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[Display omitted] • A selective molecularly imprinted polymer was synthesized. • MIP is composed of functionalized silica nanoparticle, poly methacrylic acid, and poly (N -isopropyl acrylamide). • The recognition and selectivity of MIP and NIP for template trypsin were tested. • The adsorption isotherm and adsorption kinetics were investigated. Molecularly imprinted polymers (MIPs) are innovative porous materials created through polymerization templating methods for highly selective, sensitive detection and separation of the desired chemical species, known as template molecules. Surface imprinting over nano-sized substrates with special functional groups is an effective approach for improving the mass transfer and rebinding capacity. In this study, we successfully performed surface imprinting using methacrylic acid (MAA) and thermoresponsive N -isopropyl acrylamide (NIPAm) as functional monomers on acrylic-functionalized silica nanoparticles and served as a Trypsin artificial receptor. The resulting Trypsin imprinted polymer exhibited a binding capacity of 1022.44 mg/g, surpassing the non-imprinted polymer's capacity of 292.41 mg/g within 45 min. Moreover, the imprinting factor, the main influence factor in MIP performance, was 3.5, demonstrating the significant selectivity of the polymeric products. In addition, due to the temperature sensitivity of NIPAm the template removing process was simply done by changing pore size. The silica nanoparticles and the synthesized MIP particles had diameters of approximately 95 nm and 105 nm, respectively, with the polymer layer thickness being around 5 nm. The MIP adsorption model followed the Freundlich isotherm and pseudo-second-order kinetics resulting in efficiencies of 93.0 % and 95.4 %, respectively. The developed Trypsin imprinted polymer was reusable for four consecutive uses,demonstrating both resilience and selectivity towards Trypsin. [ABSTRACT FROM AUTHOR]

In this work, a novel superparamagnetic hydrophilic molecularly imprinted nanomaterial for the removal of tetracycline (TC) was synthesized utilizing magnetite (Fe 3 O 4) as the magnetic core, TC as the template molecule, 3-aminopropyltriethoxysilane (APTES) as the functional monomer, and tetraethoxysilane (TEOS) as the cross-linker. Initially, Fe 3 O 4 magnetic nanoparticles (MNP) coated with SiO 2 (MNP@SiO 2) were synthesized, followed by TC molecular imprinting on the nanoparticles. Initially, Fe 3 O 4 MNP coated with SiO 2 (MNP@SiO 2) were synthesized, followed by TC molecular imprinting on the nanoparticles. The synthesis method for MNP@SiO 2 was optimized, and DLS analysis of 10 replicates showed a nanoparticle size of 70.1 ± 5.8 nm, indicating high method reproducibility. The MNP@SiO 2 , as well as the imprinted (MNP@SiO 2 -MIP) and non-imprinted (MNP@SiO 2 –NIP) nanomaterials, were characterized by FTIR, TEM, VSM, XRD, DLS, Z potential, and BET analysis. The saturation magnetization (Ms) values were 43 emu/g for MNP@SiO 2 and 32 emu/g for both MNP@SiO 2 -MIP and MNP@SiO 2 –NIP, confirming suitability for magnetic separation using external magnets. Batch binding experiments conducted in water and methanol assessed adsorption isotherms and binding kinetics, with data fitting the Langmuir isotherm model better than the Freundlich model. The developed MIP exhibited significant selectivity against other molecules with similar functional groups and size. In water, the adsorption capacity of the MNP@SiO 2 -MIP was 23 mg/g, with an imprinting factor of 2.2. Furthermore, the MIP demonstrated good regeneration performance. The material was tested on TC-spiked tap water samples, achieving 80.1 % TC removal with high reproducibility (3.2 %, n = 3). Combining hydrophilic superparamagnetic nanoparticles with molecular imprinting enhances their potential applications in environmental remediation, antibiotic purification, and drug delivery. [Display omitted] • Fe 3 O 4 @SiO 2 nanoparticles were molecularly imprinted with high reproducibility. • The imprinted nanomaterial obtained Fe 3 O 4 @SiO 2 -MIP is superparamagnetic and hydrophilic. • Fe 3 O 4 @SiO 2 -MIP nanoparticles show an excellent performance in water with good selectivity. • Fe 3 O 4 @SiO 2 -MIP was applied to spiked TC tap water samples with high removal efficiency. • The combination of molecular imprinting on hydrophilic magnetic nanomaterial increases its application potential. [ABSTRACT FROM AUTHOR]

This study presents novel methodologies and materials for selectively and sensitively determining gibberellin traces in licorice to address food safety concerns. A novel hydrophilic imprinted resin–graphene oxide composite (HMIR–GO) was developed with fast mass transfer, high adsorption capacity, and exceptional aqueous recognition performance for gibberellin. Leveraging the advantages of molecular imprinting, hydrophilic resin synthesis, and rapid mass transfer characteristics of GO, HMIR–GO was employed as an adsorbent, showing resistance to matrix interference. Coupled with HPLC, a rapid and selective method for determining gibberellin was established. Under optimal conditions, the method exhibited a wide linear range (0.02–5.00 μg g−1, r = 0.9999), low detection limits (3.3 ng g−1), and satisfactory recoveries (92.0–98.4%), enabling the accurate and rapid detection of gibberellin in licorice. This study introduces a pioneering strategy for the selective extraction and determination of trace gibberellin levels, offering insights for similar applications in functional foods. • A new hydrophilic imprinted resin–graphene composite (HMIR–GO) was prepared. • HMIR–GO exhibits high adsorption capacity and outstanding aqueous recognition. • HMIR–GO can recognize gibberellin traces in licorice with rapid mass transfer. • A high-selective and rapid method for gibberellin traces in licorice was developed. [ABSTRACT FROM AUTHOR]

As artificial receptors for protein recognition, epitope-imprinted polymers combined with fluorescence sensing based on quantum dots (QDs) can be potentially used for biological analysis and disease diagnosis. However, the usual way for fabrication of QD sensors through unoriented epitope imprinting is confronted with the problems of disordered imprinting sites and low template utilization. In this context, a facile and efficient oriented epitope surface imprinting was put forward based on immobilization of the epitope templates via thiol-disulfide exchange reactions. With N-succinimidyl 3-(2-pyridyldithio)-propionate (SPDP) as a heterobifunctional reagent, cysteine-modified epitopes of cytochrome c were anchored on the surface of pyridyl disulfide functionalized silica nanoparticles sandwiching CdTe QDs. After surface imprinting via a sol-gel process, the epitope templates were removed from the surface-imprinted layers simply by reduction of the thiol-disulfide, affording oriented epitope-imprinted sites. By this method, the amount of epitope templates was only 1/20 of traditionally unoriented epitopes. The resulting sensors demonstrated significantly enhanced imprinting performance and high sensitivity, with the imprinting factor increasing from 2.6 to 3.9, and the limit of detection being 91 nM. Such epitope-oriented surface-imprinted method may offer a new design strategy for the construction of high-affinity protein recognition nanomaterials with fluorescence sensing. [Display omitted] • Oriented epitope-imprinted polymers combined with fluorescence sensing. • Grafted epitope surface imprinting by thiol–disulfide exchange reaction. • Significant reduction in epitope template usage for epitope-imprinted polymers. • Great increase in the imprinting factor of the protein imprinted polymers. • Significantly enhanced fluorescence detection of proteins in fluorescence sensors. [ABSTRACT FROM AUTHOR]

• Magnetic multi-template molecularly imprinted polymers (M-mt-MIPs) were prepared by surface imprinting and multi-template imprinting strategies. • M-mt-MIPs have specific recognition sites and high adsorption capacity for five typical chlorophenols. • M-mt-MIPs showed fast mass transfer, excellent magnetic property and thermal stability. • The M-mt-MIPs-MSPE-HPLC method were applied in complicated leather industry samples, showing simple, fast, sensitive, accurate and practical. Magnetic multi-template molecularly imprinted polymers (M-mt-MIPs) were successfully synthesized by surface imprinting and multi-template imprinting strategy, using polydopamine coated magnetic multi-walled carbon nanotubes as supporting materials, five typical chlorophenols (CPs) as templates, methacrylic acid as functional monomer and ethylene glycol dimethacrylate as cross-linker. Compared to non-imprinted polymers (NIPs), the as-prepared M-mt-MIPs showed high adsorption capacity (32.58‒80.63 mg g−1), rapid mass transfer and specific selectivity for the five targeted CPs, which were applied as magnetic solid-phase extraction (MSPE) adsorbents. Parameters affecting MSPE efficiency were detailed investigated, such as adsorbents dosage, sample pH, extraction time, type and volume of desorption solvent and salt effect. Combined with HPLC-DAD, a simple, rapid and sensitive method was established, showing good linearity (2‒200 μg L−1), low limits of detection (0.32‒0.49 μg L−1), and high enrichment factors (35.2‒108). The developed M-mt-MIPs-MSPE-HPLC method was applied to enrich and determine CPs in tannery wastewater, wet-blue and crust leather, and satisfactory spiking recoveries were attained in the range of 73.95‒109.7% with relative standard deviations (RSDs) of 2.13–8.48%. This study provided a new alternative material and method to rapid simultaneously extract and analyze low concentration of typical CPs in complicated matrices. [ABSTRACT FROM AUTHOR]

