianming Yan,Hao Guo,Guoqi Fu

Molecular imprinting is a promising way for constructing artificial protein recognition materials, but it has been challenged by difficulties such as restricted biomacromolecule transfer in the cross-linked polymer networks, and reduced template-monomer interactions that are due to the required aqueous media. Herein, we propose a strategy for imprinting of histidine (His)-exposed proteins by combining previous approaches such as surface imprinting over nanostructures, utilization of metal coordination interactions, and adoption of aqueous precipitation polymerization capable of forming reversible physical crosslinks. With lysozyme as a model template bearing His residues, imprinted polymer nanoshells were grafted over vinyl-modified nanoparticles by aqueous precipitation copolymerization of a Cu2+ chelating monomer with a temperature-responsive monomer carried out at 37 °C, above the volume phase-transition temperature (VPTT) of the final copolymer. The imprinted nanoshells showed significant temperature sensitivity and the template removal could be facilitated by swelling of the imprinted layers at 4 °C, below the VPTT. The resultant core–shell imprinted nanoparticles exhibited strikingly high rebinding selectivity against a variety of nontemplate proteins. An imprinting factor up to 22.7 was achieved, which is among the best values reported for protein imprinting, and a rather high specific binding capacity of 67.3 mg/g was obtained. Moreover, this approach was successfully extended to preliminary imprinting of hemoglobin, another protein with accessible His. Therefore, it may be a versatile method for fabrication of high-performance surface-imprinted nanoparticles toward His-exposed proteins.

研究领域: 材料科学 · 生物化学 · 纳米技术 · 聚合物化学
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RSC Advances · 2015 ·Vol. 5 ·期 63 ·51392-51398 · IF 3.84

Hydrophilic molecularly imprinted microspheres functionalized with amino and carboxyl groups for highly selective recognition of human hemoglobin in aqueous solution

Jia-Ping Lai,Yue Zuo,Hui Sun,Ying Yu

The hydrophilic molecularly imprinted microspheres (HMIMs) functionalized with amino and carboxyl groups have been synthesized successfully using human hemoglobin as a template. The obtained HMIMs have been characterized using scanning electron microscopy (SEM), adsorption isotherms, dynamic binding as well as quartz crystal microbalance (QCM). The rebinding results indicate that the HMIMs exhibit highly selective recognition properties towards target human hemoglobin in Tris–HCl aqueous solution with an imprinting factor of 1.90 and a high binding capacity of 98 mg g−1. The QCM characterization results also demonstrate that the HMIMs coated electrode shows a more sensitive response to hemoglobin than that of a non-imprinted microspheres coated electrode.

研究领域: 材料科学 · 分析化学 · 生物化学
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ANALYTICAL AND BIOANALYTICAL CHEMISTRY · 2020 ·Vol. 412 ·期 26 ·7227-7236 · IF 3.637

Synthesis of a molecularly imprinted polymer using MOF-74(Ni) as matrix for selective recognition of lysozyme

Li Jie,Ma Miaoxia,Zhang Chenhui,Lu Rui,Zhang Lingyi,Zhang Weibing

A molecularly imprinted polymer and metal organic framework were combined to prepare protein imprinted material. MOF-74(Ni) was used as a matrix to prepare surface-imprinted material with lysozyme as a template and polydopamine as an imprinting polymer. MOF-74(Ni) not only provides a large surface area (150.0 m 2 /g) to modify the polymer layer with more recognition sites ( Wt (Ni) = 42.24%), but also facilitates the immobilization of lysozyme by using the chelation between Ni 2+ of the MOF-74(Ni) and protein. The thin polydopamine layer (10 nm) of the molecularly imprinted material (named MOF@PDA-MIP) enables surface imprinting. Benefiting from the thin polymer layer, MOF@PDA-MIP reached adsorption equilibrium within 10 min. The maximum adsorption capacity reaches 313.5 mg/g with the highest imprinting factor (IF) of 7.8. The specific recognition sites can distinguish target lysozyme from other proteins such as egg albumin (OVA), bovine serum albumin (BSA) and ribonuclease A (RNase A). The material was successfully applied to separation of lysozyme from egg white. Graphical abstract

CAS / MDL: 64-19-7 67-56-1 100-21-0
研究领域: 材料科学 · 生物技术 · 分析化学
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SEPARATION AND PURIFICATION TECHNOLOGY · 2023 · IF 8.6

Synthesis of a gelatin based molecularly imprinted hydrogel with high selectivity on adsorbing bovine serum albumin

Jie-Ping Fan,Jia-Hui Lai,Cong-Bo Huang,Zhi-Tao Lai,Chun-Fang Xie,Hui-Ping Chen,Hai-Long Peng,Yu-De Liu

Molecularly imprinted polymers are confronted with many challenges during application to separating proteins, this study synthesized a molecularly imprinted hydrogel (MIP hydrogel) for specifically separating bovine serum albumin (BSA) with high selectivity. By using the ionic liquid [VAFMIM]Cl as the structure functional monomer and N-isopropylacrylamide (NIPAM) as the thermo-sensitive functional monomer, the obtained gelatin based MIP hydrogel was porous, showed good mechanical properties and outstanding swelling ability. The methacrylation of gelatin improved the MIP hydrogel greatly on mechanical strength. The employment of NIPAM enabled the obtained MIP hydrogel thermo-responsive on swelling ability and adsorption capacity. The BSA adsorption capacity of MIP hydrogel was as high as 150.18 mg/g when the BSA initial concentration was used at 0.5 mg/mL, and the imprinting factor of MIP hydrogel was achieved as high as 5.17. The selectivity coefficients against bovine hemoglobin and lysozyme achieved as high as 11.83 and 9.39, respectively. In BSA/BHb mixture, the MIP hydrogel separation factor toward BSA was still as high as 23.97, and the MIP hydrogel adsorption capacity toward BSA was 4.64-fold larger than that of NIP hydrogel. The adsorption kinetics and isotherm study demonstrated the surface of the synthesized MIP hydrogel was homogenous, the adsorbing active sites were identical with equal energy, the BSA molecules were adsorbed monolayer on MIP hydrogel, the adsorption process was chemisorption and diffusion-controlled. The prepared MIP hydrogel was favorable and showed high potentiality on specific separation of BSA.

CAS / MDL: 15214-89-8 110-18-9
研究领域: 材料科学 · 生物技术 · 化学工程 · 生物化学
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