Abstract
Molecular imprinting is a well-known fabrication technique for designing artificial receptors and molecular sensors. The technique resembles a lock and key mechanism and utilizes shape-complementary cavities within polymeric materials as molecular recognition sites for various relevant molecules. In this study, we prepared molecularly imprinted polypeptide gel layers based on cyclodextrin-modified poly(l-lysine) (CD-PLL) on quartz crystal microbalance (QCM) sensor chips and investigated their molecular recognition behaviors for bisphenol A (BPA) using the QCM technique. With BPA as the template and CD as its ligand, the BPA-imprinted CD-PLL gel layers were prepared on electropolymerized polyterthiophene films, which were formed using electrochemical QCM (EQCM). The BPA-imprinted CD-PLL gel layer chip exhibited a much greater QCM response than the non-imprinted gel layer chip in an aqueous BPA solution. The greater response of the BPA-imprinted CD-PLL gel layer chip means that molecular imprinting enabled CD ligands to be arranged at optimal positions for forming molecular recognition sites. The combination of in situ electropolymerization using EQCM and molecular imprinting provides useful methods for fabricating highly selective and sensitive sensor devices for monitoring minute amounts of BPA in water.
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References
Kavlock, R. J., Daston, G. P., DeRosa, C., Fenner-Crisp, P., Gray, L. E., Kaattari, S., Lucier, G., Luster, M., Mac, M. J., Maczka, C., Miller, R., Moore, J., Rolland, R., Scott, G., Sheehan, D. M., Sinks, T. & Tilson, H. A. Research needs for the risk assessment of health and environmental effects of endocrine disruptors: a report of the U.S. EPA-sponsored workshop. Environ. Health Perspect. 104, 715–740 (1996).
Kim, H. S., Han, S. Y., Yoo, S. D., Lee, B. M. & Park, K. L. Potential estrogenic effects of bisphenol-A estimated by in vitro and in vivo combination assays. J. Toxicol. Sci. 26, 111–118 (2001).
Li, W., Seifert, M., Xu, Y. & Hock, B. Comparative study of estrogenic potencies of estradiol, tamoxifen, bisphenol-A and resveratrol with two in vitro bioassays. Environ. Int. 30, 329–335 (2004).
Suzuki, A., Sugihara, A., Uchida, K., Sato, T., Ohta, Y., Kats, Y., Watanabe, H. & Iguchi, T. Developmental effects of perinatal exposure to bisphenol-A and diethylstilbestrol on reproductive organs in female mice. Reprod. Toxicol. 16, 107–116 (2002).
Malitesta, C., Losito, I. & Zambonin, P. G. Molecularly imprinted electrosynthesized polymers: new materials for biomimetic sensors. Anal. Chem. 71, 1366–1370 (1999).
Dickert, F. L., Hayden, O. & Halikias, K. P. Synthetic receptors as sensor coatings for molecules and living cells. Analyst 126, 766–771 (2001).
Lin, J. M. & Yamada, M. Chemiluminescent flow-through sensor for 1,10-phenanthroline based on the combination of molecular imprinting and chemiluminescence. Analyst 126, 810–815 (2001).
Apodaca, D., Pernites, R., Ponnapati, R., Del Mundo, F. & Advincula, R. Electropolymerized molecularly imprinted polymer films of a bis-terthiophene dendron: folic acid quartz crystal microbalance sensing. ACS Appl. Mater. Interfaces 3, 191–203 (2011).
Pernites, R., Ponnapati, R. & Advincula, R. Surface plasmon resonance (SPR) detection of theophylline via electropolymerized molecularly imprinted polythiophenes. Macromolecules 43, 9724–9735 (2010).
Pernites, R., Ponnapati, R., Felipe, J. & Advincula, R. Electropolymerization molecularly imprinted polymer (E-MIP) SPR sensing of drug molecules: pre-polymerization complexed terthiophene and carbazole electroactive monomers. Biosens. Bioelectron. 26, 2766–2771 (2011).
Mosbach, K. Molecular imprinting. Trends Biochem. Sci. 19, 9–14 (1994).
Shea, K. J. Molecular imprinting of synthetic network polymers: the de novo synthesis of macromolecular binding and catalytic sites. Trends Polym. Sci. 2, 166–184 (1994).