• Magnetic surface-imprinted polymer microspheres (Fe 3 O 4 @MIPs) were facilely prepared. • Fe 3 O 4 @MIPs showed enhanced selectivity, rapid extraction and good reusability for amphetamines. • A selective magnetic solid-phase separation method was developed for six amphetamines in water samples. • The method offers a shorter extraction time for analyzing amphetamines in water compared to other methods. Magnetic surface imprinted polymer microspheres (Fe 3 O 4 @MIPs) were successfully synthesized via Pickering emulsion polymerization, utilizing N-Methylphenethylamine as a surrogate template for amphetamine-type drugs. Fe 3 O 4 @MIPs not only possessed excellent dispersibility and enough magnetic properties in aqueous solutions, but also displayed good selectivity towards six amphetamines, with an imprinting factor ranging from 1.8 to 2.6. The adsorption kinetics closely aligned with the pseudo-second-order model, and the adsorption efficiency exceeds 80 % for each amphetamine at equilibrium. Fe 3 O 4 @MIPs were then employed as the efficient adsorbents for the extraction of amphetamine drugs. Extraction parameters, including sample pH, the mass of adsorbent, and the type and volume of eluting solvent, were carefully optimized. In combination with the high performance liquid chromatography tandem triple quadrupole mass spectrometry (HPLC-MS/MS), a selective magnetic solid-phase extraction (MISPE) method utilizing Fe 3 O 4 @MIPs was developed for the detection of six amphetamines in water samples. The limits of detection and limits of quantitation were determined to be 5.2∼23 ng L−1 and 17∼77 ng L−1, respectively. Recoveries for the six target drugs from lake water and sewage samples fell within the range of 87.2∼110 %. Additionally, the MISPE-HPLC-MS/MS method exhibited excellent repeatability, with a precision below 8.5 % at two spiking levels. The prepared Fe 3 O 4 @MIPs possessed the advantages of high selectivity, straightforward preparation, facile separation and good reusability, and was highly suitable for the efficient extraction of amphetamine-type substances in complex environmental water. [ABSTRACT FROM AUTHOR]

• Magnetic imprinted polymers (MMIPs) were constructed by two-step immobilization strategy. • The MMIPs possessed excellent adsorption capacity for bisphenol A (BPA). • MMIPs-based method was used for detection of BPA in environmental water and milk. Molecularly imprinted polymer with water-compatibility for effective separation and enrichment of targeted trace pollutants from complicated matrix has captured extensive attention in terms of their high selectivity and matrix compatibility. This study focuses on modified β-cyclodextrin is used as a hydrophilic functional monomer to develop magnetic molecularly imprinted polymers (MMIPs). MMIPs were prepared using Fe 3 O 4 nanoparticles as carriers and bisphenol A (BPA) as templates using a two-step fixation strategy and surface imprinting technology. The structural characteristic and binding properties of the prepared MMIPs were thoroughly studied. The MMIPs exhibited high crystallinity, high adsorption capacity, fast rebinding rate, remarkable selectivity and distinguish reusability. In addition, through magnetic solid-phase extraction separation technology and high-performance liquid chromatography ultraviolet quantitative detection technology, MMIPs are used for selective enrichment and detection of BPA in complex media such as environmental water and milk. This work provides a new route to construct the hydrophilic molecularly imprinted materials and a new sight on developing more effective sample pretreatment strategies for monitoring targeted pollution in complicated aqueous media. [ABSTRACT FROM AUTHOR]

A novel covalent organic framework and molecularly imprinted polymer (COF-MIP) composite, incorporating 1,1′-bis(allylcarbamoyl)ferrocene (AC-Fc) as a cross-linker, was synthesized through free radical polymerization for the ratiometric electrochemical detection of 5-hydroxytryptamine (5-HT). The AC-Fc cross-linker was synthesized using 1,1′-ferrocenedicarboxylic acid as a reactant. Subsequently, the COF-MIP was prepared using surface imprinting technique, employing AC-Fc as the cross-linker, COF as the supporter, and 5-HT as the template. The COF-MIP was employed in the development of a ratiometric electrochemical sensor for 5-HT. Upon 5-HT introduction, the peak current of 5-HT exhibited a concentration-dependent increase, while that for ferrocene (Fc) remained nearly constant. By utilizing Fc and 5-HT peak currents as reference and indicator signals, respectively, 5-HT was quantitatively determined. The ratio of I 5-HT /I Fc for the COF-MIP sensor was 4.69, 3.69, and 1.98 times higher than those of non-imprinted polymer (NIP), traditional MIP, and COF-NIP sensors, respectively. The ratiometric sensor with COF-MIP demonstrated a linear ratiometric signal (I 5-HT /I Fc) in response to 5-HT concentrations within the range of 0.2–10 µM, with a detection limit of 0.03 µM. The relative standard deviation of the non-ratiometric and ratiometric sensors was 8.7% and 2.7%, respectively. This methodology was successfully employed for the detection of 5-HT in human serum. [Display omitted] ● AC-Fc as an alkenyl ferrocene was synthesized with 1,1′-ferrocenedicarboxylic acid as a reactant. ● COF-MIP was synthesized with AC-Fc as cross-linker by free radical polymerization. ● COF-MIP was applied for ratiometric electrochemical detection of 5-hydroxytryptamine. ● Both the I 5-HT /I Fc and I 5-HT for COF-MIP/GCE were the highest among electrodes. ● The ratiometric strategy greatly improved the reproducibility of the COF-MIP sensor. [ABSTRACT FROM AUTHOR]

A novel magnetic molecularly imprinted polymer only based on deep eutectic solvents (DESs-MMIP) was successfully synthesized. The DESs-MMIP was constructed by using 2-hydroxyethyl methacrylate/tetrabutylammonium chloride deep eutectic solvent (DES 1) as functional monomer, arylamide/(3-acrylamidopropyl) trimethylammonium chloride deep eutectic solvent (DES 2) as cross-linker and bovine hemoglobin (BHb) as template through surface imprinting technology. The obtained DESs-MMIP was characterized by transmission electron microscope, X-ray diffraction, fourier transform infrared spectrometry, thermal gravimetric analysis and vibrating sample magnetometer. Under the optimized conditions, the maximum adsorption capacity of DESs-MMIP on BHb was 229.54 mg g−1 and the imprinting factor reached up to 21.89. The selective adsorption experiments indicated that compared with seven references, DESs-MMIP showed significant selectivity for BHb. The new-type DESs-MMIP exhibited higher adsorption capacity and imprinting factor on BHb than molecularly imprinted polymers constructed with traditional functional monomer and cross-linker in reported methods. The recognition of BHb by DESs-MMIP in calf blood samples demonstrated the practicality of the particles. The DESs-MMIP only based on deep eutectic solvents with excellent selectivity is expected to become an ideal candidate for selective recognition of BHb in complicated samples. Abstract Graphic Synthesis scheme of DESs-MMIP. Image 1 • A new magnetic molecularly imprinted polymer only based on deep eutectic solvents was successfully synthesized. • Two eco-friendly DESs were used as functional monomer and cross-linker instead of traditional reagents. • The MIPs exhibited excellent selective recognition ability to BHb. • The MIPs can recognize BHb in real calf blood samples effectively. [ABSTRACT FROM AUTHOR]

A novel approach combining boronate affinity with surface molecular imprinting was developed for the specific recognition and separation of ginsenoside Rb1. Firstly, the boronic acid-functionalized polymer microspheres were prepared as inner cores via suspension polymerization using methyl methacrylate, ethyleneglycol dimethacrylate, and 4-vinylphenyl boronic pinacol ester (4-VBPE) as polymerization monomers. Then, the Ginsenoside Rb1 (GRb1) template was covalently pre-anchored onto the surface of microspheres through boronate affinity binding after the hydrolysis of 4-VBPE. Finally, dopamine and polyethyleneimine were used as co -coating monomers to form a thickness-controllable imprinting layer onto the polymer microspheres via in-water self-copolymerization. The key factors affecting specific recognition, including the boronic acid content, adsorption media, and polymerization time were carefully optimized. The resulting molecularly imprinted microspheres (MIMs) exhibited strong surface hydrophilicity. In the aqueous media, the optimal adsorption capacity for the template reached 81.45 μmol g−1, and the imprinting factor was 5.32. The specific evaluation showed that the MIMs had a much higher selectivity for GRb1 than its analogues, and the selectivity coefficients were all higher than 2.4. In addition, the MIMs can be applied as adsorbents for solid-phase extraction to selectively separate ginsenosides from American ginseng extract. The eluting recovery ratios of GRb1, GRg2, and GRd reach 92.39%, 88.90%, and 92.49%, respectively. [Display omitted] • Hydrophilic surface MIMs were prepared based on PDA/PEI co-coating. • The boronic acid-microspheres were prepared via suspension polymerization. • 4-VBPE replaced vinylphenylboronic acid as boronate-functionalized monomers. • The surface MIMs exhibited improved recognition properties in aqueous media. • The surface MIMs could separate and enrich ginsenosides from complex matrix. [ABSTRACT FROM AUTHOR]

