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The development of in silico strategies for the study of the molecular imprinting process and the properties of molecularly imprinted materials has been driven by a growing awareness of the inherent complexity of these systems and even by an increased awareness of the potential of these materials for use in a range of application areas. Here we highlight the development of theoretical and computational strategies that are contributing to an improved understanding of the mechanisms underlying molecularly imprinted material synthesis and performance, and even their rational design.

Macroporous polymer films with long-range uniformity and biotinyl-moiety selective recognition sites have been developed. A hierarchical molecular imprinting strategy afforded significant enhancements in quartz crystal microbalance (QCM) sensitivities towards biotinylated compounds.

In principle, molecularly imprinted polymer science and technology provides a means for ready access to nano-structured polymeric materials of predetermined selectivity. The versatility of the technique has brought it to the attention of many working with the development of nanomaterials with biological or biomimetic properties for use as therapeutics or in medical devices. Nonetheless, the further evolution of the field necessitates the development of robust predictive tools capable of handling the complexity of molecular imprinting systems. The rapid growth in computer power and software over the past decade has opened new possibilities for simulating aspects of the complex molecular imprinting process. We present here a survey of the current status of the use of in silico-based approaches to aspects of molecular imprinting. Finally, we highlight areas where ongoing and future efforts should yield information critical to our understanding of the underlying mechanisms sufficient to permit the rational design of molecularly imprinted polymers.

A piezoelectric microgravimetry (PM) chemosensor, featuring a film of molecularly imprinted polymer (MIP) of poly[bis(2,2'-bithienyl)methane] bearing either a 3,4-dihydroxyphenyl or benzo-18-crown-6 substituent, for selective determination of dopamine was devised and tested. A Pt/quartz resonator and a dopamine-templated MIP film, deposited by electropolymerization onto an underlayer of poly(bithiophene), served as the transducer and recognition element of the chemosensor, respectively. The UV-vis spectroscopic and XPS as well as electrochemical measurements verified completeness of the dopamine template extraction with a strong base solution. The extraction-generated molecular cavities featured recognition sites that served selective dopamine analyte binding. The SECM imaging substantiated the permeability characteristics of the template-free MIP film. The dopamine analyte was determined under FIA conditions with the PM detection. The lower limit of detection was 10nM dopamine at favorable conditions involving the 35 μL/min carrier solution flow rate and the injected sample volume of 1 mL. The sensitivity of the chemosensor increased almost fivefold when the poly(bithiophene) film coated Pt/quartz electrode was used instead of the bare Pt/quartz electrode as the substrate for deposition of the MIP film. The chemosensor successfully discriminated dopamine from structural and functional analogues, such as 2-phenylethylamine, histamine, and ascorbic acid. The optimum mean thickness of the MIP film was ∼220 nm., (Copyright © 2010 Elsevier B.V. All rights reserved.)

An adenine-templated molecularly imprinted polymer (MIP) film, deposited on a poly(bithiophene) barrier film, served as the recognition element of a piezomicrogravimetric (acoustic) chemosensor. A 10MHz AT-cut shear-thickness-mode bulk-acoustic-wave quartz crystal resonator with Pt film electrodes was used as the signal transducer. Adenine electrooxidation was prevented by the barrier film. The MIP film was deposited by electrochemical co-polymerization of two functional monomers of bis(bithiophene) derivatives, bearing either the 18-crown-6 or dioxaborinane substituent, in the presence of the adenine template. A strong base solution was then used to extract the template. Completeness of the template removal was substantiated by the UV-vis, XPS, DPV, and EIS measurements. The chemosensor performance was evaluated with the piezoelectric microgravimetry detection at QCM under FIA conditions using a carrier acetonitrile-water (1:1, v:v) mixed solvent solution. The linear dynamic concentration range extended from at least 0.1 to 1mM for the 35 microL/min flow rate, and 100 microL volume of the injected adenine solution. The chemosensor selectivity allowed for discrimination of the adenine analyte from structurally and functionally related interferants, such as 2-aminopurine, guanine, and ascorbic acid. The determined from the FIA kinetic studies stability constant of the MIP-adenine complex, (18+/-2.4)x10(4)M(-1), was much higher than that of the MIP-(2-aminopurine), (650+/-90)M(-1), MIP-guanine, (122+/-11)M(-1), and MIP-(ascorbic acid), (92+/-10)M(-1), complexes. The concentration limit of detection was as low as 5 nM adenine for the 35 microL/min flow rate, and 1 mL volume of the injected sample solution., (Copyright (c) 2010 Elsevier B.V. All rights reserved.)

A histamine piezoelectric (acoustic) sensor using a molecularly imprinted polymer (MIP) film has been devised and tested. The sensor comprises an electrodeposited MIP film as the recognition element and a 10 MHz AT-cut shear-thickness-mode bulk-acoustic-wave quartz crystal resonator with Pt film electrodes as the signal transducer. Preparation of the sensing film involved two consecutive electrochemical polymerizations, performed under cyclic voltammetric conditions, with the use of a supporting electrolyte of 0.1 M tetra-n-butylammonium perchlorate in acetonitrile. First, a poly(bithiophene) barrier film was deposited by electropolymerization on the Pt/quartz resonator to prevent histamine electro-oxidation and avoid possible contamination of the Pt electrode surface. Next, the histamine-templated MIP film was deposited by electropolymerization on top of this barrier film. For that purpose, two functional monomers of bis(bithiophene) derivatives, i.e., one bearing the 18-crown-6 and the other dioxoborinane substituent, were copolymerized in the presence of the histamine template. The consecutive growth of both these overlaid films was monitored with an electrochemical quartz crystal microbalance (EQCM). Subsequently, the histamine was extracted from MIP with 0.01 M NaOH for 12 h. The UV-vis and X-ray photoelectron spectroscopic measurements confirmed the completeness of the removal of the histamine template from the MIP film. The analytical performance of the chemosensor was assessed under flow injection analysis (FIA) conditions using the carrier 0.5 M HEPES buffer (pH = 7.5) solution and the piezoelectric microgravimetry detection at QCM. The negative peaks of resonant frequency linearly decreased with the increase of the histamine concentration in the range 10-100 mM for 150 microL/min flow rate, and 100 microL volume of the injected sample. The sensitivity of the chemosensor (0.33 Hz/mM) was more than twice as that of the chemosensor without the poly(bithiophene) barrier film (0.15 Hz/mM). The chemosensor performance was superior for selective histamine recognition if the poly(bithiophene) barrier film thickness exceeded 200 nm. The chemosensor discriminated histamine from functionally or structurally similar compounds, such as dopamine, tryptamine, and imidazole. Stability constants of the affinity complexes of MIP and analyte or the interfering agent were determined from kinetic studies. For the MIP-histamine complex, the stability constant thus evaluated was equal to 57.0 M(-1) being much higher than those for the MIP-tryptamine and MIP-dopamine complexes determined to be 10.7, and 6.4 M(-1), respectively. The concentration limit of detection was as low as 5 nM histamine if the carrier solution flow rate was as low as 35 microL/min and the injection sample volume as large as 1 mL.