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Advanced Drug Delivery Reviews (v.57, #12)
Molecularly imprinted polymers: technology and applications
by Chris J. Allender Theme Editor (pp. 1731-1732).
Molecularly imprinted polymers: A bridge to advanced drug delivery by Börje Sellergren; Chris J. Allender (pp. 1733-1741).
Specific molecular recognition is a fundamental requirement of living systems on which processes as diverse as neural transmittance, respiration, immune defence, cellular differentiation and nutrition rely. It is therefore not surprising that scientists have invested huge amounts of time and effort into harnessing, and more recently mimicking, biological function. A number of synthetic approaches have been developed and one of the most promising of these is molecular imprinting. Molecular imprinted polymers have routinely been used, as robust and effective synthetic molecular receptors, in a diverse range of technologies. But it is perhaps in the area of drug delivery, in particular ‘intelligent drug release’ and ‘magic bullet’ drug targeting, that significant future opportunities lie.
Keywords: Molecularly imprinted polymers; Controlled drug delivery; Targeted drug delivery; Magic bullet; Synthetic receptors
Synthetic strategies for the generation of molecularly imprinted organic polymers by A.G. Mayes; M.J. Whitcombe (pp. 1742-1778).
Molecular imprinting is a method of inducing molecular recognition properties in synthetic polymers in response to the presence of a template species during formation of the three-dimensional structure of the polymer. The molecularly imprinted polymers (MIPs) prepared in this way have been termed “plastic antibodies� and combine the robustness of the polymer scaffold with binding properties more readily associated with biological receptors. Smart polymers of this type may find applications in drug delivery, controlled release and monitoring of drug and metabolite concentrations. In this review the main synthetic strategies used in the preparation of imprinted organic polymers are described in terms of the chemical principles used in the templating step. These are illustrated with examples taken from the literature and are classified as covalent, semi-covalent, non-covalent, metal-mediated and non-polar. Finally strategies for the selection of monomers, optimisation and modification of the properties of imprinted polymers are reviewed.
Keywords: Functional monomer; Cross-linker; Self-assembly; Artificial antibodies; Affinity separation; Nanoparticles; Targeted delivery; Combinatorial methods; Chemometrics; Molecular modelling
Optimization, evaluation, and characterization of molecularly imprinted polymers by David A. Spivak (pp. 1779-1794).
The underlying mechanisms for molecular recognition exhibited by the imprinting effect can be attributed to two processes. The pre-organization of complementary functional groups in the polymer by the template and the formation of a shape-selective cavity that is complementary to the template. However, measurements of binding and selectivity combine all effects contributing to molecular recognition in MIPs into one figure of merit. If the two molecules being compared are not enantiomers, then there are other factors which contribute to differential binding such as size or different partitioning effects due to differences in polarity, hydrophobicity, ionization state or shape and/or conformational effects. The best probe for the imprinting effect is therefore an enantiomeric pair. Therefore, the first section of this article discusses enantioselective optimization of polymerization, the second section will review methods employed for evaluation of MIPs and the last section will cover materials science methods used to characterize the physical properties of MIP materials.
Keywords: Molecularly imprinted polymer; Optimization; Evaluation; Characterization; Pre-polymerization complex; Functional monomer; Crosslinking monomer
How to find effective functional monomers for effective molecularly imprinted polymers? by Kal Karim; Florent Breton; Regis Rouillon; Elena V. Piletska; Antonio Guerreiro; Iva Chianella; Sergey A. Piletsky (pp. 1795-1808).
Molecularly imprinted polymers (MIPs) are materials mimicking biological receptors in their specific recognition of analytes. Although molecular imprinting has been around for over 30 years, recently this technology has made rapid developments. However, recent investigations have led mainly to the synthesis of new polymers imprinted for a wider range of compounds without real and better understanding of the mechanisms occurring during the polymerisation and the recognition process. This review covers work developed in understanding these mechanisms and presents different strategies utilised in optimising MIP design.
Keywords: Molecularly imprinted polymer; Optimisation; Molecular modelling; Monomer selection
Molecularly imprinted polymers for the enantioseparation of chiral drugs by Richard J. Ansell (pp. 1809-1835).
Molecularly imprinted polymers have been applied for many years in chiral separations and increasingly have been applied to drugs. Separation speed and efficiency in methods such as HPLC and CEC are increasingly competitive with alternative established CSPs. The literature on separation of drug enantiomers using MIPs via HPLC, TLC, SFC and CEC are reviewed. Issues for method development, particularly the monomer–template interactions during the imprinting process, and the mechanism of solute retention on MIP CSPs in chromatography using normal phase or reverse-phase mobile phases are considered.
Keywords: Enantiomers; Chiral stationary phase (CSP); High performance liquid chromatography (HPLC); Thin layer chromatography (TLC); Supercritical fluid chromatography (SFC); Capillary electrochromatography (CEC)
Molecularly imprinted drug delivery systems by David Cunliffe; Andrew Kirby; Cameron Alexander (pp. 1836-1853).
Imprinted polymers are well established as molecular recognition materials but are now being increasingly considered for active biomedical applications such as drug delivery. In this review some highlights of recent research into molecularly imprinted drug delivery and controlled release systems are presented. The key factors controlling recognition and release by imprinted polymer matrices are discussed, the current limiting factors in their properties arising from the synthesis of these materials are considered, and the future prospects for imprinted polymers in drug delivery are outlined.
Keywords: Imprinted polymers; Cross-linked matrices; Controlled release; Molecular recognition; Drug delivery; MIP
Molecularly imprinted polymers in the drug discovery process by Daniel L. Rathbone (pp. 1854-1874).
Since molecularly imprinted polymers (MIPs) are designed to have a memory for their molecular templates it is easy to draw parallels with the affinity between biological receptors and their substrates. Could MIPs take the place of natural receptors in the selection of potential drug molecules from synthetic compound libraries? To answer that question this review discusses the results of MIP studies which attempt to emulate natural receptors. In addition the possible use of MIPs to guide a compound library synthesis towards a desired biological activity is highlighted.
Keywords: Combinatorial chemistry; Molecular imprinting; Receptor mimics; Cross-reactivity; Multiple templates; Composite template
Molecular imprinted polymer sensors: Implications for therapeutics by A.L. Hillberg; K.R. Brain; C.J. Allender (pp. 1875-1889).
A biosensor is a sensor that uses biological selectivity to limit its perception to particular key molecules and can be defined as an analytical device possessing a biological or biologically derived sensing element integrated with or associated closely with a physicochemical transducer. In the future it is likely that a number of key developments in therapeutic monitoring and intelligent drug delivery will rely on real-time feedback information in order to deliver an appropriate response. However due to issues of integration and the fragility and unreliability of the bio-molecule, biosensors are currently unable to fulfil this role. Molecular imprinted polymers are viable alternatives to both antibodies and enzymes and this review considers the current position of molecular imprinted polymer sensing.
Keywords: Biosensor; Molecularly imprinted polymer; Therapeutic monitoring; Intelligent drug delivery; Controlled release; BioMEMS