Wulff, G. Molecular imprinting in cross-linked materials with the aid of molecular templates- a way towards artificial antibodies. Angew. Chem. Int. Ed. 34, 1812–1832 (1995).
Byrnea, M. E., Parka, K. & Peppas, N. A. Molecular imprinting within hydrogel. Adv. Drug Delivery Rev. 54, 149–161 (2002).
Asanuma, H., Hishiya, T. & Komiyama, M. Tailor-made receptors by molecular imprinting. Adv. Mater. 12, 1019–1030 (2000).
Hishiya, T., Shibata, M., Kakazu, M., Asanuma, H. & Komiyama, M. Molecularly imprinted cyclodextrins as selective receptors for steroids. Macromolecules 32, 2265–2269 (1999).
Tanaka, T., Fillmore, D., Sun, S.-T., Nishio, I., Swislow, G. & Shah, A. Phase transitions in ionic gels. Phys. Rev. Lett. 45, 1636–1644 (1980).
Annaka, M. & Tanaka, T. Multiple phases of polymer gels. Nature 335, 430–432 (1992).
Amiya, T., Horikawa, Y., Hirose, Y., Li, Y. & Tanaka, T. Reentrant phase transition of N-isopropylacrylamide gels in mixed solvents. J. Chem. Phys. 86, 2375–2379 (1987).
Chen, G. & Hoffman, A. S. Graft copolymers that exhibit temperature-induced phase transitions over a wide range of pH. Nature 373, 49–52 (1995).
Yoshida, R., Uchida, K., Kaneko, T., Sakai, K., Kikuchi, A., Sakurai, Y. & Okano, T. Comb-type grafted hydrogels with rapid deswelling response to temperature changes. Nature 374, 240–242 (1995).
Tanaka, T. Gels. Sci. Am. 244, 124–136 (1981).
Dusek, K. Responsive Gels: Volume Transitions I. Adv. Polym. Sci. 109, (Springer, Berlin, Germany, 1993).
Dusek, K. Responsive Gels: Volume Transitions II. Adv. Polym. Sci. 110, (Springer, Berlin, Germany, 1993).
Okano, T. Biorelated Polymers and Gels, (Academic, Boston, MA, USA, 1998).
Hoffman, A.S. “Intelligent” polymers in medicine and biotechnology. Macromol. Symp. 98, 645–664 (1995).
Miyata, T. Preparation of smart soft materials using molecular complexes. Polym. J. 42, 277–289 (2010).
Miyata, T., Asami, N. & Uragami, T. Structural design of stimuli-responsive bioconjugated hydrogels that respond to a target antigen. J. Polym. Sci. Part B: Polym. Phys. 47, 2144–2157 (2009).
Miyata, T., Jige, M., Nakaminami, T. & Uragami, T. Tumor marker-responsive behavior of gels prepared by biomolecular imprinting. Proc. Natl Acad. Sci. USA 103, 1190–1193 (2006).
Miyata, T., Asami, N. & Uragami, T. A reversibly antigen-responsive hydrogel. Nature 399, 766–769 (1999).
Kawamura, A., Kiguchi, T., Nishihata, T., Uragami, T. & Miyata, T. Target molecule-responsive hydrogels designed via molecular imprinting using bisphenol A as a template. Chem. Commun. 50, 11101–11103 (2014).
Matsumoto, K., Kawamura, A. & Miyata, T. Structural transition of pH-responsive poly(L-lysine) hydrogel prepared via chemical cross-linking. Chem. Lett. 44, 1284–1286 (2015).
Advincula, R., Brittain, B., Ruhe, J. & Caster, K. Polymer Brushes: Synthesis Characterizations, Applications, (Wiley- VCH, Weinheim, Germany, 2004).
Duran, H., Ogura, K., Nakao, K., Vianna, S., Usui, H., Advincula, R. & Knoll, W. High-vacuum vapor deposition and in situ monitoring of N-carboxy anhydride benzyl glutamate polymerization. Langmuir 25, 10711–10718 (2009).
Wang, X., Kim, Y., Drew, C., Ku, B., Kumar, J. & Samuelson, L. Electrostatic assembly of conjugated polymer thin layers on electrospun nanofibrous membranes for biosensors. Nano Lett. 4, 331–334 (2004).
