Polymer Bulletin

, Volume 76, Issue 6, pp 3073–3092 | Cite as

Synthesis and characterization of stimuli-responsive hydrogel based on starch and methyl-3-aminocrotonate: swelling and degradation kinetics

  • Muhammad Aslam MalanaEmail author
  • Faryal Aftab
  • Syeda Rabia Batool
Original Paper


Focus of the present studies was to synthesize a novel pH sensitive and thermoresponsive hydrogel which may show swelling behavior suitable for drug delivery at colon part of body. For this purpose, starch was copolymerized with methyl-3-aminocrotonate through free radical polymerization. The structural and thermal characterization of wheat starch/methyl-3-aminocrotonate hydrogel was carried out by XRD, FTIR and TGA. FTIR and XRD confirmed successful formation of the gel. Thermal data were further subjected to the isoconversional method for the determination of kinetic triplet (activation energy Ea, frequency factor A and g(α) function) to predict mechanism for thermal degradation of the synthesized gel. The first step showed a complex mechanism of thermal degradation, i.e., A2 followed by A3/2. Thermodynamic parameters ΔS* and ΔG* were also calculated. Moreover, swelling investigations unveiled these gels to be pH sensitive and thermoresponsive. The swelling percentage markedly increased with increasing pH and temperature. Kinetic order of swelling, diffusion mechanism and network parameters (i.e., molecular weight between cross-links and volume faction of polymers) of the synthesized hydrogel was also determined.


Swelling kinetics Starch-based hydrogels Isoconversional method Stimuli-responsive hydrogel Methyl-3-aminocrotonate 


