Quantum mechanical studies on dioxin‐imprinted polymer precursor composites: Fundamental insights to enhance the binding strength and selectivity of biomarkers

Abstract

We present a benchmark study of binding energies for dioxin-imprinted polymer complexes. A density functional theory approach was used for screening the polymerization precursors in the rational design of molecularly imprinted polymers (MIPs). Tetrachlorodibenzo-p-dioxin (TCDD) was taken as an imprinted molecule. The geometry optimization, natural bond orbital charge, and molecular electrostatic potential of TCDD and acrylamide (AM) were studied at the M062X level and 6-31G(d,p) belonging to one of the hybrid density functional theories. The results of molecular electrostatic potential and natural bond orbital charge analysis were comparable. Among the studied functional monomers-AM, methacrylic acid (MAA), itaconic acid, and vinyl pyridine-AM was confirmed as the best functional monomer, because the strongest interaction (the maximum number of hydrogen bonds and the lowest binding energy) occurs between TCDD and AM. The stability property was excellent when the ratio of TCDD and AM was 1:4. The polarizable continuum model was used for solvent calculations. Computational results showed that acetonitrile plays an important role in the MIP formation, as it seems to control the size and the shape of the cavity. The atoms in molecule and Becke surface method have also been applied to understand the nature and strength of the hydrogen bonding interactions in complexes. TCDD-AM complexes were found involving C-O···Cl and N-H···Cl hydrogen bonds. Good correlations have been established between hydrogen bond lengths versus atoms in molecule topological parameter like electron density ρ(r) and its Laplacian ▽ ρ(r) at the bond critical points. On ground of theoretical results, a series of MIPs were synthesized. The MIP prepared using TCDD as the template, the functional monomer (AM), and the cross-linker (TRIM) in acetonitrile solvent exhibited the highest adsorption capacity for TCDD. The maximum binding capacity of TCDD on the MIP was 3.7 μg/mg. This research work can provide a theoretical reference for the fabrication and characterization of novel TCDD-MIPs for environmental applications.

A molecularly imprinted nanofilm‐based quartz crystal microbalance sensor for the real‐time detection of pirimicarb

“…The polymer matrix is an artificial synthetic polymer matrix that possesses specific cavities and recognition sites and binds specifically with the target molecule . Molecularly imprinted polymers (MIPs) are easily prepared, stable, and cheap, and these materials are produced in large quantities with good reusability; they have been used in many different areas such as biological molecules and analytical applications . Studies in recent years have shown that MIPs have received considerable scientific attention in the field of sensors .…”

An Update on Molecularly Imprinted Polymer Design through a Computational Approach to Produce Molecular Recognition Material with Enhanced Analytical Performance

“…These functionals also yield good results for systems containing dispersion forces [ 77 , 78 , 79 , 80 ]. To select the appropriate DFT method, Khan et al [ 81 ] used several methods—B3LYP, BHandHLYP, M062X, and ωB97xD—and basis sets—6-31G(d,p) and 6-31++G(d,p)—to optimize of the template structure. They analyzed and compared the optimized results with earlier experimental data available in the literature.…”

3,4-Methylenedioxypyrovalerone (MDPV) Sensing Based on Electropolymerized Molecularly Imprinted Polymers on Silver Nanoparticles and Carboxylated Multi-Walled Carbon Nanotubes

“…One also may realize that MDPV's tertiary amine is rather hindered while the MDPV molecule interacts with an o-PD shell-a key conclusion driven by Monte Carlo sampling-to be able to contribute to the cavities' selectivity. To evaluate the distribution of non-covalent interactions between o-PD monomers and MDPV in the MIP pre-polymerization complexes, analysis of Becke surface [113] was performed for the pre-polymerization cavities with higher representativity, i.e., the complexes with 19, 20 and 21 monomers. This analysis was based on Hirshfeld surface [114], applying the Becke's [115], instead of the Hirschfeld's, partition.…”