Ultrasensitive Specific Stimulant Assay Based on Molecularly Imprinted Photonic Hydrogels

Taking theophylline and (1R,2S)-(−)-ephedrine as template molecules, two imprinted photonic-hydrogel films are prepared by a combination of colloidal-crystal and molecular-imprinting techniques. This paper shows a new approach for rapid and handy stimulant detection with high sensitivity and specificity. One film is proposed for analogous molecule assay, another one for chiral recognition. The key point of this approach is that the imprinted photonic polymer (IPP) consists of a three-dimensional (3D), highly-ordered and interconnected macroporous array with a thin hydrogel wall, where nanocavities complementary to analytes in shape and binding sites are distributed. This special, bicontinuous, hierarchical structure enables this polymer to report quickly, easily, sensitively and directly a molecular recognition event without any transducers and treatments for analytes (label-free). The inherent affinity of the nanocavities, deriving from molecular imprinting, makes these sensors highly specific to analytes, even if in a competitive environment. Their sensitive and specific responses to stimulants in buffer are determined by Bragg diffractive shifts due to the lattice change of their 3D ordered macroporous arrays resulting from their preferential rebinding to the target molecules. The measurements show that the prepared hydrogel films exhibit high sensitivity in such a 0.1 fM concentration of analytes and specificity even in a competitive urinous buffer. The reported method provides a rapid and handy approach for stimulant assay and drug analysis in athletic sports.

[1]  Olof Ramström,et al.  Molecular imprinting technology: challenges and prospects for the future , 1998 .

[2]  Klaus Mosbach,et al.  Drug assay using antibody mimics made by molecular imprinting , 1993, Nature.

[3]  Wilhelm Schänzer,et al.  Doping control analysis of intact rapid-acting insulin analogues in human urine by liquid chromatography-tandem mass spectrometry. , 2006, Analytical chemistry.

[4]  H. White,et al.  pH- and ionic strength-controlled cation permselectivity in amine-modified nanoporous opal films. , 2006, Langmuir : the ACS journal of surfaces and colloids.

[5]  Daniel M. Mittleman,et al.  Template-Directed Preparation of Macroporous Polymers with Oriented and Crystalline Arrays of Voids , 1999 .

[6]  Shengyang Tao,et al.  Imprinted photonic polymers for chiral recognition. , 2006, Angewandte Chemie.

[7]  G. Wulff Molecular Imprinting in Cross‐Linked Materials with the Aid of Molecular Templates— A Way towards Artificial Antibodies , 1995 .

[8]  Yanxiu Zhou,et al.  Potentiometric Sensing of Chiral Amino Acids , 2003 .

[9]  P. Marriott,et al.  Application of comprehensive two-dimensional gas chromatography to drugs analysis in doping control. , 2003, Journal of chromatography. A.

[10]  S. Asher,et al.  Polymerized colloidal crystal hydrogel films as intelligent chemical sensing materials , 1997, Nature.

[11]  Sanford A. Asher,et al.  Photonic Crystal Chemical Sensors: pH and Ionic Strength , 2000 .

[12]  K. Mosbach,et al.  Molecularly imprinted polymers and their use in biomimetic sensors. , 2000, Chemical reviews.

[13]  D. Thieme,et al.  Introduction to the application of capillary gas chromatography of performance-enhancing drugs in doping control. , 1999, Journal of chromatography. A.

[14]  W. Stöber,et al.  Controlled growth of monodisperse silica spheres in the micron size range , 1968 .

[15]  H. Lee,et al.  Surface-Imprinted, Thermosensitive, Core-Shell Nanosphere for Molecular Recognition , 2006 .

[16]  L. Amendola,et al.  Determination of clenbuterol in human urine by GC-MS-MS-MS: confirmation analysis in antidoping control. , 2002, Journal of chromatography. B, Analytical technologies in the biomedical and life sciences.

[17]  E. Ban,et al.  Cyclodextrin-mediated micellar electrokinetic chromatography and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry for the enantiomer separation of racemorphan in human urine. , 1999, Journal of chromatography. A.

[18]  S. Asher,et al.  Modeling of stimulated hydrogel volume changes in photonic crystal Pb2+ sensing materials. , 2005, Journal of the American Chemical Society.