  1. 1.
    Xavier JR, Thakur T, Desai P, Jaiswal MK, Sears N, Cosgriff-Hernandez E, Kaunas R, Gaharwar AK (2015) Bioactive nanoengineered hydrogels for bone tissue engineering: a growth-factor-free approach. ACS Nano 9:3109–3118. CrossRefGoogle Scholar
  2. 2.
    Ahmed EM (2015) Hydrogel: preparation, characterization, and applications: a review. J Adv Res 6:105–121. CrossRefGoogle Scholar
  3. 3.
    Zhou T, Wang Y, Huang S, Zhao Y (2018) Synthesis composite hydrogels from inorganic-organic hybrids based on leftover rice for environment-friendly controlled-release urea fertilizers. Sci Total Environ 615:422–430. CrossRefGoogle Scholar
  4. 4.
    Zhou G, Luo J, Liu C, Chu L, Ma J, Tang Y, Zeng Z, Luo S (2016) A highly efficient polyampholyte hydrogel sorbent based fixed-bed process for heavy metal removal in actual industrial effluent. Water Res 89:151–160. CrossRefGoogle Scholar
  5. 5.
    Hu H, Xin JH, Hu H (2014) PAM/graphene/Ag ternary hydrogel: synthesis, characterization and catalytic application. J Mater Chem A 2:11319–11333. CrossRefGoogle Scholar
  6. 6.
    Niranjana PT, Prashantha K (2016) A review on present status and future challenges of starch based polymer films and their composites in food packaging applications. Polym Compos. Google Scholar
  7. 7.
    Woo K, Seib PA (1997) Cross-linking of wheat starch and hydroxypropylated wheat starch in alkaline slurry with sodium trimetaphosphate. Carbohydr Polym 33:263–271.,00037-4 CrossRefGoogle Scholar
  8. 8.
    Sulaiman NS, Hashim R, Hiziroglu S, Amini MHM, Sulaiman O, Ezwanselamat M (2016) rubberwood particleboard manufactured using epichlorohydrin-modified rice starch as a binder. Cellul Chem Technol 50:329–338Google Scholar
  9. 9.
    Gui-Jie M, Peng W, Xiang-Sheng M, Xing Z, Tong Z (2006) Crosslinking of corn starch with sodium trimetaphosphate in solid state by microwave irradiation. J Appl Polym Sci 102:5854–5860. CrossRefGoogle Scholar
  10. 10.
    El-Tahlawy K, Venditti RA, Pawlak JJ (2007) Aspects of the preparation of starch microcellular foam particles crosslinked with glutaraldehyde using a solvent exchange technique. Carbohydr Polym 67:319–331. CrossRefGoogle Scholar
  11. 11.
    Singh B, Khurana RK, Garg B, Saini S, Kaur R (2017) Stimuli-responsive systems with diverse drug delivery and biomedical applications: recent updates and mechanistic pathways. Crit Rev Ther Drug Carrier Syst 34. pubmed/28845760Google Scholar
  12. 12.
    Bates FL, French D, Rundle RE (1943) Amylose and amylopectin content of starches determined by their iodine complex formation. J Am Chem Soc 65:142–148. CrossRefGoogle Scholar
  13. 13.
    Perez LAB, Agama-Acevedo E (2018) Starch. Starch based Mater Food Packag. Google Scholar
  14. 14.
    Liang R, Yuan H, Xi G, Zhou Q (2009) Synthesis of wheat straw-g-poly (acrylic acid) superabsorbent composites and release of urea from it. Carbohydr Polym 77:181–187. CrossRefGoogle Scholar
  15. 15.
    Koh JJ, Zhang X, He C (2017) Fully biodegradable poly (lactic acid)/starch blends: a review of toughening strategies. Int J Biol Macromol. Google Scholar
  16. 16.
    Otey FH, Westhoff RP, Russell CR (1976) Starch graft copolymers-degradable fillers for poly (vinyl chloride) plastics. Ind Eng Chem Product Res Dev 15:139–142CrossRefGoogle Scholar
  17. 17.
    Morita I et al (1987) Synthesis and antihypertensive activities of 1, 4-dihydropyridine-5-phosphonate derivatives. II. Chem Pharm Bull 35:4144–4154. CrossRefGoogle Scholar
  18. 18.
    Zhou K, Wang XM, Zhao YZ, Cao YX, Fu Q, Zhang SQ (2011) Synthesis and antihypertensive activity evaluation in spontaneously hypertensive rats of nitrendipine analogues. Med Chem Res 20(8):1325–1330. CrossRefGoogle Scholar
  19. 19.
    Chiang CL, Chang RC, Chiu YC (2007) Thermal stability and degradation kinetics of novel organic/inorganic epoxy hybrid containing nitrogen/silicon/phosphorus by sol–gel method. Thermochim Acta 453:97–104. CrossRefGoogle Scholar
  20. 20.
    Chiang CL, Ma CCM (2002) Synthesis, characterization and thermal properties of novel epoxy containing silicon and phosphorus nanocomposites by sol–gel method. Eur Polym J 38:2219–2224.,00123-4 CrossRefGoogle Scholar
  21. 21.
    Omrani A, Rostami AA, Sedaghat E (2010) Kinetics of cure for a coating system including DGEBA (n = 0)/1, 8-NDA and barium carbonate. Thermochim Acta 497:21–26. CrossRefGoogle Scholar