• Surface imprinted tubular carbon nanofibers (SIPTCFs) are first developed. • SIPTCFs have self-driven property. • The structure of SIPTCFs is good for rapid adsorption. • The adsorption amount of SIPTCFs to BSA can reach 541.99 mg/g within 60 min. • SIPTCFs show high selectivity to BSA from mixed proteins and actual samples. Increasing mass transfer rate and adsorption amount are always challenges in the field of surface protein imprinting. In order to promote the development of protein purification, surface imprinted tubular carbon nanofibers (SIPTCFs) with self-driven property are first developed in this paper. The carrier is tubular carbon nanofiber obtained by hypercrosslinking reaction, carbonization and carboxyl functionalization. Bovine serum albumin (BSA) and polydopamine (PDA) are used as template and imprinted polymer layer, respectively. The resulted materials contain cavity and porous tube wall, which make the osmotic pressure difference between inside and outside of SIPTCFs during the adsorption process. Thereby it endows the SIPTCFs self-driven specific adsorption performance. The SIPTCFs have high specific surface area, reasonable pore structure and self-driven properties. They are the main reasons for accelerating the adsorption process and increasing the adsorption amount. The adsorption amount of SIPTCFs to BSA can reach 541.99 mg/g within 60 min. In addition, SIPTCFs can recognize the target protein BSA with high selectivity from the mixed proteins of HSA, Lyz, Cyt C and Bhb as well as fetal bovine serum (FBS). Because of the excellent reusability and separation ability for actual samples, SIPTCFs will be intensely promising materials for protein separation and purification. [ABSTRACT FROM AUTHOR]

Abstract A novel magnetic molecularly imprinted polymer on a magnetic graphene oxide surface, GO@Fe 3 O 4 -MIP, was successfully synthesized and applied as adsorbent for the extraction of microcystin-LR (MC-LR) from water samples prior to analysis using high performance liquid chromatography (HPLC). A variety of characterizations have proven successful preparation of this material. The GO@Fe 3 O 4 -MIPs showed high adsorption capacity with maximum adsorption capacity of 1.24 mg/g, fast adsorption rate (25 min) and high selectivity toward MC-LR. The adsorption processes followed the Freundlich isotherm and pseudo-second-order kinetic models. Various extraction conditions were optimized. The linearity of the method was studied from 2 to 10,000 μg/L, obtaining a correlation coefficient of 0.9985. The limit of detection was calculated as 0.08 μg/L (S/N = 3), and the recoveries from spiked samples were 86%–113%, with relative standard deviations of 1.0%–6.8%. The developed method was suitable for the rapid and sensitive determination of MC-LR in water samples. Highlights • A facile and green imprinting strategy for MC-LR extraction and detection was proposed. • Dopamine was used to functionalize GO, acted as functional monomer and cross-linker. • Fe 3 O 4 @GO-MIP had high imprinting efficiency, binding capacity and simple separation. [ABSTRACT FROM AUTHOR]

Molecular recognition plays an important role in the numerous living systems. Molecularly imprinted polymers (MIPs) are tailor-made recognition particles that can mimic biological receptors and capable of sensitively and selectively recognize specific target molecules. In recent years, application of nanoparticles as sorbent has gained the significant attention in bioanalysis field. Molecular imprinting has performed effectively for low-molecular weight compounds (<1500 Da) and the number of reports on the macromolecules imprinting (>1500 Da) is increasing considerably during the recent years. Proteins are vital markers of some diseases and protein imprinting is one of the applicable tools to generate tailor-made biomimetic receptors with antibody-like specific recognition sites that compared with small-molecular imprinting, due to the variety of reasons such as the large size, structural and chemical complexity, and environmentally instability, relatively little advancement has been done in this field. In this review, the main topics of concern are protein-imprinting approaches, rational designs of protein-MIPs, metrics for successful proteins imprinting, and protein biomarkers. Additionally, we focus on gathering, summarizing, and critically evaluating the reports, which have recently been employed MIP based synthetic nanoparticles as sorbent for sensing and separating proteins. Also, we offer suggestions for future successful attainment in the field of protein-imprinted polymers. Image 1 • Description of protein imprinting and critical barriers to the protein recognition. • Review on the recent achievements of MIP-based protein imprinting approaches. • Introducing the rational designs of protein-MIPs and metrics for successful protein imprinting. • Describing the future studies requirements in the field of protein imprinting and protein biomarkers. [ABSTRACT FROM AUTHOR]

During the last decade, templating polymers using molecular imprinting has developed into an efficient strategy for the creation of selective synthetic receptor materials based on cross-linked polymeric networks. However, incubation studies and scavenger applications using conventional molecularly imprinted polymers (MIPs) are rather time consuming, as they require centrifugation and extraction steps. An innovative method circumnavigating this problem is the use of magnetic particles facilitating separations via magnetic field. Nowadays, magnetic materials and especially nanoparticles find widespread applications in analytical chemistry, medicine, and biotechnology. Consequently, combining molecularly imprinting materials with magnetic properties provides a new class of smart synthetic receptors, i.e., magnetic molecularly imprinted polymers (MMIPs). This review gives an overview on these multifunctional materials prepared for biomacromolecules such as enzymes, proteins, DNA and viruses including synthesis, applications and also highlights future trends and perspectives in this emerging research field. • Synthesis of MMIPs. • Imprinting strategies and selected applications. • Current challenges and future trends in MMIPs. [ABSTRACT FROM AUTHOR]

Highlights • Double affinity integrated MIPs nanoparticles (D-MIPs) were simply synthesized. • Gentle oxidation of APBA endowed boronate affinity and maintenance of protein activity. • D-MIPs showed excellent recognition selectivity, large rebinding capacity and fast kinetics. • Multiple bindings and imprinting effect was the mechanism for enhancing specific separation. Abstract The selective recognition, isolation, and subsequent enrichment of target glycoproteins are becoming more and more important in clinical diagnosis. In this work, nano-sized molecularly imprinted polymers integrated double affinity (i.e. metal ion affinity and boronate affinity) (D-MIPs) were prepared for specific separation of ovalbumin (OVA). Poly(styrene-glycidyl methacrylate) nanoparticles (PSG) with epoxy bonds were firstly grafted with iminodiacetic acid (IDA) by ring-opening reaction, and then the Cu2+ was chelated to prepare PSG/IDA-Cu2+. Subsequently, imprinted OVA molecules were pre-immobilized through Cu2+ ion affinity. Finally, a surface imprinting layer was formed though the gentle self-oxidization of a kind of boronic acid ligand (i.e. 3-aminophenylboronic acid, APBA). By washing out imprinted molecules, as-prepared D-MIPs posed higher monolayer binding capacity (138.92 mg g−1) and faster capture kinetics (30 min) for OVA, when compared with single affinity integrated MIPs (S-MIPs) and non-imprinted polymers (NIPs), and the chemical adsorption dominated double affinity was the rate-determining step for whole adsorption process. The imprinting factor (IF) of OVA, horseradish peroxidase (HRP) and bovine serum albumin (BSA) by the available D-MIPs were 4.44, 2.23 and 1.47, respectively, which confirmed the better selectivity for OVA. D-MIPs performed favorable regeneration ability and a promising application in actual sample. In addition, a combination of synergistic multiple bindings and imprinting effect, as the mechanism for enhancing specific separation, was also demonstrated. [ABSTRACT FROM AUTHOR]

Abstract In this work, surface molecularly imprinted polymers (SMIPs) were prepared as a specific sorbent to remove the limonin from the lemon juice for the first time, and then the MIPs containing limonin were directly made into a water-soluble gel to treat inflammation of mice. The resulting polymers were characterized by scanning electron microscopy, transmission electron microscopy and Fourier transform infrared spectrometer spectra. And the polymerization conditions and adsorption performances of the resultant nanomaterials were further investigated in detail. Results showed that the MIPs have higher adsorption capacity (27.72 mg/g) compared with surface molecularly non-imprinted polymers (NIPs) (8.12 mg/g). The selectivity experiment indicated that the polymers had excellent selective recognition for limonin and the selectivity factors were calculated as 2.75 and 1.83 for nomilin and obakunone, respectively. The MIPs were successfully used as adsorbent for selectively removing limonin from lemon juice and the MIPs extracted almost all the limonin from lemon juice according to the HPLC results. Furthermore, the MIPs with limonin were processed into water-soluble gel, which can be used to reduce the inflammation and enhance wound healing of model mice. Highlights • The molecularly imprinted solid-phase extraction debitterize technology was reported for the first time. • Molecularly imprinted polymers for limonin were prepared. • The adsorption effects of the MIPs and NIPs for limonin were investigated. • The molecularly imprinted polymers with limonin can be used to treat external infections with significant effects. [ABSTRACT FROM AUTHOR]

