Analytical and Bioanalytical Chemistry

, Volume 407, Issue 22, pp 6747–6758 | Cite as

Morphology and kinetic modeling of molecularly imprinted organosilanol polymer matrix for specific uptake of creatinine

  • Qian Yee Ang
  • Siew Chun LowEmail author
Research Paper


Molecular imprinting is an emerging technique to create imprinted polymers that can be applied in affinity-based separation, in particular, biomimetic sensors. In this study, the matrix of siloxane bonds prepared from the polycondensation of hydrolyzed tetraethoxysilane (TEOS) was employed as the inorganic monomer for the formation of a creatinine (Cre)-based molecularly imprinted polymer (MIP). Doped aluminium ion (Al3+) was used as the functional cross-linker that generated Lewis acid sites in the confined silica matrix to interact with Cre via sharing of lone pair electrons. Surface morphologies and pore characteristics of the synthesized MIP were determined by field emission scanning electron microscopy (FESEM) and Brunauer-Emmet-Teller (BET) analyses, respectively. The imprinting efficiency of MIPs was then evaluated through the adsorption of Cre with regard to molar ratios of Al3+. A Cre adsorption capacity of up to 17.40 mg Cre g–1 MIP was obtained and adsorption selectivity of Cre to its analogues creatine (Cr) and N-hydroxysuccinimide (N-hyd) were found to be 3.90 ± 0.61 and 4.17 ± 3.09, respectively. Of all the studied MIP systems, chemisorption was predicted as the rate-limiting step in the binding of Cre. The pseudo-second-order chemical reaction kinetic provides the best correlation of the experimental data. Furthermore, the equilibrium adsorption capacity of MIP fit well with a Freundlich isotherm (R 2 = 0.98) in which the heterogeneous surface was defined.

Graphical Abstract

Affinity binding of Cre to specific recognition sites based on shape factor


Molecularly imprinted polymer Creatinine Sol-gel Isotherm Shape recognition Chemisorption 



The authors gratefully acknowledge financial support from The Institution of Higher Education FRGS Grant (6071251), ScienceFund (6013393), and Membrane Science and Technology Cluster. Q.Y. Ang is financially assisted by the Ministry of Higher Education (MOHE) and Universiti Malaysia Perlis (UniMAP).


