Polymer Catalysts Imprinted with Metal Ions as Biomimics of Metalloenzymes

Abstract

This work presents the preparation and properties of molecularly imprinted polymers (MIPs) with catalytic centers that mimic the active sites of metalloenzymes. The MIP synthesis was based on suspension polymerization of functional monomers (4-vinylpyridine and acrylonitrile) with trimethylolpropane trimethacrylate as a crosslinker in the presence of transition metal ions and 4-methoxybenzyl alcohol as a template. Four metal ions have been chosen for imprinting from among the microelements that are the most essential in the native enzymes: Cu2+, Co2+, Mn2+, and Zn2+. To prepare catalysts, the required loading of metal ions was obtained during sorption process. The catalysts imprinted with Cu2+, Co2+, and Zn2+were successfully used for hydroquinone oxidation in the presence of hydrogen peroxide. The Mn2+-imprinted catalyst showed no activity due to the insufficient metal loading. Cu2+MIP showed the highest efficiency. In case of Cu- and Co-MIP catalysts, their activity was additionally increased by the use of surface imprinting technique.

Molecularly Imprinted Polymers for Catalysis and Synthesis

“…Czulak, in collaboration with Jakubiak-Marcinkowska, prepared MIPs with catalytic centers containing transition metal ions in order to mimic the active sites of metalloenzymes, using the oxidation of hydroquinone by hydrogen peroxide as a model reaction [41]. The suspension polymerization technique was used in order to obtain two kinds of cavities: in the volume, and on the surface of the polymer matrix.…”

Molecularly Imprinted Polymers as Tools for Bioassays and Biotransformation

“…Joanna et al [73] chose four metal ions Cu 2+ , Co 2+ , Mn 2+ , and Zn 2+ among the microelements that are essential in the native enzymes for imprinting based on suspension polymerization of 4-vinylpyridine, acrylonitrile, and trimethylolpropanetrimethacrylate in the presence of the transition metal ions and 4-methoxybenzyl alcohol as a template. The Cu 2+ , Co 2+ , and Zn 2+ imprinted MIPs showed catalytic activity for hydroquinone oxidation whereas the Mn 2+ imprinted catalyst showed no activity due to the insufficient metal loading.…”

Molecularly Imprinted Polymers (MIPs) in Sensors for Environmental and Biomedical Applications: A Review

“…MIPs have been fabricated for solid phase extraction [ 14 , 15 , 16 , 17 , 18 ], chromatographic separation [ 19 , 20 , 21 , 22 , 23 ], catalysis [ 24 , 25 , 26 , 27 , 28 ], drug delivery [ 29 , 30 , 31 , 32 , 33 ], study of the structure and function of proteins [ 34 , 35 , 36 , 37 , 38 ], environmental and biomedical sensing [ 39 , 40 , 41 , 42 , 43 ], water and wastewater treatment [ 44 , 45 , 46 , 47 , 48 ], and membrane-based separations [ 49 , 50 , 51 , 52 , 53 ]. MIP use for purification purposes is the most commercially available application, particularly in analytical chemistry; other uses are still in need of further development [ 54 ].…”