Advertisement

Kinetic and thermodynamic studies of molecularly imprinted polymers for the selective adsorption and specific enantiomeric recognition of D-mandelic acid

  • T. Sajini
  • M. G. Gigimol
  • Beena MathewEmail author
ORIGINAL PAPER
  • 53 Downloads

Abstract

In the present article, we fabricated an artificial sorbents of D-mandelic acid (D-MA) on vinyl functionalized multiwalled carbon nanotube (MWCNT) by molecular imprinting technology. Here molecular imprinted polymers (MIPs) were tailored by D-MA as a template molecule on the surface of the vinyl functionalized MWCNT with 4-vinyl pyridine (4-VP) as the functional monomer, ethylene glycol dimethacrylate (EGDMA) as the crosslinking agent and 2,2′-azo-bis-isobutyronitrile (AIBN) as the initiatorvia a thermal polymerization technique. For better evaluation, blank polymer (MWCNT-NIP) was prepared by the same procedure, only without using the template molecule in the polymerization process. To get a better knowledge of the role of MWCNT on chiral recognition, D-MA imprinted and non-imprinted polymers without MWCNT were also prepared and analysed. Fourier transform infrared spectra (FT-IR), X-ray diffraction technique (XRD), Thermogravimetric analysis (TGA), Scanning electron microscopy (SEM) and Transmission electron microscopy (TEM) were used to characterize the composite structure, morphology and determine the grafted MIP quantities in the composite. Selective adsorption and specific chiral recognition of synthesised polymers were examined using the theory of kinetics and thermodynamics. The resulting MWCNT-MIP demonstrated favorable selectivity, good stability and a higher adsorption capacity for the template particle compared to products created by bulk polymerization. The thermodynamic studies revealed that the adsorption was controlled by enthalpy and that MWCNT-MIPs had higher enthalpy and entropy than conventional polymers which contributed to the specific recognition of MWCNT-MIPs. D-MA adsorption on MWCNT-MIP is in good agreement with Langmuir adsorption isotherm and kinetics obey second order rate expression with rate constant k2 = 0.1482 mol−1 min −1. Kinetic correlation indicated that there was fast and selective adsorption equilibrium for D-MA molecules in MWCNT-MIPs happen because of the homogenous binding sites of template molecules on the surface of nanotubes.

Keywords

D-mandelic acid Molecular imprinting Multiwalled carbon nanotube Binding isotherm Kinetics Thermodynamics Selectivity 