  22. 22.
    Fanta GF et al (1966) Graft copolymers of starch. I. Copolymerization of gelatinized wheat starch with acrylonitrile. Fractionation of copolymer and effect of solvent on copolymer composition. J. Appl Polym Sci 10(6):929–937. CrossRefGoogle Scholar
  23. 23.
    Lanthong P, Nuisin R, Kiatkamjornwong S (2006) Graft copolymerization, characterization, and degradation of cassava starch-g-acrylamide/itaconic acid superabsorbents. Carbohydr Polym 66:229–245. CrossRefGoogle Scholar
  24. 24.
    Wang Y, Zhang L, Li X, Gao W (2011) Physicochemical properties of starches from two different yam (Dioscorea opposita Thunb.) residues. Braz Arch Biol Technol 54:243–251. CrossRefGoogle Scholar
  25. 25.
    Fares MM, El-faqeeh AS, Osman ME (2003) Graft copolymerization onto starch–I. Synthesis and optimization of starch grafted with N-tert-butylacrylamide copolymer and its hydrogels. J Polym Res 10:119–125. CrossRefGoogle Scholar
  26. 26.
    Akbar J, Iqbal MS, Massey S, Masih R (2012) Kinetics and mechanism of thermal degradation of pentose-and hexose-based carbohydrate polymers. Carbohydr Polym 90:1386–1393. CrossRefGoogle Scholar
  27. 27.
    Senum GI, Yang RT (1977) Rational approximations of the integral of the Arrhenius function. J Therm Anal 11:445–447. CrossRefGoogle Scholar
  28. 28.
    Coats AW, Redfern JP (1964) Kinetic parameters from thermogravimetric data. Nature 201:68. CrossRefGoogle Scholar
  29. 29.
    Vlaev L, Nedelchev N, Gyurova K, Zagorcheva A (2008) A comparative study of non-isothermal kinetics of decomposition of calcium oxalate monohydrate. J Anal Appl Pyrolysis 81:253–262. CrossRefGoogle Scholar
  30. 30.
    Bamford CH, Tipper CFH, Compton RG (1986) Electrode kinetics: principles and methodology, vol 26. Elsevier, AmsterdamGoogle Scholar
  31. 31.
    Georgieva V, Zvezdova D, Vlaev L (2013) Non-isothermal kinetics of thermal degradation of chitin. J Therm Anal Calorim 111:763–771. CrossRefGoogle Scholar
  32. 32.
    Liu J, Li Q, Su Y, Yue Q, Gao B (2014) Characterization and swelling–deswelling properties of wheat straw cellulose based semi-IPNs hydrogel. Carbohydr Polym 107:232–240. CrossRefGoogle Scholar
  33. 33.
    Hiremath JN, Vishalakshi B (2012) Effect of crosslinking on swelling behaviour of IPN hydrogels of Guar Gum and Polyacrylamide. Der Pharma Chem 4: 946–955. ISSN 0975-413XGoogle Scholar
  34. 34.
    Anirudhan TS, Parvathy J (2014) Novel semi-IPN based on crosslinked carboxymethyl starch and clay for the in vitro release of theophylline. Inter J Biol Macromol 67:238–245. CrossRefGoogle Scholar
  35. 35.
    Peppas NA, Bures P, Leobandung W, Ichikawa H (2000) Hydrogels in pharmaceutical formulations. Eur J Pharm Biopharm 50:27–46.,00090-4 CrossRefGoogle Scholar
  36. 36.
    Karadag E, Saraydin D (1995) Swelling of acrylamide-tartaric acid hydrogels. Iran J Polym, Sci Technol, p 4Google Scholar
  37. 37.
    Ritger PL, Peppas NA (1987) A simple equation for description of solute release II. Fickian and anomalous release from swellable devices. J Control Release 5:37–42.,90035-6 CrossRefGoogle Scholar
  38. 38.
    Yarimkaya S, Basan H (2007) Swelling behavior of poly (2-hydroxyethyl methacrylate-co-acrylic acid-co-ammonium acrylate) hydrogels. J Macromol Sci Part A Pure Appl Chem 44:939–946. CrossRefGoogle Scholar
  39. 39.
    Ding ZY, Aklonis JJ, Salovey R (1991) Model filled polymers. VI. Determination of the crosslink density of polymeric beads by swelling. J Polym Sci Part B Polym Phys 29:1035–1038. CrossRefGoogle Scholar
  40. 40.
    Flory PJ, Rehner JJ (1943) Statistical mechanics of cross-linked polymer networks II. Swelling. J Chem Phys 11:512–520. CrossRefGoogle Scholar
  41. 41.
    Sohail K, Khan IU, Shahzad Y, Hussain T, Ranjha NM (2014) pH-sensitive polyvinylpyrrolidone-acrylic acid hydrogels: impact of material parameters on swelling and drug release. Braz J Pharm Sci 50(1):173–184. CrossRefGoogle Scholar
  42. 42.
    Wong RSH, Ashton M, Dodou K (2015) Effect of crosslinking agent concentration on the properties of unmedicated hydrogels. Pharmaceutics 7(3):305–319. CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  • Muhammad Aslam Malana
    • 1
    Email author
  • Faryal Aftab
    • 1
  • Syeda Rabia Batool
    • 1
  1. 1.Institute of Chemical SciencesBahauddin Zakariya UniversityMultanPakistan

Personalised recommendations