  1. 1.
    Wyss M, Kaddurah-Daouk R (2000) Creatine and creatinine metabolism. Physiol Rev 80(3):1107–1213Google Scholar
  2. 2.
    Killard AJ, Smyth MR (2000) Creatinine biosensors: principles and designs. Trends Biotechnol 18(10):433–437CrossRefGoogle Scholar
  3. 3.
    Soldatkin AP, Montoriol J, Sant W, Martelet C, Jaffrezic-Renault N (2002) Creatinine sensitive biosensor based on ISFETs and creatinine deiminase immobilized in BSA membrane. Talanta 58(2):351–357CrossRefGoogle Scholar
  4. 4.
    Arndt T (2009) Urine-creatinine concentration as a marker of urine dilution: reflections using a cohort of 45,000 samples. Forensic Sci Int 186(1/3):48–51CrossRefGoogle Scholar
  5. 5.
    Mǎdǎraş MB, Buck RP (1996) Miniaturized biosensors employing electropolymerized permselective films and their use for creatinine assays in human serum. Anal Chem 68(21):3832–3839CrossRefGoogle Scholar
  6. 6.
    Tsai H-A, Syu M-J (2005) Synthesis and characterization of creatinine imprinted poly(4-vinylpyridine-co-divinylbenzene) as a specific recognition receptor. Analytica Chimica Acta 539(1–2):107–116Google Scholar
  7. 7.
    Osaka T, Komaba S, Amano A, Fujino Y, Mori H (2000) Electrochemical molecular sieving of the polyion complex film for designing highly sensitive biosensor for creatinine. Sensors Actuators B Chem 65(1/3):58–63CrossRefGoogle Scholar
  8. 8.
    Weber JA, van Zanten AP (1991) Interferences in current methods for measurements of creatinine. Clin Chem 37(5):695–700Google Scholar
  9. 9.
    Börner U, Staehler F, Stinshoff K, Szasz G (1976) Evaluation of an enzymatic method for creatinine. Z Anal Chem 279(2):171–171CrossRefGoogle Scholar
  10. 10.
    Kandimalla V, Ju H (2004) Molecular imprinting: a dynamic technique for diverse applications in analytical chemistry. Anal Bioanal Chem 380(4):587–605CrossRefGoogle Scholar
  11. 11.
    Spégel P, Schweitz L, Nilsson S (2002) Molecularly imprinted polymers. Anal Bioanal Chem 372(1):37–38CrossRefGoogle Scholar
  12. 12.
    Haginaka J (2004) Molecularly imprinted polymers for solid-phase extraction. Anal Bioanal Chem 379(3):332–334CrossRefGoogle Scholar
  13. 13.
    Feng L, Pamidighantam B, Lauterbur P (2010) Microwave-assisted sol-gel synthesis for molecular imprinting. Anal Bioanal Chem 396(4):1607–1612CrossRefGoogle Scholar
  14. 14.
    Sharma P, Pietrzyk-Le A, D’Souza F, Kutner W (2012) Electrochemically synthesized polymers in molecular imprinting for chemical sensing. Anal Bioanal Chem 402(10):3177–3204CrossRefGoogle Scholar
  15. 15.
    Fischer E (1894) Einfluss der Configuration auf die Wirkung der Enzyme. Berichte der deutschen chemischen Gesellschaft. 27(3):2985–2993Google Scholar
  16. 16.
    Dickert FL, Hayden O (1999) Imprinting with sensor development—on the way to synthetic antibodies. Fresenius J Anal Chem 364(6):506–511CrossRefGoogle Scholar
  17. 17.
    Al-Kindy S, Badía R, Suárez-Rodríguez JL, Díaz-García ME (2000) Molecularly imprinted polymers and optical sensing applications. Crit Rev Anal Chem 30(4):291–309CrossRefGoogle Scholar
  18. 18.
    Vasapollo G, Sole RD, Mergola L, Lazzoi MR, Scardino A, Scorrano S, Mele G (2011) Molecularly imprinted polymers: present and future prospective. Int J Mol Sci 12(9):5908–5945CrossRefGoogle Scholar
  19. 19.
    Martin-Esteban A (2004) Molecular imprinting technology: a simple way of synthesizing biomimetic polymeric receptors. Anal Bioanal Chem 378(8):1875–1875CrossRefGoogle Scholar
  20. 20.
    Resmini M (2012) Molecularly imprinted polymers as biomimetic catalysts. Anal Bioanal Chem 402(10):3021–3026CrossRefGoogle Scholar
  21. 21.
    Dickert F (2007) Molecular imprinting. Anal Bioanal Chem 389(2):353–354CrossRefGoogle Scholar
  22. 22.
    Li T-J, Chen P-Y, Nien P-C, Lin C-Y, Vittal R, Ling T-R, Ho K-C (2012) Preparation of a novel molecularly imprinted polymer by the sol-gel process for sensing creatinine. Anal Chim Acta 711:83–90CrossRefGoogle Scholar
  23. 23.
    Brinker CJ, Scherer GW (1990) Sol-gel science: the physics and chemistry of sol-gel processing. Academic Press, San DiegoGoogle Scholar
  24. 24.
    Lin J, Brown CW (1997) Sol-gel glass as a matrix for chemical and biochemical sensing. TrAC Trends Anal Chem 16(4):200–211CrossRefGoogle Scholar