Notes

References

  1. 1.
    Chemie O, Bonn BDU, Sarhan A (1977) Enzyme-analogue built polymers. Makromol Chem 178:2799–2816CrossRefGoogle Scholar
  2. 2.
    Fonseca Silva C, Bastos Borges K, Soares do Nascimento Jr C (2018) Rational Design of a Molecularly Imprinted Polymer for Dinotefuran: theoretical and experimental studies aimed at the development of an efficient adsorbent for microextraction by packed sorbent. Analyst 143:141–149CrossRefGoogle Scholar
  3. 3.
    Hosoya K, Shirasu Y, Kimata K, Tanaka N (1998) Molecularly imprinted chiral stationary phase prepared with racemic template. Anal Chem Acta 70(5):943–945CrossRefGoogle Scholar
  4. 4.
    Ou J, Dong J, Tian T, Hu J, Ye M, Zou H (2007) Enantioseparation of Tetrahydropalmatine and Tröger ’ s base by molecularly imprinted monolith in capillary Electrochromatography. J Biochem Biophys Methods 70:71–76CrossRefGoogle Scholar
  5. 5.
    Lu Y, Li C, Zhang H, Liu X (2003) Study on the mechanism of chiral recognition with molecularly imprinted polymers. Anal Chim Acta 489(489):33–43CrossRefGoogle Scholar
  6. 6.
    Yoshida M, Hatate Y, Uezu K, Goto M (2000) Chiral-recognition polymer prepared by surface molecular imprinting technique. Colloids Surf A Physicochem Eng Asp 169:259–269CrossRefGoogle Scholar
  7. 7.
    Lingxin S, Wang X, Lu W, Wu X, Li J (2016) Molecular imprinting : perspectives and applications. Chem Soc Rev 45:2137–2211CrossRefGoogle Scholar
  8. 8.
    Chianella I, Karim K, Piletska EV, Preston C, Piletsky SA (2006) Computational design and synthesis of molecularly imprinted polymers with high binding capacity for pharmaceutical applications-model case: adsorbent for Abacavir. Anal Chim Acta 559(1):73–78CrossRefGoogle Scholar
  9. 9.
    Karim K, Breton F, Rouillon R, Piletska EV, Guerreiro A, Chianella I, Piletsky SA (2005) How to find effective functional monomers for effective molecularly imprinted polymers? Adv Drug Deliv Rev 57(12):1795–1808CrossRefGoogle Scholar
  10. 10.
    Spivak DA (2005) Optimization , evaluation , and characterization of molecularly imprinted polymers B. Adv Drug Deliv Rev 57:1779–1794CrossRefGoogle Scholar
  11. 11.
    Fu Y, Chen Q, Zhou J, Han Q, Wang Y (2012) Enantioselective recognition of Mandelic acid based on c -globulin modified glassy carbon electrode. Anal Biochem 421(1):103–107CrossRefGoogle Scholar
  12. 12.
    Hwang C (2005) Molecular recognition properties of mandelic acid by using molecularly imprinted polymer. J Appl Polym SciGoogle Scholar
  13. 13.
    Bai L, Chen X, Huang Y (2013) Chiral separation of racemic Mandelic acids by use of an ionic liquid-mediated imprinted monolith with a metal ion as self-assembly pivot. Anal Bioanal Chem 405:8935–8943CrossRefGoogle Scholar
  14. 14.
    Zhou J, Liu Q, Fu G, Zhang Z (2013) Separation of Mandelic acid and its derivatives with new immobilized cellulose chiral stationary phase. Zhou al. / J Zhejiang Univ-Sci B (Biomed Biotechnol) Press J. Zhejiang Univ. B (Biomedicine Biotechnol. 1–6Google Scholar
  15. 15.
    Mao S, Zhang Y, Rohani S, Ray AK (2012) Chromatographic Resolution and Isotherm Determination of ( R , S ) -Mandelic Acid on Chiralcel-OD Column. 2273–2281Google Scholar
  16. 16.
    Kan X, Zhao Y, Geng Z, Wang Z, Zhu J (2008) Composites of multiwalled carbon nanotubes and molecularly imprinted polymers for dopamine recognition. J Phys Chem C 112:4849–4854CrossRefGoogle Scholar
  17. 17.
    Xu L, Xu Z (2012) Molecularly imprinted polymer based on multiwalled carbon nanotubes for ribavirin recognition. J Polym Res 19:1–6CrossRefGoogle Scholar
  18. 18.
    Rezaei B, Rahmanian O (2012) Direct Nanolayer preparation of molecularly imprinted polymers immobilized on multiwalled carbon nanotubes as a surface-recognition sites and their characterization. J Appl Polym Sci 125:798–803CrossRefGoogle Scholar
  19. 19.