Abstract With the extensive applications of lithium ion batteries, the exploitation and recycle of lithium resources is essential for the manufacture of lithium ion batteries. This work reports that novel lithium ion imprinted polymers (LIPs) loaded on the surface of multi-wall carbon nanotubes (MWCNTs) were prepared by surface imprinting polymerization. The performance of the prepared LIPs was analyzed by UV–vis recording spectrophotometry, ICP-AES, FT-IR and SEM. The maximum adsorption capacity of the 15 mg LIPs was calculated to be 1362.56 μmol / g at a 300 mg/L Li+ solution. In the presence of Na+, K+, Cu2+ and Zn2+, the selectivity factors of the LIPs for Li+ were 3.66, 3.01, 2.05 and 2.10, respectively, suggesting that the LIPs had ideal selectivity for Li+. In addition, the experimental data can be described well by the pseudo-first-order and Langmuir adsorption isotherm models. The regeneration of the LIPs was performed by being eluted with 1 M nitric acid, and the adsorption capacity of the regenerated LIPs only decreased about 10.3% after ten cycle experiments. Therefore, the strategy described in this work is worth further exploring its application on the extraction and separation of lithium to realize the recovery utilization of lithium in water. Graphical abstract Image Highlights • The maximum adsorption capacity of the LIPs is 1362.56 μmoL/g. • DB14C4 is used to decorate MWCNTs to improve their selectivity. • The adsorption capacity of the LIPs only decreases 8.6% after three cycles. • The LIPs have high selectivity for Li+ in the preference of Na+, K+, Cu2+ and Zn2+. • The adsorption behavior of the LIPs can be well fitted by Langmuir model. [ABSTRACT FROM AUTHOR]

Highlights • Biopolymer chitosan as natural substrate with multifunctionality for surface imprinting. • Faster simultaneous removal of salicylic acid and cadmium within 40 min. • Higher removal efficiency for salicylic acid (45.77 mg/g) and cadmium (53.42 mg/g). • Grafted chitosan, an ecofriendly substitute for surface imprinting. Abstract The present work demonstrates functionalized chitosan as an ecofriendly substitute to the conventional costly substrates and monomers for simultaneous surface imprinting of salicylic acid (SA) and cadmium (Cd). Dual surface imprinted acrylamide functionalized chitosan based polymer (AGDMIP), with higher numbers of imprinted sites for SA and Cd was synthesized using acrylamide grafted chitosan, epichlorohydrin as crosslinker, Cd as template and 4 hydroxy benzoic acid (4HBA) as mimic template (supported by computational modeling). FTIR, SEM, XRD, BET surface area and TEM analysis confirmed successful preparation, mesoporous nature and surface imprinting of AGDMIP. The adsorption data could be fitted into Langmuir isotherm model with the maximum adsorption capacity of 45.77 mg g−1 (SA) and 53.42 mg g−1 (Cd). Temkin and Intraparticle diffusion models confirmed the chemical nature and presence of imprint sites within AGDMIP respectively. AGDMIP could be reused for six cycles and exhibited good removal efficiency in real samples. [ABSTRACT FROM AUTHOR]

We synthesized and characterized surface-imprinted poly (ethyleneimine) (PEI)-grafted mesoporous silica SBA-15 (Cu-imprinted PEI-SBA-15) for selective Cu(II) sorption from aqueous solutions. To enhance the Cu(II) selectivity of Cu-imprinted PEI-SBA-15, Cu(II) loading on PEI-SBA-15 was increased via Cu(II) sorption under high-molar-concentration ratios of chloride (Cl) and Cu(II) ions. Then, selective Cu(II) sorption sites were increased through imprinting processes (crosslinking and elution) on Cu-loaded PEI-SBA-15. Selective experiments were performed using Cu-imprinted PEI-SBA-15 prepared at various [Cl − ]/[Cu(II)] ratios, ranging from 2 to 1000. In multinary solutions containing divalent ions, such as Cu(II), Pb(II), Zn(II), Ni(II), and Co(II), Cu(II) selectivity was highest (79.62) at a [Cl − ]/[Cu(II)] ratio of 500; the relative Cu(II) selectivity for Cu-imprinted PEI-SBA-15 over PEI-SBA-15 was 29.24. In multinary solutions containing Cu(II) along with trivalent and tetravalent ions, such as Al(III), Cr(III), and Zr(IV), the Cu(II) selectivity was also highest (3.40) at a ratio of 500; the relative Cu(II) selectivity was 3.96. In this study, we demonstrated that the Cu(II) selectivity of surface-imprinted SBA-15 could be enhanced through its preparation under high [Cl − ]/[Cu(II)] ratios. [ABSTRACT FROM AUTHOR]

[Display omitted] • A boronic acid-based surface imprinted polymer (MSi-MIP) is fabricated. • The nanozyme (Ni-Fe-MOF-BA) exhibits the properties of recognition ability. • A colorimetric sandwich method based on MIPs and Ni-Fe-MOF-BA is established. • A low detection limit for colorimetric detection of OVA. • Application of OVA allergen detection in vaccines. Ovalbumin (OVA) is the main allergen in vaccines, and the sensitive detection of it could protect hypersensitive people. However, traditional detection technologies usually require natural antibodies, natural enzymes and long analysis time, which is not conducive to transportation, preservation and rapid detection. To solve this problem, the sandwich colorimetric strategy using Ni-Fe-MOF nanozyme linked with magnetic silicon dioxide surface molecularly imprinted particles (MSi-MIPs) are proposed for the first time to rapidly detect OVA in vaccines. The high sensitivity of this strategy depends on the sandwich structure of surface molecularly imprinted nanoparticles, OVA and nanozymes. Ultra-thin Ni-Fe-MOF nanozyme exhibits large specific surface area and more peroxidase active sites. This has enabled the establishment of a specific and stable detection tool for OVA in vaccines. Under the optimal conditions, the assay exhibited a wide linear response range of 2.5 to 25 ng mL−1. The low limit of detection (1.02 ng mL−1) and the short analysis time (20 min) demonstrated the great potential of the strategy for OVA detection in vaccine samples. [ABSTRACT FROM AUTHOR]

• A facile method was developed to imprint protein on the surface of flower-like NiO. • The NiO@PDA/MIPs possessed flower-like sandwich-structure. • The NiO@PDA/MIPs exhibited excellent binding capacity, selectivity and reusability. • The NiO@PDA/MIPs could efficiently extraction OVA from egg white samples. In this work, a facile method for synthesis of flower-like sandwich-structured molecularly imprinted polymers (NiO@PDA/MIPs) was proposed for protein recognition. Polydopamine modified flower-like NiO was used as substrate to immobilize the target protein (ovalbumin, OVA), and dopamine was utilized as functional monomer to form the imprinted layer. The whole preparation process was conducted in aqueous solution at room temperature. The key preparation conditions were studied systematically. Owing to the large surface-to-volume of the flower-like structure and the multifunctional groups on the polydopamine layer, the NiO@PDA/MIPs showed large binding capacity (143.2 mg/g), efficient adsorption kinetics (60 min) and excellent selectivity toward OVA. Meanwhile, the NiO@PDA/MIPs possessed satisfactory stability and reusability. Finally, successful capture of OVA from egg white suggested its potential value in practical applications. [ABSTRACT FROM AUTHOR]

The rapid, efficient and selective extraction of heavy metal ions is significant for wastewater pretreatment and metal ion recycle. Using montmorillonite as the template substrate and Pb 2+ as template ions, a novel two-dimensional montmorillonite-based surface ion imprinted polymer (IIP-MMT) adsorbent is successfully synthesized via activators generated by electron transfer for atom transfer radical polymerization (AGET-ATRP). Batch adsorption experiments are performed to assess the properties of the imprinted polymer sorbent, along with its selectivity and reusability in practical extraction of Pb 2+ . It is interesting that the crosslinking density of the imprinted polymer has impact on the sorption property, where suitable density is coupled with the highest adsorption capacity and the best selectivity. Benefiting from the surface-imprinting technique and AGET-ATRP, IIP2-MMT is proved to own a highly effective Pb 2+ adsorption capacity to reach 158.68 mg/g within 30 min, where the corresponding maximum adsorption capacity is 201.84 mg/g. Moreover, this material exhibits satisfactory stability and reusability that the high adsorptive capability of IIP-MMT retains more than 95% after six cycles. Thus, it is expected to reduce the wastewater disposal expenses. Besides, owing to the characteristics of PHEMA brushes and SHA chelating ligand, IIP-MMT has strong anti-interference and anti-blockage abilities to extract Pb 2+ from smelting wastewater, slag and contaminated soil. Considering the low cost, excellent stability, high extraction efficiency, environmental friendliness, it is expected that the proposed material is very promising for treatment of heavy metals-contaminated wastewaters and soil, or ion recycle. [ABSTRACT FROM AUTHOR]

