Polymer imprinted

Another way to realize the shape recognition ability is through the process known as molecular imprinting (Diaz-Garcia and Badia, 2004 Haupt, 2004). The process is depicted in Fig. 2.6. 

There are two processes by which the bulk imprinted polymers are formed covalent imprinting and noncovalent imprinting. In the former, the template molecule is first covalently functionalized with the monomer, and then copolymerized with the pure monomer. After that the covalent bond is broken and the template molecule is removed by extraction. In order to facilitate the extraction step, a so-called porogenic solvent is used. It effectively swells the polymer matrix. 

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. 

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Aromatic solvents or polycyclic aromatic hydrocarbons (PAFI) in water, e.g. can be detected by QCM coated with bulk-imprinted polymer layers. Flere, the interaction sites are not confined to the surface of the sensitive material but are distributed within the entire bulk leading to very appreciable sensor responses. Additionally, these materials show high selectivity aromatic solvents e.g. can be distinguished both by the number of methyl groups on the ring (toluene vs. xylene, etc.) and by their respective position. Selectivity factors in this case reach values of up to 100. 

SENSORS BASED ON FREE-STANDING MOLECULARLY IMPRINTED POLYMER MEMBRANES. COMPUTATIONAL MODELLING OF SYNTHETIC MIMICKS OF BIORECEPTORS... 

The development of highly selective chemical sensors for complex matrixes of medical, environmental, and industrial interest has been the object of greate research efforts in the last years. Recently, the use of artificial materials - molecularly imprinted polymers (MIPs) - with high recognition properties has been proposed for designing biomimetic sensors, but only a few sensor applications of MIPs based on electrosynythesized conductive polymers (MIEPs) have been reported [1-3]. 

METAL-LOADED SORBENTS AND MOLECULARLY IMPRINTED POLYMERS IN SPE-LC... 

Recently, molecularly imprinted polymers (MIPs) have gained attention as new, selective sorbents for chromatography and SPE. The cavities in the polymer... 

The sorbents that are most frequently used in environmental analysis are Cig-silica based sorbents, polymeric sorbents (usually styrenedivinilbenzene) and graphitized carbon. In order to increase the selectivity of these sorbents, immunosorbents (35, 36) have been developed and used with good results, while recently, molecularly imprinted polymers have started be to used (35, 36). 

Fig. 5-5. Schematic representation of the preparation procedure of molecular imprinted polymers (MIP).

Molecularly imprinted polymers (MIPs) can be prepared according to a number of approaches that are different in the way the template is linked to the functional monomer and subsequently to the polymeric binding sites (Fig. 6-1). Thus, the template can be linked and subsequently recognized by virtually any combination of cleavable covalent bonds, metal ion co-ordination or noncovalent bonds. The first example of molecular imprinting of organic network polymers introduced by Wulff was based on a covalent attachment strategy i.e. covalent monomer-template, covalent polymer-template [12]. 

Fig. 6-7. Asymmetry factor (AJ of the L-enantiomer versus sample load (A) and versus flow rate (B) on L-PA-imprinted polymers. Flow rate 1.0 ml min . Mobile phase MeCN/[potassium phosphate 0.05 M, pH 7] (7/3, v/v).

Table 6-4. Association constants for complexes between carboxylic acids and nitrogen bases in aprotic solvents and corresponding association constants and site densities for binding of the base to a molecu-larly imprinted polymer.

In summary, the present limitations in saturation capacities and selectivity of imprinted polymers preclude their applications in the above-mentioned preparative separation formats. 

R. A. Bartseh, M. Maeda, Moleeular and ionie reeognition with imprinted polymers, AC5 Symposium Series 703, Oxford University Press, Washington 1998. 

Gel materials are utilized in a variety of technological appUcations and are currently investigated for advanced exploitations such as the formulation of intelligent gels and the synthesis of molecularly imprinted polymers. 

Toth E, Hehn L, Merbach AE (2002) Relaxivity of MRI Contrast Agents. 221 61-101 Tovar GEM, Krauter I, Gruber C (2003) Molecularly Imprinted Polymer Nanospheres as Fully Affinity Receptors. 227 125-144... 

Ansell, RJ Mosbach, K, Magnetic Molecularly Imprinted Polymer Beads for Drug Radioligand Binding Assay, Analyst 123, 1611, 1998. 

Piletsky, SA Andersson, HS Nicholls, LA, Combined Hydrophobic and Electrostatic Interaction-Based Recognition in Molecularly Imprinted Polymers, Macromolecules 32, 633, 1999. 

Tan, ZJ Remcho, VT, Molecular Imprint Polymers as Highly Selective Stationary Phases for Open Tubular Liquid Chromatography and Capillary Elechophoresis, Elechophoresis 19, 2055, 1998. 

Advanced techniques like molecularly imprinted polymers (MIPs), infrared/near infrared spectroscopy (FT-IR/NIR), high resolution mass spectrometry, nuclear magnetic resonance (NMR), Raman spectroscopy, and biosensors will increasingly be applied for controlling food quality and safety. 

Zougagh, M., Valcarcel, M., and Rios, A., Automatic selective determination of caffeine in coffee and tea samples by using a supported liquid membrane-modified piezoelectric flow sensor with molecularly imprinted polymer. Trends Anal. Chem., 23, 399, 2004. 

The current trend in analytical chemistry applied to evaluate food quality and safety leans toward user-friendly miniaturized instruments and laboratory-on-a-chip applications. The techniques applied to direct screening of colorants in a food matrix include chemical microscopy, a spatial representation of chemical information from complex aggregates inside tissue matrices, biosensor-based screening, and molec-ularly imprinted polymer-based methods that serve as chemical alternatives to the use of immunosensors. 

Yano, K. and Karube, I., Molecularly imprinted polymers for biosensor applications. Trends Anal. Chem., 18, 199, 1999. 

The most widely employed techniques for the extraction of water samples for triazine compounds include liquid-liquid extraction (LLE), solid-phase extraction (SPE), and liquid-solid extraction (LSE). Although most reports involving SPE are off-line procedures, there is increasing interest and subsequently increasing numbers of reports regarding on-line SPE, the goal of which is to improve overall productivity and safety. To a lesser extent, solid-phase microextraction (SPME), supercritical fluid extraction (SEE), semi-permeable membrane device (SPMD), and molecularly imprinted polymer (MIP) techniques have been reported. 

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