    Scida K, Stege PW, Haby G, Messina GA, García CD (2011) Recent applications of carbon-based nanomaterials in analytical chemistry : critical review. Anal Chim Acta 691(1–2):6–17CrossRefGoogle Scholar
  20. 20.
    Wang S (2009) Optimum degree of functionalization for carbon nanotubes. Curr Appl Phys 9(5):1146–1150CrossRefGoogle Scholar
  21. 21.
    Wackerlig J, Schirhagl R Applications of molecularly imprinted polymer nanoparticles and their advances toward industrial use: a review. Anal Chem 88:250–261CrossRefGoogle Scholar
  22. 22.
    Meng L, Fu C, Lu Q (2009) Advanced technology for functionalization of carbon nanotubes. Prog Nat Sci 19(7):801–810CrossRefGoogle Scholar
  23. 23.
    Han Z, Fina A (2011) Progress in polymer science thermal conductivity of carbon nanotubes and their polymer nanocomposites : a review. Prog Polym Sci 36(7):914–944CrossRefGoogle Scholar
  24. 24.
    Zhang X, Zhang Y, Yin X, Du B, Zheng C, Yang HA (2013) Facile approach for preparation of molecularly imprinted polymers layer on the surface of carbon nanotubes. Talanta 105:403–408CrossRefGoogle Scholar
  25. 25.
    Hone J (2004) Carbon nanotubes : thermal properties. Dekker Encycl Nanosci Nanotechnolog:603–611Google Scholar
  26. 26.
    Senger RT (2004) Functionalized carbon nanotubes and device applications. J Phys Condens MATTER 16:901–960CrossRefGoogle Scholar
  27. 27.
    Valle M, Pumera M, Llopis X, Pe B (2005) New materials for electrochemical sensing VI : carbon nanotubes. Trends Anal Chem 24(9):826–838CrossRefGoogle Scholar
  28. 28.
    Belin T, Epron F (2005) Characterization methods of carbon nanotubes : a review. Mater Sci Eng B 119:105–118CrossRefGoogle Scholar
  29. 29.
    Iijima S (2006) Carbon nanotubes. Electrochem Soc Interface:23–26Google Scholar
  30. 30.
    Yang W, Thordarson P, Gooding JJ, Ringer SP, Braet F (2007) Carbon nanotubes for biological and biomedical applications. Nanotechnology 18:412001CrossRefGoogle Scholar
  31. 31.
    Xu L, Xu Z (2012) Molecularly imprinted polymer based on multiwalled carbon nanotubes for ribavirin recognition. J Polym Res 19(8):9942CrossRefGoogle Scholar
  32. 32.
    Rosca ID (2005) Oxidation of multiwalled carbon nanotubes by nitric acid. Carbon N Y 43:3124–3131CrossRefGoogle Scholar
  33. 33.
    Polimer P, Molekul C (2010) Synthesis and characterization of a molecularly imprinted polymer for Pb 2 + uptake using 2-Vinylpyridine as the complexing monomer. Sains Malaysiana 39(5):829–835Google Scholar
  34. 34.
    Zhang W, Li Q, Cong J, Wei B, Wang S (2018) Mechanism analysis of selective adsorption and specific recognition by molecularly imprinted polymers of Ginsenoside Re. Polymers (Basel) 10(216)CrossRefGoogle Scholar
  35. 35.
    Zhang H, Zhang Z, Hu Y, Yang X, Yao S (2011) Synthesis of a novel composite imprinted material based on multiwalled carbon nanotubes as a selective melamine absorbent. J Agric Food Chem 59:1063–1071CrossRefGoogle Scholar
  36. 36.
    Zakaria ND, Yusof NA, Haron J, Abdullah AH (2009) Synthesis and evaluation of a molecularly imprinted polymer. Int J Mol Sci 10(1):354–365CrossRefGoogle Scholar
  37. 37.
    Mahanandia P, Vishwakarma PN, Nanda KK, Prasad V (2006) Multiwall carbon nanotubes from pyrolysis of tetrahydrofuran. Mater Res Bull 41(41):2311–2317CrossRefGoogle Scholar
  38. 38.
    Panahi R, Vasheghani-farahani E, Shojaosadati SA (2008) Determination of adsorption isother for L-lysine imprinted polymer. Iran J Chem Eng Chem Eng 5(4)Google Scholar

Copyright information

© The Polymer Society, Taipei 2019

Authors and Affiliations

  1. 1.Research & Post Graduate Department of Chemistry, St Berchmans Autonomous CollegeAffiliated to Mahatma Gandhi UniversityKottayamIndia
  2. 2.Research & Post Graduate Department of Chemistry, St Thomas CollegeAffiliated to Mahatma Gandhi UniversityPalaIndia
  3. 3.School of Chemical SciencesMahatma Gandhi UniversityKottayamIndia

Personalised recommendations