Boronate-functionalized surface imprinted nanoparticles that function under physiological pH would be highly desirable for specific enrichment of target glycoproteins. In this work, magnetic molecularly imprinted polymers integrated with low pKa teamed boronate affinity (Fe 3 O 4 @PGMA-TBA/MIPs) were fabricated for selective separation of glycoprotein at pH = 7.4. The teamed boronate affinity (TBA) was formed by boron-nitrogen (B-N) coordination between 1,6-hexamethylenediamine and 3-aminophenylboronic acid, and then was fixed on the surface of magnetic poly(glycidyl methacrylate) (Fe 3 O 4 @PGMA) through ring-opening reaction. After immobilizing the template glycoproteins (ovalbumin, OVA), surface imprinting layer was deposited onto Fe 3 O 4 @PGMA-TBA surface via redox polymerization of aniline, and Fe 3 O 4 @PGMA-TBA/MIPs with obvious core–shell-shell structure were prepared by removing template. Fe 3 O 4 @PGMA-TBA/MIPs were demonstrated with an imprinted polymer film (10–20 nm) and exhibited superparamagnetic property ( M s  = 32 emu g −1 ) and magnetic stability after multiple regenerations. Besides, the results of 11 B MAS NMR spectrum and zeta potentials confirmed the presence of TBA resulting from B-N coordination. Additionally, taking advantage of surface imprinting and TBA, as-prepared Fe 3 O 4 @PGMA-TBA/MIPs posed high binding capacity (190.7 mg g −1 ) and fast capture kinetics (50 min) toward OVA under physiological pH. More importantly, because of the TBA was electroneutral at pH = 7.4, Fe 3 O 4 @PGMA-TBA/MIPs not only exhibited superior specific recognition toward OVA (imprinting factor IF = 7.51), but also maintained the activity of OVA from practical samples analysis. Therefore, this work opened up a universal route for developing intelligent controllability molecular imprinting materials for the specific separation of glycoproteins in biomedical filed under physiological pH. [ABSTRACT FROM AUTHOR]

Bromelain, a cysteine endopeptidase enzyme of great commercial value, has been widely used in food, pharmaceutical, and cosmetic industries. Conventional methods for purification of bromelain are still limited by a low binding efficiency, time-consuming process, and expensive equipment. Therefore, for selective absorption of bromelain, we developed a facile and effective method to fabricate magnetic mesoporous molecularly imprinted polymers using pericarpium granati -derived carbon as the carrier for the first time. The characterizations of the imprinted polymers indicated that a polydopamine layer was coated on the surface of the carrier and the crystallinity of the carrier did not change. The obtained imprinted polymers exhibited favourable saturation magnetization, a high adsorption capacity of 135.96 mg g −1 , a fast equilibrium time, and satisfactory reusability. The imprinted polymers were prepared by an eco-friendly method and exhibited rapid separation and good adsorption performance, thus making the method applicable to biomacromolecular separation, proteomic analysis, and biomedical research. [ABSTRACT FROM AUTHOR]

In view of the significance of glycoprotein biomarkers for early clinical diagnostics and treatments of diseases, it is essential to develop efficient and selective enrichment approaches for glycoproteins. Molecularly imprinted polymers (MIPs) have found important applications for separation and enrichment of glycoproteins. In this study, we use boronate affinity-based controllable oriented surface imprinting to prepare glycoprotein-imprinted magnetic nanoparticles. A glycoprotein was first immobilized onto the surface of boronic acid functionalized magnetic nanoparticles by boronate affinity. Subsequently, self-polymerization of 2-anilinoethanol was carried out to form thin imprinting coating on the magnetic nanoparticles surface with appropriate thickness. After removing the template with an acidic solution containing sodium dodecyl sulfate, 3D cavities complementary to the template were efficiently formed in the imprinting layer. The imprinting coating was highly hydrophilic and presented limited residual boronic acid, thus non-specific binding was avoided. Using horseradish peroxidase as a model target, the effects of imprinting conditions on the properties and performance of the prepared MIPs were investigated. The obtained MIPs exhibited several highly favorable features, including excellent specificity, high binding strength and low binding pH. The MIPs were successfully applied to the analysis of transferrin (TRF) in human serum. [ABSTRACT FROM AUTHOR]

A highly sensitive electrochemical sensor using a carbon paste electrode (CPE) modified with surface molecularly imprinted polymeric microspheres (SMIPMs) was developed for methyl parathion (MP) detection. Molecular imprinting technique based on distillation precipitation polymerization was applied to prepare SMIPMs and non-surface imprinted microspheres (MIPMs). The polymer properties including morphology, size distribution, BET specific surface area and adsorption performance were investigated and compared carefully. Both MIPMs and SMIPMs were adopted to prepare CPE sensors and their electrochemical behaviors were characterized via cyclic voltammetry and electrochemical impedance spectroscopy. Compared with MIPMs packed sensor, SMIPMs/CPE exhibits a higher sensing response towards MP with linear detection range of 1 × 10 −12 –8 × 10 −9 mol L −1 and detection limit of 3.4 × 10 −13 mol L −1 (S/N = 3). Moreover, SMIPMs/CPE exhibits good selectivity and stability in multiple-cycle usage and after long-time storage. Finally, the developed sensor was used to determine MP in real samples including soil and vegetables and only simple pretreatment is needed. The detection results were consistent with those obtained from liquid chromatography. Collectively, this newly developed sensor system shows significant potential for use in a variety of fields like food safety, drug residue determination and environmental monitoring. [ABSTRACT FROM AUTHOR]

Novel water-compatible magnetic molecularly imprinted polymers were developed. The magnetic core was firstly grafted by methyl acrylate and ethanediamine to increase the number of amino groups, which could immobilize more templates and form high-density recognition sites. Dopamine was adopted as functional monomer and crosslinker to retighten templates and prepare hydrophilic polymers. The characterization, adsorption capability, selectivity, and reusability were investigated in detail. The limit of detection and quantification of the method were 0.01 μg mL −1 and 0.038 μg mL −1 . The experimental results exhibited that the resultant nanomaterials had high crystallinity, satisfactory magnetic property, fast kinetics, favorable adsorption capacity, excellent specificity, and pleasing recovery after a mild elution. In addition, the recoveries of the proposed method at four spiked levels analysis were between 98.4% to 101.3%. The obtained imprinted nanoparticles were used as sorbents for selective separation and determination of chlorogenic acid in Honeysuckle tea. [ABSTRACT FROM AUTHOR]

This paper introduces a novel method to electrochemically grow surface imprinted poly(3-TAA-co-EDOT) patterns from a gold pinhole array inside an inverse silica opal monolayer for the detection of aspartame. Using colloidal lithography, the designed 2D silica opal photonic crystal acts as an insulating porous mask with exposed gold pinhole arrays to form molecularly imprinted conducting polymers (MICPs). As the number of cyclic voltammetry (CV) cycles is increased, the MICPs grew toward the silica inner wall retaining the imprinted pillar array formed on the gold pinholes. For all three types of MICP films investigated (i.e., CV1, CV3, and CV5), artificial recognition sites were successfully generated after aspartame extraction; aspartame adsorption was then investigated using quartz crystal microbalance measurements. In the case of MICP-CV5, all of its sensing properties such as sensing response (Δ f ), imprinting effect (I f ), and selectivity were found to be superior to those measured for the other polymers (i.e., MICP-CV1 and −CV3). Furthermore, the MICP-CV5 film demonstrated significantly enhanced sensing behavior relative to 2D inverse porous MICP ( p -MICP) films with similar surface morphologies, which were grown electrochemically by conventional polystyrene colloidal lithography. Overall, the results presented herein clearly demonstrate that this novel lithographical method leads to an increased number of imprinting sites in MICP structures, which impart the resultant polymers with enhanced sensing properties. [ABSTRACT FROM AUTHOR]

[Display omitted] • A SMI electrochemical biosensor is fabricated for SARS-CoV-2 S protein detection. • Cu 7 S 4 -Au is used as the built-in probe and modified on the surface of SPCE. • 4-MPBA is anchored to Cu 7 S 4 -Au surface for the immobilization of the template. • 3-APBA is electropolymerized on the electrode surface and used as the MIPs. • Boronate ester bonds play a crucial role in the fabrication of the SMI biosensor. Sensitive detection of severe acute respiratory syndrome coronavirus-2 (SARS-CoV-2) spike protein (S protein) is of significant clinical importance in the diagnosis of COVID-19 pandemic. In this work, a surface molecularly imprinted (SMI) electrochemical biosensor is fabricated for the detection of SARS-CoV-2 S protein. Cu 7 S 4 -Au is used as the built-in probe and modified on the surface of a screen-printed carbon electrode (SPCE). 4-Mercaptophenylboric acid (4-MPBA) is anchored to the surface of the Cu 7 S 4 -Au through Au–SH bonds, which can be used for the immobilization of the SARS-CoV-2 S protein template through boronate ester bonds. After that, 3-aminophenylboronic acid (3-APBA) is electropolymerized on the electrode surface and used as the molecularly imprinted polymers (MIPs). The SMI electrochemical biosensor is obtained after the elution of the SARS-CoV-2 S protein template with an acidic solution by the dissociation of the boronate ester bonds, which can be utilized for sensitive detection of the SARS-CoV-2 S protein. The developed SMI electrochemical biosensor displays high specificity, reproducibility and stability, which might be a potential and promising candidate for the clinical diagnosis of COVID-19. [ABSTRACT FROM AUTHOR]