  25. 25.
    Basabe-Desmonts L, Reinhoudt DN, Crego-Calama M (2007) Design of fluorescent materials for chemical sensing. Chem Soc Rev 36(6):993–1017CrossRefGoogle Scholar
  26. 26.
    Mujahid A, Lieberzeit PA, Dickert FL (2010) Chemical sensors based on molecularly imprinted sol-gel materials. Materials 3(4):2196–2217CrossRefGoogle Scholar
  27. 27.
    Jerónimo PCA, Araújo AN, Conceição BSM, Montenegro M (2007) Optical sensors and biosensors based on sol-gel films. Talanta 72(1):13–27CrossRefGoogle Scholar
  28. 28.
    Graham AL, Carlson CA, Edmiston PL (2002) Development and characterization of molecularly imprinted sol-gel materials for the selective detection of DDT. Anal Chem 74(2):458–467CrossRefGoogle Scholar
  29. 29.
    Maier N, Lindner W (2007) Chiral recognition applications of molecularly imprinted polymers: a critical review. Anal Bioanal Chem 389(2):377–397CrossRefGoogle Scholar
  30. 30.
    Tsai H-A, Syu M-J (2005) Synthesis of creatinine-imprinted poly(β-cyclodextrin) for the specific binding of creatinine. Biomaterials 26(15):2759–2766Google Scholar
  31. 31.
    Chang YS, Ko TH, Hsu TJ, Syu MJ (2009) Synthesis of an imprinted hybrid organic-inorganic polymeric sol-gel matrix toward the specific binding and isotherm kinetics investigation of creatinine. Anal Chem 81(6):2098–2105CrossRefGoogle Scholar
  32. 32.
    Tsai H-A, Syu M-J (2011) Preparation of imprinted poly(tetraethoxysilanol) sol-gel for the specific uptake of creatinine. Chem Eng J 168(3):1369–1376CrossRefGoogle Scholar
  33. 33.
    Ling T-R, Syu YZ, Tasi Y-C, Chou T-C, Liu C-C (2005) Size-selective recognition of catecholamines by molecular imprinting on silica–alumina gel. Biosens Bioelectron 21(6):901–907CrossRefGoogle Scholar
  34. 34.
    Karak D, Lohar S, Sahana A, Guha S, Banerjee A, Das D (2012) An Al3+ induced green luminescent fluorescent probe for cell imaging and naked eye detection. Anal Methods 4(7):1906–1908CrossRefGoogle Scholar
  35. 35.
    Jeyanthi D, Iniya M, Krishnaveni K, Chellappa D (2013) A ratiometric fluorescent sensor for selective recognition of Al3+ ions based on a simple benzimidazole platform. RSC Adv 3(43):20984–20989CrossRefGoogle Scholar
  36. 36.
    Qiu C, Xing Y, Yang W, Zhou Z, Wang Y, Liu H, Xu W (2015) Surface molecular imprinting on hybrid SiO2-coated CdTe nanocrystals for selective optosensing of bisphenol A and its optimal design. Appl Surface Sci 345:405–417CrossRefGoogle Scholar
  37. 37.
    Guo W, Hu W, Pan J, Zhou H, Guan W, Wang X, Dai J, Xu L (2011) Selective adsorption and separation of BPA from aqueous solution using novel molecularly imprinted polymers based on kaolinite/Fe3O4 composites. Chemi Eng J 171(2):603–611CrossRefGoogle Scholar
  38. 38.
    Ren Y, Ma W, Ma J, Wen Q, Wang J, Zhao F (2012) Synthesis and properties of bisphenol A molecular imprinted particle for selective recognition of BPA from water. J Colloid Interface Sci 367(1):355–361CrossRefGoogle Scholar
  39. 39.
    Foo KY, Hameed BH (2010) Insights into the modeling of adsorption isotherm systems. Chem Eng J 156(1):2–10CrossRefGoogle Scholar
  40. 40.
    Johnson RD, Arnold FH (1995) The temkin isotherm describes heterogeneous protein adsorption. Biochim Biophys Acta Prot Struct Mol Enzymol 1247(2):293–297CrossRefGoogle Scholar
  41. 41.
    Subrahmanyam S, Piletsky SA, Piletska EV, Chen B, Karim K, Turner APF (2001) ‘Bite-and-Switch’ approach using computationally designed molecularly imprinted polymers for sensing of creatinine. Biosens Bioelectron 16(9/12):631–637CrossRefGoogle Scholar
  42. 42.
    Hsieh R-Y, Tsai H-A, Syu M-J (2006) Designing a molecularly imprinted polymer as an artificial receptor for the specific recognition of creatinine in serums. Biomaterials 27(9):2083–2089CrossRefGoogle Scholar
  43. 43.
    Miura C, Funaya N, Matsunaga H, Haginaka J (2013) Monodisperse, molecularly imprinted polymers for creatinine by modified precipitation polymerization and their applications to creatinine assays for human serum and urine. J Pharmaceut Biomed Anal 85:288–294CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2015

Authors and Affiliations

  1. 1.School of Chemical EngineeringUniversiti Sains MalaysiaNibong TebalMalaysia

Personalised recommendations