Binding capacity of molecularly imprinted polymers and their nonimprinted analogs.

Molecularly imprinted polymers bind their target compounds at binding sites. The binding sites are typically based on some type of functional group, such as carboxyl group. The total amount of such functional groups and their distribution into available and unavailable groups is not well known. The total binding capacity is usually indirectly determined from adsorption isotherms, which are measured much below the theoretical binding capacity. This work shows that in a variety of differently prepared, methacrylic acid based molecularly imprinted and nonimprinted polymers, all carboxylic groups used for the polymer synthesis are retained in the polymer, 80-90% of them can be accessed by strong bases and essentially the same amount can be used for adsorption of weak bases. This high level of adsorption can only be achieved, however, if the adsorbed weak base is strong enough, if the polymer is sufficiently elastic and if the solvent does not compete too strongly for the binding sites. These results may explain why the maximum binding capacities obtained from isotherm measurements are usually not equal to the total amount of available binding sites. This study confirms the usefulness of nonimprinted polymers at high loadings.

[1]  P. Carrott,et al.  Development of a selective sorbent for the solid-phase extraction of terbuthylazine in olive oil samples: a molecular imprinting strategy. , 2015, Journal of separation science.

[2]  Shih-Hsien Yang,et al.  Theoretical and experimental research on the self-assembled system of molecularly imprinted polymers formed by salbutamol and methacrylic acid. , 2015, Journal of separation science.

[3]  P. Manesiotis,et al.  Molecularly imprinted polymers for the isolation of bioactive naphthoquinones from plant extracts. , 2013, Journal of chromatography. A.

[4]  P. Manesiotis,et al.  Molecularly imprinted polymers for the extraction of imiquimod from biological samples using a template analogue strategy , 2013 .

[5]  B. Sellergren,et al.  An artificial estrogen receptor through combinatorial imprinting. , 2012, Chemistry.

[6]  B. Örmeci,et al.  Application of molecularly imprinted and non-imprinted polymers for removal of emerging contaminants in water and wastewater treatment: a review , 2012, Environmental Science and Pollution Research.

[7]  I. Chianella,et al.  Selective Recognition of Bifunctional Molecules by Synthetic Polymers Prepared by Covalent Molecular Imprinting , 2012 .

[8]  F. Borrull,et al.  Preparation of a polar monolithic stir bar based on methacrylic acid and divinylbenzene for the sorptive extraction of polar pharmaceuticals from complex water samples. , 2012, Journal of chromatography. A.

[9]  Laura Anfossi,et al.  A connection between the binding properties of imprinted and nonimprinted polymers: a change of perspective in molecular imprinting. , 2012, Journal of the American Chemical Society.

[10]  David A Barrow,et al.  Current practices for describing the performance of molecularly imprinted polymers can be misleading and may be hampering the development of the field , 2011, Journal of molecular recognition : JMR.

[11]  S. Piletsky,et al.  Development of the custom polymeric materials specific for aflatoxin B1 and ochratoxin A for application with the ToxiQuant T1 sensor tool. , 2010, Journal of chromatography. A.

[12]  I. Chianella,et al.  Attenuation of Vibrio fischeri quorum sensing using rationally designed polymers. , 2010, Biomacromolecules.

[13]  Surong Mei,et al.  Determination of trace tetracycline antibiotics in foodstuffs by liquid chromatography–tandem mass spectrometry coupled with selective molecular-imprinted solid-phase extraction , 2009, Analytical and bioanalytical chemistry.

[14]  P. Buvat,et al.  Novel Stoichiometric, Noncovalent Pinacolyl Methylphosphonate Imprinted Polymers: A Rational Design by NMR Spectroscopy , 2008 .

[15]  Lennart Mathiasson,et al.  Selective determination of acidic pharmaceuticals in wastewater using molecularly imprinted solid-phase extraction. , 2008, Analytica chimica acta.

[16]  B. Mattiasson,et al.  Preliminary evaluation of new polymer matrix for solid-phase extraction of nonylphenol from water samples. , 2008, Analytica chimica acta.

[17]  I. Chianella,et al.  Design of molecular imprinted polymers compatible with aqueous environment. , 2008, Analytica chimica acta.

[18]  C. Legido-Quigley,et al.  Chromatographic characterisation, under highly aqueous conditions, of a molecularly imprinted polymer binding the herbicide 2,4-dichlorophenoxyacetic acid. , 2007, Analytica chimica acta.

[19]  S. Piletsky,et al.  Comparison of thin-layer and bulk MIPs synthesized by photoinitiated in situ crosslinking polymerization from the same reaction mixtures , 2005 .

[20]  L. Nie,et al.  Adsorption Isotherms and Sites Distribution of Caffeic Acid – Imprinted Polymer Monolith from Frontal Analysis , 2004 .

[21]  Wolfgang Lindner,et al.  Molecularly imprinted polymer-assisted sample clean-up of ochratoxin A from red wine: merits and limitations. , 2004, Journal of chromatography. B, Analytical technologies in the biomedical and life sciences.

[22]  B. Sellergren,et al.  Effect of solvents on the selectivity of terbutylazine imprinted polymer sorbents used in solid-phase extraction. , 2002, Journal of chromatography. A.

[23]  B. Sellergren,et al.  Studies on the Process of Formation, Nature and Stability of Binding Sites in Molecularly Imprinted Polymers , 2002 .

[24]  J. Haginaka,et al.  Uniform-sized molecularly imprinted polymer material for (S)-propranolol. , 2000, Journal of pharmaceutical and biomedical analysis.

[25]  Georges Guiochon,et al.  Study of the thermodynamics and mass transfer kinetics of two enantiomers on a polymeric imprinted stationary phase , 1998 .

[26]  F. Trotta,et al.  Chromatographic characterization of a molecularly imprinted polymer binding theophylline in aqueous buffers , 1997 .

[27]  B. Sellergren,et al.  Influence of template basicity and hydrophobicity on the molecular recognition properties of molecularly imprinted polymers , 1996 .

[28]  B. Sellergren,et al.  Chiral ion-exchange chromatography. Correlation between solute retention and a theoretical ion-exchange model using imprinted polymers. , 1993, Journal of chromatography. A.

[29]  B. Sellergren,et al.  Influence of polymer morphology on the ability of imprinted network polymers to resolve enantiomers , 1993 .

[30]  G. Manecke.  Ionenaustauscher, Band I: Grundlagen. Struktur ‐ Herstellung ‐ Theorie, von F. Helfferich. Verlag Chemie GmbH., Weinheim/Bergstraße 1959. 1. Aufl., VIII, 520 S., 153 Abb., 14 Tab., geb. DM 48.– , 1962 .

[31]  H. Gregor,et al.  Studies on Ion Exchange Resins. XIV. Titration, Capacity and Swelling of Methaerylic Acid Resins , 1955 .

[32]  R. Kunin,et al.  Routine Exchange Capacity Determinations of Ion Exchange Resins , 1955 .

[33]  G. Guiochon,et al.  Comparison of the thermodynamic properties of particulate and monolithic columns of molecularly imprinted copolymers. , 2005, Analytical chemistry.

[34]  Börje Sellergren,et al.  Molecularly imprinted polymers : man-made mimics of antibodies and their applications in analytical chemistry , 2001 .

[35]  L. Andersson,et al.  Application of molecular imprinting to the development of aqueous buffer and organic solvent based radioligand binding assays for (s)-propranolol. , 1996, Analytical chemistry.

[36]  K Mosbach,et al.  Molecular Imprinting , 1994, Trends in biochemical sciences.