[Display omitted] • Lyz-imprinted SPR biosensor was fabricated for Lyz detection in complex matrix. • MIPs were prepared by surface imprinting and post-imprinting modification strategy. • Introducing non-covalent reaction into MIPs improved its specificity. • Grafting protein-resistant polymer reduced nonspecific adsorption. • Lyz-MIPs biosensor exhibited high selectivity and good reusability. The aim of this study is to fabricate surface plasmon resonance (SPR) biosensors for real-time detection of protein in complex media. Lysozyme (Lyz) was chosen as a model, and dopamine was used as functional monomer and cross-linker to prepare Lyz surface imprinted SPR biosensors (Lyz-MIPs). Non-covalent interaction was introduced into Lyz-MIPs via a self-assembled monolayer of 3-mercaptopropionic acid to improve the specificity, and protein-resistant poly(2-methyl-2-oxazoline-co-ethylene imine) was also introduced to resist nonspecific adsorption of polydopamine toward proteins in noncavity regions. The prepared Lyz-MIPs biosensor was characterized by X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, atomic force microscopy, variable angle spectroscopic ellipsometry, static water contact angle, and zeta potential measurements. SPR adsorption studies were carried out in aqueous Lyz solutions, and the limits of detection and quantification were obtained as 0.19 μg mL−1 and 0.58 μg mL−1, respectively. In addition, Lyz-MIPs biosensor exhibited high selectivity and good reusability. Finally, Lyz-MIPs biosensor was used to detect Lyz in complex media. The recovery of Lyz in simulated egg white was 95.3–105.0%, and 0.23 μg mL−1 Lyz was detected by using Lyz-MIPs biosensor in 20,000 times diluted hen egg white. [ABSTRACT FROM AUTHOR]

There is a significant need for the development of the novel adsorbents in the field of protein purification. In this study, thin hemoglobin imprinted film (MIP) was fabricated onto the bacterial cellulose nanofibers’ (BCNFs) by surface imprinting method using metal ion coordination interactions with N-methacryloyl–(L)-histidinemethylester (MAH) and copper ions. The hemoglobin surface imprinted bacterial cellulose nanofibers (MIP-BCNFs) was applied to selective recognition of hemoglobin and purification from hemolysate. The characterization of the MIP-BCNFs was carried out by the Fourier Transformed Infrared Spectroscopy (FT-IR), Scanning Electron Microscopy (SEM), micro-Computerized Tomography (μCT), atomic force microscopy (AFM) and surface area measurements. The adsorption experiments of hemoglobin onto the MIP-BCNFs and NIP-BCNFs from aqueous hemoglobin solutions were investigated in a batch system. The results showed that MIP-BCNFs are promising materials for purification of hemoglobin with high adsorption capacity, significant selectivity and reusability. [ABSTRACT FROM AUTHOR]

Nanostructured artificial receptor materials with unprecedented hierarchical structure for determination of human serum albumin (HSA) are designed and fabricated. For that purpose a new hierarchical template is prepared. This template allowed for simultaneous structural control of the deposited molecularly imprinted polymer (MIP) film on three length scales. A colloidal crystal templating with optimized electrochemical polymerization of 2,3′-bithiophene enables deposition of an MIP film in the form of an inverse opal. Thickness of the deposited polymer film is precisely controlled with the number of current oscillations during potentiostatic deposition of the imprinted poly(2,3′-bithiophene) film. Prior immobilization of HSA on the colloidal crystal allows formation of molecularly imprinted cavities exclusively on the internal surface of the pores. Furthermore, all binding sites are located on the surface of the imprinted cavities at locations corresponding to positions of functional groups present on the surface of HSA molecules due to prior derivatization of HSA molecules with appropriate functional monomers. This synergistic strategy results in a material with superior recognition performance. Integration of the MIP film as a recognition unit with a sensitive extended-gate field-effect transistor (EG-FET) transducer leads to highly selective HSA determination in the femtomolar concentration range. [ABSTRACT FROM AUTHOR]

We report a significant enhancement of hydrophillity of polysulfone (Psf) membranes after modification with graphene oxide (GO) as a filler followed by surface imprinting on the surface of GO/Psf composite imprinted membranes (CIMs). The surface imprinting on the GO-Psf membrane was employed in order to enhance its selectivity towards polycyclic aromatic hydrocarbons (PAHs) in water. The CIMs were prepared through a process of phase inversion of a mixture of graphene oxide and polysulfone (Psf) in N-methylpyrrolidone (NMP). Fourier-transform spectroscopy (FT-IR) of the imprinted showed new peaks at 935 cm −1 and 1638 cm −1 indicating success in surface imprinting on the GO-Psf membrane. The CIM also showed improvement in flux from 8.56 LM −2 h −1 of unmodified polysulfone membrane to 15.3 LM −2 h −1 in the CIM, salt rejection increased from 57.2 ± 4.2% of polysulfone membrane to 76 ± 4.5%. The results obtained from the contact angle measurements showed a decrease with increase in GO content from 72 ± 2.7% of neat polysulfone membrane to 62.3 ± 2.1% of CIM indicating an improvement in surface hydrophilicity. The results from this study shows that, it is possible to improve the hydrophilicity of the membranes without affecting the performance of the membranes. [ABSTRACT FROM AUTHOR]

A new ion-imprinted polymer (IIP) was synthesized from sodium carboxymethyl cellulose and used for the adsorption of hexavalent chromium from aqueous solution. Epichlorohydrin was used to stabilize the polymer before ethylenediamine (EDA) ligand and Cr(VI) were introduced. The obtained IIP was characterized with FTIR, XPS, TGA, 13 C NMR, SEM, EDX, BET and zeta sizer. The kinetics of adsorption followed a pseudo-second-order model while the Langmuir adsorption isotherm provided the best fit with a maximum adsorption capacity of 177.62 mg/g at 25 °C. The Langmuir adsorption capacity for the non-imprinted polymer (NIP) at 25 °C was 149.93 mg/g. Thermodynamic parameters indicated an endothermic process and spontaneous adsorption of Cr (VI) on the polymers. IIP adsorbent was successfully recycled 5 times using 0.1 M NaOH as a leachate; 98% Cr(VI) was desorbed during the last adsorption-desorption cycle. [ABSTRACT FROM AUTHOR]

As biomarkers of many diseases, glycoproteins are of great significance to clinical diagnostics. However, the determination of low abundant glycoproteins in complex biological samples without any pretreatment process is still a problem. In this study, a rapid and convenient separation method for highly efficient enrichment of glycoproteins is reported, based on pH double-responsive imprinted magnetic microspheres. Thin imprinted polymer shells were fabricated onto the surface of magnetic microspheres by free radical polymerization, using 2-(Dimethylamino) ethyl methacrylate as pH-sensitive monomer, 4-vinylphenylbronic acid as boronate affinity monomer, and ovalbumin (OVA) as template molecule. Combining the advantages of pH-sensitive monomer and boronate affinity monomer, rapidly capture-release of OVA could be modulated by changing solution pH. Moreover, high absorption ability (81.2 mg/g) was achieved within about 10 min. This study provided responsible way to imprint glycoproteins and showed great potential for glycoprotein detection in clinical diagnostic. [ABSTRACT FROM AUTHOR]

A novel fluorescent sensor nitrogen-doped graphene quantum dots (N-GQDs)/SiO 2 /molecular imprinting polymer（N-GQDs/SiO 2 /MIP）was fabricated by surface imprinting and epitope imprinting to recognize and detect the target protein cytochrome c (Cyt C) with fluorescence quenching. In the polymerization process, the C- and N-terminal nonapeptides of Cyt C were selected as the double templates which were fixed by functional monomer (zinc acrylate) through metal chelation and steady six-membered ring. The linear range of fluorescence quenching for this receptor towards Cyt C was 0.20–60 μM, and the detection limit was 0.11 μM. The precision for six times replicate determination of Cyt C at 30 μM was 1.20%, and the imprinting factor (IF) was 3.06. The recoveries of the material to Cyt C in urine were 99.3–114.0%. In brief, this work proposed a strategy to prepare a new type fluorescent imprinting polymer based on N-GQDs and provided an attractive perspective for the detection of protein by using the combination of N-GQDs and molecular imprinting technique. [ABSTRACT FROM AUTHOR]