[19]  Haibing Li,et al.  Preparation and characteristics of sol-gel-coated calix[4]arene fiber for solid-phase microextraction. , 2004, Journal of chromatography. A.

[20]  Ludovico Cademartiri,et al.  From colour fingerprinting to the control of photoluminescence in elastic photonic crystals , 2006 .

[21]  K. Shea,et al.  Selective protein capture by epitope imprinting. , 2006, Angewandte Chemie.

[22]  K. Severin Buchbesprechung: Molecularly Imprinted Polymers. Man-Made Mimics of Antibodies and their Applications in Analytical Chemistry. (Techniques and Instrumentation in Analytical Chemistry – Vol. 23). Herausgegeben von Börje Sellergren , 2002 .

[23]  Kevin Ke,et al.  Label-free affinity assays by rapid detection of immune complexes in submicrometer pores. , 2006, Angewandte Chemie.

[24]  Masayoshi Watanabe,et al.  A thermally adjustable multicolor photochromic hydrogel. , 2007, Angewandte Chemie.

[25]  Hisashi Saito,et al.  Simple and precision design of porous gel as a visible indicator for ionic species and concentration. , 2003, Chemical communications.

[26]  S. Marx,et al.  Molecular imprinting in thin films of organic-inorganic hybrid sol-gel and acrylic polymers , 2001 .

[27]  Wei Wang,et al.  Molecularly imprinted solid-phase extraction of (-)-ephedrine from Chinese Ephedra. , 2005, Journal of chromatography. A.

[28]  M. Bogusz,et al.  Reversed-phase high-performance liquid chromatographic database of retention indices and UV spectra of toxicologically relevant substances and its interlaboratory use. , 1994, Journal of chromatography. A.

[29]  Osamu Sato,et al.  Three-Dimensionally Ordered Macroporous Polymer Materials: An Approach for Biosensor Applications , 2002 .

[30]  J. Z. Hilt,et al.  Configurational biomimesis in drug delivery: molecular imprinting of biologically significant molecules. , 2004, Advanced drug delivery reviews.

[31]  Pierre Wiltzius,et al.  Humidity-sensing inverse opal hydrogels. , 2006, Langmuir : the ACS journal of surfaces and colloids.

[32]  D. Tai,et al.  Discrimination of peptides by using a molecularly imprinted piezoelectric biosensor. , 2003, Chemistry.

[33]  Paul V. Braun,et al.  Tunable Inverse Opal Hydrogel pH Sensors , 2003 .

[34]  F. Tagliaro,et al.  Use of beta-cyclodextrin in the capillary zone electrophoretic separation of the components of clandestine heroin preparations. , 2001, Journal of chromatography. A.

[35]  T Nagaoka,et al.  Potential-induced enantioselective uptake of amino acid into molecularly imprinted overoxidized polypyrrole. , 2000, Analytical chemistry.

[36]  C. Georgakopoulos,et al.  Doping control analysis in human urine by liquid chromatography-electrospray ionization ion trap mass spectrometry for the Olympic Games Athens 2004: determination of corticosteroids and quantification of ephedrines, salbutamol and morphine. , 2006, Analytica chimica acta.

[37]  Buddy D. Ratner,et al.  Template-imprinted nanostructured surfaces for protein recognition , 1999, Nature.

[38]  Kazunori Kataoka,et al.  Simple and precise preparation of a porous gel for a colorimetric glucose sensor by a templating technique. , 2003, Angewandte Chemie.

[39]  R. Ventura,et al.  Detection of diuretic agents in doping control. , 1996, Journal of chromatography. B, Biomedical applications.

[40]  A. Stein,et al.  Tuning solvent-dependent color changes of three-dimensionally ordered macroporous (3DOM) materials through compositional and geometric modifications , 2001 .

[41]  X. Zhu,et al.  Specific binding of cholic acid by cross-linked polymers prepared by the hybrid imprinting method , 2007 .

[42]  Dmitry A Markov,et al.  Photobiotin surface chemistry improves label-free interferometric sensing of biochemical interactions. , 2006, Angewandte Chemie.