Pernites, R., Venkata, S., Tiu, B., Yago, A. & Advincula, R. Nanostructured, molecularly imprinted, and template-patterned polythiophenes for chiral sensing and differentiation. Small 8, 1669–1674 (2012).
Park, J., Pernites, R.,. Estillore, N., Hyakutake, T., Ponnapati, R., Tiu, B., Nishide, H. & Advincula, R. Capsulation of carbon nanotubes on top of colloidally templated and electropolymerized polythiophene arrays. Chem. Commun. 47, 8871–8873 (2011).
Tong, H., Wang, L., Jing, X. & Wang, F. “Turn-on” conjugated polymer fluorescent chemosensor for fluoride ion. Macromolecules 36, 2584–2586 (2003).
McCullough, R., Ewbank, P. & Loewe, R. Self-assembly and disassembly of regioregular, water soluble polythiophenes: chemoselective ionchromatic sensing in water. J. Am. Chem. Soc. 119, 633–634 (1997).
Tiu, B., Pernites, R., Foster, E. & Advincula, R. Conducting polymer–gold co-patterned surfaces via nanosphere lithography. J. Colloid Interface Sci. 459, 86–96 (2015).
Evans-Kennedy, U., Clohessy, J. & Cunnane, V. J. Spectroelectrochemical study of 2,2’:5’,2’’-terthiophene polymerization at a liquid/liquid interface controlled by potential-determining ions. Macromolecules 37, 3630–3634 (2004).
Zotti, G., Marin, R. & Gallazzi, M. Electrochemical polymerization of mixed alkyl−alkoxybithiophenes and -terthiophenes. Substitution-driven polymerization from thiophene hexamers to long-chain polymers. Chem. Mater. 9, 2945–2950 (1997).
Taranekar, P., Fulghum, T., Baba, A., Patton, D. & Advincula, R. Quantitative electrochemical and electrochromic behavior of terthiophene and carbazole containing conjugated polymer network film precursors: EC-QCM and EC-SPR. Langmuir 23, 908–917 (2007).
Byun, H. S. & Bittman, R. Hydrophilic cholesterol-binding molecular imprinted polymers. Tetrahedron Lett. 42, 1839–1841 (2001).
Prabaharan, M. & Mano, J. F. Hydroxypropyl chitosan bearing β-cyclodextrin cavities: synthesis and slow release of its inclusion complex with a model hydrophobic Drug. Macromol. Biosci. 5, 965–973 (2005).
Girek, T. & Ciesielski, W. Polymerization of β-cyclodextrin with succinic anhydride and thermogravimetric study of the polymers. J. Incl. Phenom. Macrocycl. Chem. 69, 439–444 (2011).
Adrian, F., Budtova, T., Tarabukina, E., Pinteala, M., Mariana, S., Peptu, C., Harabagiu, V. & Simionescu, B. C. Inclusion complexes of γ-cyclodextrin and carboxyl-modified γ-cyclodextrin with C60: synthesis, characterization and controlled release application via microgels. J. Incl. Phenom. Macrocycl. Chem. 64, 83–94 (2009).
Sauerbrey, G. Z. Verwendung von schwingquarzen zur wägung dünner schichten und zur mikrowägung. Phys. A Hadrons Nucl. 155, 206–222 (1959).
Acknowledgements
This work was supported in part by the Grant-in-Aid for Scientific Research on Innovative Areas of ‘New Polymeric Materials Based on Element-Blocks’ (No. 15H00768) from The Ministry of Education, Culture, Sports, Science and Technology of Japan, by the Grant-in-Aid for Scientific Research (B; No. 15H03026) from the Japan Society for the Promotion of Science (JSPS), and by the grants from the National Science Foundation (NSF STC-0423914 and NSF CMMI 1333651).
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Matsumoto, K., Tiu, B., Kawamura, A. et al. QCM sensing of bisphenol A using molecularly imprinted hydrogel/conducting polymer matrix. Polym J 48, 525–532 (2016). https://doi.org/10.1038/pj.2016.23
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DOI: https://doi.org/10.1038/pj.2016.23
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