Constructing High-Recognition Protein-Imprinted Materials Using “Specially Designed” Block Macromolecular Chains as Functional Monomers and Crosslinkers

Abstract

The use of a macromolecularly functional monomer and crosslinker (MFM) to stabilize and imprint a template protein is a new method to construct high-recognition protein-imprinted materials. In this study, for the first time, a “specially designed” block MFM with both “functional capability” and “crosslinking capability” segments was synthesized via reversible addition–fragmentation chain-transfer polymerization and used to fabricate bovine serum albumin (BSA)-imprinted microspheres (SiO2@MPS@MIPs-MFM) by the surface imprinting strategy. Results from circular dichroic spectrum experiments reflected that the block MFM could maintain the natural form of BSA, whereas its corresponding and equivalent micromolecularly functional monomer (MIM) seriously destroyed the secondary structure of proteins. Batch rebinding experiments showed that the maximum adsorption capacity and imprinting factor of SiO2@MPS@MIPs-MFM reached 314.9 mg g–1 and 4.02, which were significantly superior to that of MIM-based imprinted materials. In addition, since the crosslinking capability segments in block MFM involved zwitterionic functional groups with a protein-repelling effect, SiO2@MPS@MIPs-MFM showed better specific rebinding ability than the imprinted material prepared by MFM without this component. Besides, scanning electron microscopy and transmission electron microscopy images showed that the shell thickness of SiO2@MPS@MIPs-MFM was approximately 15 nm, and such a thin imprinted layer ensured its rapid adsorption equilibrium (120 min). As a result, SiO2@MPS@MIPs-MFM revealed fantastic selectivity and recognition ability in a mixed protein solution and could efficiently extract BSA from biological samples of bovine calf serum. The proposal of block MFM enriched the options and designability of monomers in protein imprinting technology, thereby laying a foundation for developing high-performance protein-imprinted materials.

Ring -opening of polythiolactones to construct protein-imprinted nanospheres with high recognition and regulation capabilities

“…The shell thickness of MS@PTL was determined to be ∼50 nm, which provided adequate evidence for the successful ATRP reaction. Compared with previous studies, 31,33 the relatively thick polymer layers produced by the ATRP reaction in this work provide enough functional sites for the recognition of proteins. The identical morphologies of MS@PTL, MS@PTLR and MS@PTLR-MIPs illustrated that the aminolysis reaction and crosslinking process had little effect on the morphology of the nanospheres.…”

“…It was noteworthy that the PEG segments on the crosslinker could reduce nonspecific adsorption on the surface of materials because of its protein-repelling effect. 33,40 Non-imprinted nanospheres (MS@PTLR-NIPs) were also synthesized using the same procedures as above without the participation of BSA.…”

“…The saturated adsorption capacity of the materials for BSA was 314.9 mg g −1 and the imprinting factor (IF) was 4.02. 33 Although the block copolymer improved the specificity and adsorption capacity of PIPs compared with random imprinted polymers, the synthesis of block copolymers was time consuming and the synthesized block copolymers were very difficult to integrate with nanomaterials for the slow grafting reaction kinetics of polymers.…”

“…The crosslinking sites (i.e., the thiol groups) are proximate to the recognition sites (i.e., the alcohols, acids and amines in Scheme 1), dramatically increasing the regulation ability of the imprinting cavities in the subsequent cross-linking process. The difficulty of the low grafting efficiency of polymers on nanomaterials in previous studies 33,34 was effectively overcome in this work because the polythiolactones were polymerized in situ on the surface of the nanospheres. As a consequence, the maximum saturated rebinding capacity of the imprinted materials for BSA was up to 285 ± 15 mg g −1 and the highest imprinting factor was 5.79, which is comparable to those of the best-performing protein-imprinted materials reported when both recognition capability and specificity are considered.…”

Carbon Nanofibers Coated with Fe3O4 Nanoparticles and MnO2 Nanosheets further Modified with Molecularly Imprinted Polydopamine for Fluorescence Sensing of Carcinoembryonic Antigen

“…Molecular imprinted polymers (MIPs) are artificial receptors synthesized through polymerization in the presence of the target that have been used as adsorbents for sample pretreatment, identification units for chemical sensors, and antibody alternatives in immunoassays. − Fluorescence sensors are based on electron transfer, inner filter effects, and fluorescence resonance energy transfer mechanisms in which fluorescent dyes, quantum dots, carbon dots, or noble metal nanoclusters are employed and have been widely used because of their high sensitivity and designability. , Molecular imprinted fluorescence sensors (MIFS), which combine the advantages of MIPs with those of fluorescence sensors, have been widely applied for the detection of metal ions, proteins, and organic compounds . Benefitting from the high selectivity of MIPs, MIFS display high selectivity for target compounds.…”