A combination strategy of moderate self-polymerization and assembly technique was proposed to fabricate superparamagnetic surface imprinted nanocomposites (SSINs) for efficient protein recognition. Homogeneous Fe 3 O 4 /Poly (methyl methacrylate) (PMMA)/Poly (dihydroxyphenylacetic acid) (PDOPA) SSINs were obtained via self-polymerization of DOPA on the surface of Fe 3 O 4 /PMMA nanospheres in the presence of lysozyme (Lyz) as a template. The Lyz-imprinted Fe 3 O 4 /PMMA/PDOPA SSINs possessed average diameters of 200 nm, high magnetic content, high saturation magnetization, as well as excellent specific recognition capacity toward Lyz template, exhibiting their great potential for biomacromolecular recognition. [ABSTRACT FROM AUTHOR]

A novel core-shell structured composite of Fe 3 O 4 nanoparticles and molecularly imprinted polymers (MIPs), namely, magnetic MIPs (M-MIPs), was synthesized by surface imprinting technique combined with precipitation polymerization for the selective and sensitive fluorescent detection of 17β-estradiol (17β-E 2 ) based on the competitive desorption of fluorescein as a fluorescent indicator from the M-MIPs. The resulting M-MIPs were well characterized, and they showed ideal spherical morphology and magnetic property. Competitive rebinding of 17β-E 2 to the corresponding recognition sites regulated the release of fluorescein and resulted in an enhanced fluorescence signal. The fluorescence increase linearly coincided with the concentration of 17β-E 2 within the range of 0.10–70 μM with a detection limit of 0.03 μM. The recovery of 17β-E 2 from spiked lake and river water samples ranged from 98.2 to 103.8% with relative standard deviations between 1.1 and 3.8%. This study successfully integrated surface imprinting, competitive adsorption, magnetic separation and fluorescent detection, and also demonstrated fast binding kinetics, easy separation and reusability, and sensitive determination of template molecules. Thus, the M-MIP-based method may provide a simple, rapid, convenient, cost-effective and environmentally friendly way for the highly selective and sensitive recognition and detection of non-fluorescent molecules at trace levels. [ABSTRACT FROM AUTHOR]

[Display omitted] • Molecularly imprinted PANI was immobilized on Fe 3 O 4 /ZnO by surface imprinting technique. • The Fe 3 O 4 /ZnO@MI-PANI displayed selective photodegradation activity towards amoxycillin. • Fe 3 O 4 /ZnO@MI-PANI displayed better photocatalytic efficiency than Fe 3 O 4 /ZnO@NI-PANI. • The presence of Fe 3 O 4 enhanced visible light harvesting ability. In the present study, molecularly imprinted polyaniline was immobilized on Fe 3 O 4 /ZnO composite by surface imprinting technique. The obtained molecularly imprinted photocatalyst was used for selective degradation of amoxycillin under visible light irradiation. The presence of Fe 3 O 4 not only endowed the photocatalyst with magnetic separation feature but also enhanced visible light harvesting ability. Compared with Fe 3 O 4 /ZnO composite, photocatalytic performance of the molecularly imprinted photocatalyst was significantly improved because polyaniline could form a heterojunction with ZnO to enhance photocatalytic performance. The molecularly imprinted photocatalyst displayed better photocatalytic efficiency and selective photodegradation activity towards amoxycillin than the non-imprinted photocatalyst, because the photodegradation reaction could take place not only on surface of the photocatalyst but also in imprinted cavities for the molecularly imprinted photocatalyst, while the photodegradation only occurred on surface of the non-imprinted photocatalyst. Active species capture experiments showed that.O 2- and h+ played a crucial role in the degradation of amoxycillin. The current research provided new insight for fabrication of molecularly imprinted photocatalyst with selective degradation ability for organic pollutants. [ABSTRACT FROM AUTHOR]

• Molecularly imprinted hollow spheres (MIHS) were prepared based on surface imprinting and boronate affinity. • The MIHS exhibited superior affinity and quick mass transfer rate towards ribavirin. • The MIHS were successfully applied to separate ribavirin from environmental water and bovine serum samples. A facile method is proposed to prepare pH-responsive molecularly imprinted hollow spheres (MIHS) for selective separation of ribavirin from water samples based on surface imprinting and boronate affinity. The polymerization conditions are optimized and the binding performance toward ribavirin is investigated. Benefiting from the hollow structure and the synergistic effect of surface imprinting and boronate affinity, the MIHS exhibit fast equilibrium kinetics of 18 min, excellent binding affinity of 12.30 mg g−1 as well as preferable reusability toward ribavirin. Moreover, the MIHS exhibit pH-sensitivity due to the interaction between boronate affinity and the cis -diol structure of the ribavirin. Finally, the MIHS are used to separate ribavirin from river water and bovine serum samples, and>90 % ribavirin is recovered. The as-prepared MIHS are expected to be a promising candidate for ribavirin separation in complex systems. [ABSTRACT FROM AUTHOR]

Schematic representation of the preparation of Fe 3 O 4 @MIPs. [Display omitted] • Magnetic molecularly imprinted polymers (Fe 3 O 4 @MIPs) for chlorogenic acid were successfully prepared. • The Fe 3 O 4 @MIPs could be easily collected and separated from the complex matrix by using an external powerful magnet. • The Fe 3 O 4 @MIPs were successfully applied for the detection of chlorogenic acid in juice samples. In this study, magnetic molecularly imprinted polymers (Fe 3 O 4 @MIPs) were successfully synthesized through surface molecular imprinting method with chlorogenic acid (CGA) as the template molecule. The adsorption properties of Fe 3 O 4 @MIPs for CGA were carefully evaluated through adsorption kinetics, adsorption isotherms and selectivity experiments. The obtained Fe 3 O 4 @MIPs displayed high adsorption capacity (35.84 mg/g), excellent reusability and significant selectivity for CGA, and the adsorption equilibrium could be achieved within 40 min. Finally, the resulting Fe 3 O 4 @MIPs were successfully employed as effective adsorbents combined with high-performance liquid chromatography for the detection of CGA in juice samples with excellent selectivity. A good linear relationship in the range of 0.1–100 μg/mL and the limit of detection (LOD) (0.03 µg/mL) were obtained under the optimized conditions. The satisfactory recoveries of proposed method at three spiked levels analysis were 93.5 %–101.6 % with the relative standard deviation (RSD) less than 5 %. [ABSTRACT FROM AUTHOR]

A novel gold nanoparticles (AuNPs)-based fluorescence assay had been developed for the detection of hemoglobin (Hb). The method relied on the high selectivity of surface imprinting technique and the strong fluorescence property of AuNPs. Herein, firstly, the carboxyl modified AuNPs were initially anchored on the amino-functionalized silica nanoparticles under the assistance of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC) and 1-hydroxy-5-pyrrolidinedione (NHS). Then, the Hb-imprinted polymer layer was wrapped on the surface of SiO 2 /AuNPs via a sol–gel surface imprinting technique. The generated SiO 2 /Au/MIPs as fluorescence sensor owned both sensitive detection of AuNPs and specific selectivity of molecularly imprinted polymer. The conditions such as pH, stability and effect of the fluorescence sensor concentration were investigated to search the optimized detection conditions. For the optimized conditions, the fluorescence-quenching detection presented a satisfactory linearity with Hb concentrations in the range of 0.1–20 μmol L −1 and the detection limit was 0.03 μmol L −1 . Moreover, through the investigation of selective and competitive quenching, the fluorescence sensor exhibited satisfying selectivity and high binding affinity to Hb under the existence of its possibly competing molecules, such as bovine serum albumin (BSA), bovine hemoglobin (BHb), albumin, chicken egg (ACE). The results proved that the fluorescence sensor was succeeded to be used in the field of rapid recognition and determination of Hb even though existing of other complex proteins. [ABSTRACT FROM AUTHOR]

A novel virus-recognition fluorescent sensor based on virus-imprinted polymers (VIP) for highly selective and highly sensitive detection of Japanese encephalitis virus (JEV) was presented. The virus-imprinted method went beyond simple shape imprinting through surface imprinting with magnetic silicon microspheres acting as carrier materials and tetraethyl orthosilicate (TEOS) functioning as building blocks. The resulting VIP film could selectively capture target JEV via recognition cavities, and a high imprinting factor of 2.98 was achieved. Furthermore, fast magnetic separation and highly sensitive fluorescent detection in water were offered for JEV, showing a good linearity within 2.5–45 nM ( R 2 = 0.9948). Finally, the specificity study confirmed that the virus-imprinted magnetic silicon microspheres demonstrated excellent selectivity for JEV in several different types of virus. [ABSTRACT FROM AUTHOR]

