Solvents monomer-template assemblies

An important part of the optimization process is the stabilization of the monomer-template assemblies by thermodynamic considerations (Fig. 6-11). The enthalpic and entropic contributions to the association will determine how the association will respond to changes in the polymerization temperature [18]. The change in free volume of interaction will determine how the association will respond to changes in polymerization pressure [82]. Finally, the solvent s interaction with the monomer-template assemblies relative to the free species indicates how well it will stabilize the monomer-template assemblies in solution [16]. Here each system must be optimized individually. Another option is simply to increase the concentration of the monomer or the template. In the former case, a problem is that the crosslinking as well as the potentially nonselective binding will increase simultaneously. In the... 

Some limitations of this molecular imprinting technique are obvious the template must be available in preparative amounts, it must be soluble in the monomer mixture and it must be stable and unreactive under the conditions of the polymerization. The solvent must be chosen considering the stability of the monomer-template assemblies and it should result in the porous structure necessary for rapid kinetics of the template interaction with the binding sites. If these criteria are satisfied, a robust material capable of selectively rebinding the template can be easily prepared and evaluated in a short period of time. 

In the self-assembly approach to molecular imprinting (Fig. 7.1) studies have indicated that the solution structure of the monomer-template assemblies defines the subsequently formed binding sites.3 In other words, the amount and quality of recognition sites in the MIP depends on the number and strength of specific interactions occurring between the template and the monomers in the prepolymerisation mixture (Fig. 7.4). These are in turn influenced by the quality of the solvent, cross-linking monomer, temperature, and pressure used in the polymerisation. 

Another possible way of overcoming the limitations posed by the presence of water in the suspension polymerisation process is to substitute the continuous water phase with alternative solvents that could still act as dispersing medium for the monomer mixture but better preserve noncovalent interactions in the template-monomer assembly. For example, liquid fluorocarbons are chemically inert and do not affect interactions which are used in noncovalent imprinting. Use of such solvents for the preparation of MIP microbeads has been demonstrated already in 1996 by Mayes and Mosbach [16,17]. A range of MIPs were prepared using Boc-l-phenylalanin as the template, MAA as the functional monomer and different kinds and amounts of crosslinkers and porogenic solvents. The resulting MIP microbeads... 

MIP films, applied to a QCM transducer, have been employed for chiral recognition of the R- and 5-propranolol enantiomers [107]. MIP films were prepared for that purpose by surface grafted photo-radical polymerization. First, a monolayer of 11-mercaptoundecanoic acid was self-assembled on a gold electrode of the quartz resonator. Then, a 2,2 -azobis(2-amidinopropane) hydrochloride initiator (AAPH), was attached to this monolayer. Subsequently, this surface-modified resonator was immersed in an ACN solution containing the MAA functional monomer, enantiomer template and trimethylolpropane trimethacrylate (TRIM) cross-linker. Next, the solution was irradiated with UV light for photopolymerization. The resulting MIP-coated resonator was used for enantioselective determination of the propranolol enantiomers under the batch [107] conditions and the FIA [107] conditions with an aqueous-ACN mixed solvent solution as the carrier. The MIP-QCM chemosensor was enantioselective to 5-propranolol at concentrations exceeding 0.38 mM [107]. 

In the noncovalent approach, the monomer is self-assembled around the tern-plating molecule and then again copolymerized with the additional monomer. The template is then removed by using a porogenic solvent. 

An example of the first approach is the integration of hydrogels into nanostructured silica films by addition of a suitable monomer (e.g., methyl methacrylate, /V-isopropyl acrylamide, etc.) and an initiator for radical polymerization to a solution containing a structure-directing surfactant and a prehydrolyzed silica precursor. During self-assembly, the monomers partition within the hydrophobic core of the surfactant mesophase postsynthesis polymerization (for instance, by UV treatment) followed by solvent washing to remove the surfactant template yields a polymer-silica nanohybrid. 

The noncovalent self-assembly method relies on less specific types of interactions, including electrostatic, hydrogen bonding, metal ion coordination, Van der Waals forces, and/or hydrophobic attractions.8 In this approach, the template and the polymerizable monomer (i.e., an organoalkoxysilane) are judiciously chosen so that they will have complementary interactions. Removal of the template is easier than in the covalent assembly approach and often involves simply washing the materials in a suitable solvent.8... 

Conventionally, MlPs are obtained by bulk co-polymerization from a mixture consisting of a functional monomer, cross-linker, chiral template, and a porogenic solvent mixture. Nowadays, imprinting via non-covalent template binding is preferred over the covalent mode and involves three major steps (see Fig. 9.9). (i) Functional monomers (e.g. methacrylic acid, MAA) and a cross-linker (e.g. ethyleneglycol dimethacrylate, EDMA) assemble around the enantiomeric print molecule, e.g. (S)-phenylalanine anilide (1), driven by non-covalent intermolecular interactions, e.g. ionic interactions, hydrogen bonding, dipole-dipole interaction. Tr-rt-interaction. (ii) By thermally or photochemi-... 

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