Virtually imprinted polymers (VIPs): understanding molecularly templated materials via molecular dynamics simulations.

Molecularly imprinted polymers are advanced recognition materials selectively rebinding a target molecule present during the synthesis of the polymer matrix. It is commonly understood that the templating process is based on embedding the complex formed between a template and functional monomers into a co-polymer matrix. This happens by a polymerization of the complex with a cross-linker while maintaining their spatial arrangement forming a molecular imprint. Template removal then leads to synthetic recognition sites ready to selectively rebind their targets, which are complementary in functionality, size and shape to the target. In this study, an innovative theoretical concept using fully atomistic molecular dynamics simulations for modeling molecular templating processes is introduced yielding virtually imprinted polymers (VIPs). VIPs created for the template 17-ß-estradiol and applied in modeled chromatography experiments demonstrated selectivity for their template. This evidenced the creation of virtual imprints as a result of a templated synthesis protocol, which represents a theoretical confirmation of the governing imprinting theory.

Efficient prediction of suitable functional monomers for molecular imprinting via local density of states calculations.

Synthetic molecular recognition materials, such as molecularly imprinted polymers (MIPs), are of increasing importance in biotechnology and analytical chemistry, as they are able to selectively bind their respective template. However, due to their specificity, each MIP has to be individually designed for the desired target leading to a molecularly tailored synthesis strategy. While trial-and-error remains the common approach for selecting suitable functional monomers (FMs), the study herein introduces a radically new approach towards rationally designing MIPs by rapidly screening suitable functional monomers based on local density of states (LDOS) calculations in a technique known as Electronic Indices Methodology (EIM). An EIM-based method of classification of FMs according to their suitability for imprinting was developed. Starting from a training set of nine different functional monomers, the prediction of suitability of four functional monomers was possible. These predictions were subsequently experimentally confirmed.