Surface imprinting strategy is one of the promising approaches to synthesize plastic antibodies while overcoming the problems in the protein imprinting research. In this study, we focused our attentions on developing two-step polymerization to imprint on the bare surface employing polyethyleneimine (PEI) assisted-coordination of template molecules, lysozyme. For this aim, we firstly synthesized poly(2-hydroxyethyl methacrylate-glycidyl methacrylate), poly(HEMA-GMA) cryogels as a bare structure. Then, we immobilized PEI onto the cryogels through the addition reaction between GMA and PEI molecules. After that, we determined the amount of free amine (NH 2 ) groups of PEI molecules, subsequently immobilized methacrylate functionalities onto the half of them and another half was used to chelate Cu(II) ions as a mediator between template, lysozyme and PEI groups. After the characterization of the materials developed by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and the micro-computed tomography (μCT), we optimized the lysozyme adsorption conditions from aqueous solution. Before performing lysozyme purification from chicken egg white, we evaluated the effects of pH, interaction time, the initial lysozyme concentration, temperature and ionic strength on the lysozyme adsorption. Moreover, the selectivity of surface imprinted cryogels was examined against cytochrome c and bovine serum albumin (BSA) as the competitors. Finally, the mathematical modeling, which was applied to describe the adsorption process, showed that the experimental data is very well-fitted to the Langmuir adsorption isotherm. [ABSTRACT FROM AUTHOR]

Abstract 1 1 Rhodamine B, RhB; RhB-imprinted polymers, RhB-MIPs; liquid-liquid extraction, LLE; solid-phase extraction, SPE; molecularly imprinted polymers, MIPs; nanoparticles, NPs; transmission electron microscopy, TEM; lemon yellow, Ly; chrysoidine, Chd; orange II, Org; sunset yellow, Sy; tetraethyl orthosilicate, TEOS; ethylene glycol dimethacrylate, EGDMA; azobisisobutyronitrile, AIBN; methacrylic acid, MAA; 3-methacryloxypropyl trimethoxysilane, γ-MPS; non-imprinted polymers, NIPs. A new and facile rhodamine B (RhB)-imprinted polymer nanoshell coating for SiO 2 nanoparticles was readily prepared by a combination of silica gel modification and molecular surface imprinting. The RhB-imprinted polymers (RhB-MIPs) were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, and UV–vis spectroscopy; the binding properties and selectivity of these MIPs were investigated in detail. The uniformly imprinted nanoparticles displayed a rather thin shell thickness (23 nm) with highly effective recognition sites, showing homogenous distribution and monolayer adsorption. The maximum MIP adsorption capacity ( Q m ) was as high as 45.2 mg g −1 , with an adsorption equilibrium time of about 15 min at ambient temperature. Dynamic rebinding experiments showed that chemical adsorption is crucial for RhB binding to RhB-MIPs. The adsorption isotherm for RhB-MIPs binding could also be described by the Langmuir equation at different temperatures and pH values. Increasing temperature led to an enhanced Q m , a decreased dissociation constant ( K' d ), and a more negative free energy (Δ G ), indicating that adsorption is favored at higher temperatures. Moreover, the adsorption capacity of RhB was remarkably affected by pH. At pH > 7, the adsorption of RhB was driven by hydrogen bonding interactions, while at pH < 7 electrostatic forces were dominant. Additionally, the MIPs also showed specific recognition of RhB from the standard mixture solution containing five structurally analogs. This method was also successfully employed to determine RhB content in red wine and beverages using three levels of spiking, with recoveries in the range of 91.6–93.1% and relative standard deviations lower than 4.1%. [ABSTRACT FROM AUTHOR]

A novel polysulfone-based molecularly imprinted membrane (MIM) with graft type (designated as GMIM) was successfully prepared by a combination of film-forming method of immersion–precipitation phase transformation with molecule surface-imprinting technique. The porous asymmetry membrane of chloromethylated polysulfone (CMPSF) was first prepared by a phase inversion method, and then the CMPSF membrane was amination-modified with ethanediamine as reagent, resulting aminated polysulfone membrane AMPSF, on whose surface primary amino groups were contained. Then the graft-polymerization of methacrylic acid (MAA) was realized by initiating of the surface-initiating system of –NH 2 /S 2 O 8 − , obtaining the grafted membrane PSF-g-PMAA. After PSF-g-PMAA membrane adsorbed matrine, the crosslinking reaction of the grafted PMAA was allowed to be carried out with ethylene glycol diglycidyl ether (EGDE) as crosslinker, resulting in the matrine imprinted membrane with graft type, GMIM. The binding characteristics of the imprinted membrane GMIM, the permeability and separation property for matrine were investigated in depth. The experimental results show that the imprinted membrane consists of a thin imprinted layer, a thin skin layer containing channels at nanoscale and a support layer with macroporous structure. The imprinted membrane GMIM has specific recognition selectivity and excellent binding affinity for matrine, and its selectivity coefficient for matrine relative to cytisine is 4.85. More importantly, the imprinted membrane can produce good “gate effect” because of its own structure characteristic, so that it has fine permselectivity for the template, matrine molecule. The separation coefficient of the imprinted membrane GMIM for matrine relative to cytisine as a contrast reaches up to 5.9, displaying the excellent performance of a selectively permeable membrane. [ABSTRACT FROM AUTHOR]

Straw-supported ion imprinted polymer sorbent was prepared by surface imprinting technique combined with activators generated by electron transfer for atom transfer radical polymerization (AGET ATRP). The ability of the imprinted sorbent to adsorb La 3+ ions was assessed by batch adsorption technique. The crosslinking density of the ion imprinted polymer (IIP) on the surface of straw exerted great influence on the sorption property. The IIP with appropriate crosslinking density displayed the highest sorption capacity, fastest sorption rate and best selective sorption ability. The maximum sorption amount was 125 mg/g, and the sorption equilibrium could be reached within several minutes. The adsorption mechanism studied by X-ray photoelectron spectroscopy (XPS) revealed that the sorption of La 3+ ions was realized mainly through interactions with the C N, C O and C O groups. The imprinted sorbent could be repeatedly used for ten times without any significant loss in the initial binding affinity. [ABSTRACT FROM AUTHOR]

Molecularly imprinted polymers (MIPs) for the recognition of proteins are expected to possess high affinity through the establishment of multiple interactions between the polymer matrix and the large number of functional groups of the target. However, while highly affine recognition sites need building blocks rich in complementary functionalities to their target, such units are likely to generate high levels of non-specific binding. This paradox, that nature solved by evolution for biological receptors, needs to be addressed by the implementation of new concepts in molecular imprinting of proteins. Additionally, the structural variability, large size and incompatibility with a range of monomers made the development of protein MIPs to take a slow start. While the majority of MIP preparation methods are variants of chemical polymerization, the polymerization of electroactive functional monomers emerged as a particularly advantageous approach for chemical sensing application. Electropolymerization can be performed from aqueous solutions to preserve the natural conformation of the protein templates, with high spatial resolution and electrochemical control of the polymerization process. This review compiles the latest results, identifying major trends and providing an outlook on the perspectives of electrosynthesised protein-imprinted MIPs for chemical sensing. [ABSTRACT FROM AUTHOR]

Crosslinking degree is difficult to determine on the premise of simultaneously considering response performance and recognition capability in the thermosensitive imprinted materials due to their mutually contradictory relationship. In addition, the effect of thickness of thermosensitive imprinted layers on the recognition of target protein is also difficult to evaluate quantitatively. To solve these two problems, a series of thermosensitive magnetic imprinted microspheres with different crosslinking degree and imprinted layer thickness were fabricated. The adsorption results showed that imprinted layer thickness of 17 nm was the most appropriate for BSA imprinting. Crosslinking degree of 20% was determined as the balance point by simultaneously considering response performance and recognition capability. Under such conditions, the elution efficiency after once washing process was up to 78.60%, which guaranteed the satisfactory regeneration capability. The adsorption capacity and the imprinting factor could reach 42.01 mg/g and 3.41, respectively, which were greatly increased compared to those imprinted materials reported previously. Furthermore, the practical separation performance of the imprinted microspheres was investigated by separating BSA from the protein mixture sample, and the results were exciting. All these results indicated that these imprinted microspheres were expected to be applied to the rapid isolation and purification of BSA. [ABSTRACT FROM AUTHOR]

A strategy based on water-in-oil emulsion for the dispersion of a sol–gel mixture into small droplets was employed with the view of the production of naproxen-imprinted micro- and nanospheres. The procedure, aiming at a surface imprinting process, comprised the synthesis of a naproxen-derived surfactant. The imprinting process occurred at the interface of the emulsions or microemulsions, by the migration of the NAP-surfactant head into the sol–gel drops to leave surficial imprints due mainly to ion-pair interaction with a cationic group contained within the growing sol–gel network. The surface-imprinted microspheric particles exhibited a log-normal size distribution with geometric mean diameter of 3.1 μm. A mesoporous texture was found from measurements of the specific surface area (206 m 2 /g) and pore diameter (D p 2 nm). Evaluation of the microspheres as packed HPLC stationary phases resulted in the determination of the selectivity factor against ibuprofen ( α = 2.1), demonstrating the successful imprinting. Chromatographic efficiency, evaluated by the number of theoretical plates (222 plates cm −3 ), emerged as an outstanding feature among the set of all relatable formats produced before, an advantage intrinsic to the location of the imprinted sites on the surface. The material presented a capacity of 3.2 μmol g −1 . Additionally, exploratory work conducted on their nanoscale counterparts resulted in the production of nanospheres in the size order of 10 nm providing good indications of a successful imprinting process. [ABSTRACT FROM AUTHOR]