pp 1–14 | Cite as

Temperature/pH dual sensitive Hericium erinaceus residue carboxymethyl chitin/poly (N-isopropyl acrylamide) sequential IPN hydrogels

  • Jing Liao
  • Huihua HuangEmail author
Original Research


In this study, a novel temperature/pH dual responsive hydrogel, based on Hericium erinaceus residue carboxymethyl chitin (HCMC) and poly (N-isopropylacrylamide) (PNIPAm), was synthesized by sequential IPN technique. Series of IPN hydrogels were obtained by varying initial N-isopropylacrylamide (NIPAm) concentrations. The structure, morphology, thermal property, transparency, mechanical property, swelling kinetics, temperature/pH responses and 5-Fu release behavior of the prepared hydrogels were systematically investigated. The structure analysis results showed that the IPN hydrogels were successfully synthesized. The prepared hydrogels showed more compact network structure and enhanced mechanical property as NIPAm concentration increased, but reduced transparency, swelling degree and 5-Fu release ratio. More importantly, HCMC and PNIPAm ensured the pH and temperature responses, respectively. 5-Fu could be gradually released from the prepared hydrogels, which followed Fickian diffusion model. Therefore, the prepared hydrogels may be served as promising materials for drug delivery systems.


Hericium erinaceus residue Carboxymethyl chitin Poly (N-isopropylacrylamide) IPN hydrogel Temperature/pH response 



This work is supported by National Natural Science Foundation of China under Grant Nos. 31471673 and 31271978.

Supplementary material

10570_2019_2837_MOESM1_ESM.docx (374 kb)
Supplementary material 1 (DOCX 374 kb)


  1. Azarova YA, Pestov AV, Bratskaya SY (2016) Application of chitosan and its derivatives for solid-phase extraction of metal and metalloid ions: a mini-review. Cellulose 23:2273–2289CrossRefGoogle Scholar
  2. Bilbao-Sainz C, Chiou BS, Williams T, Wood D, Du WX, Sedej I et al (2017) Vitamin D-fortified chitosan films from mushroom waste. Carbohydr Polym 167:97–104PubMedCrossRefPubMedCentralGoogle Scholar
  3. Chen JP, Cheng TH (2006) Thermo-responsive chitosan-graft-poly (N-isopropylacrylamide) injectable hydrogel for cultivation of chondrocytes and meniscus cells. Macromol Biosci 6:1026–1039PubMedCrossRefPubMedCentralGoogle Scholar
  4. Chien RC, Yen MT, Mau JL (2016) Antimicrobial and antitumor activities of chitosan from shiitake stipes, compared to commercial chitosan from crab shells. Carbohydr Polym 138:259–264PubMedCrossRefPubMedCentralGoogle Scholar
  5. Clarke DE, Pashuck ET, Bertazzo S, Weaver JVM, Stevens MM (2017) Selfhealing, self-assembled beta-sheet peptide-poly(gamma-glutamic acid) hybrid hydrogels. J Am Chem Soc 139:7250–7255PubMedPubMedCentralCrossRefGoogle Scholar
  6. Croisier F, Jérôme C (2013) Chitosan-based biomaterials for tissue engineering. Eur Polym J 49:780–792CrossRefGoogle Scholar
  7. Dai H, Ou S, Liu Z, Huang H (2017) Pineapple peel carboxymethyl cellulose/polyvinyl alcohol/mesoporous silica SBA-15 hydrogel composites for papain immobilization. Carbohydr Polym 169:504–514PubMedCrossRefGoogle Scholar
  8. Dai H, Ou S, Huang Y, Liu Z, Huang H (2018a) Enhanced swelling and multiple-responsive properties of gelatin/sodium alginate hydrogels by the addition of carboxymethyl cellulose isolated from pineapple peel. Cellulose 25:593–606CrossRefGoogle Scholar
  9. Dai H, Huang Y, Huang H (2018b) Eco-friendly polyvinyl alcohol/carboxymethyl cellulose hydrogels reinforced with graphene oxide and bentonite for enhanced adsorption of methylene blue. Carbohydr Polym 185:1–11PubMedCrossRefGoogle Scholar
  10. Dai H, Zhang Y, Ma L, Zhang H, Huang H (2019a) Synthesis and response of pineapple peel carboxymethyl cellulose-g-poly (acrylic acid-co-acrylamide)/graphene oxide hydrogels. Carbohydr Polym 215:366–376PubMedCrossRefPubMedCentralGoogle Scholar
  11. Dai H, Zhang H, Ma L, Zhou HY, Yu Y, Guo T, Zhang Y, Huang H (2019b) Green pH/magnetic sensitive hydrogels based on pineapple peel cellulose and polyvinyl alcohol: synthesis, characterization and naringin prolonged release. Carbohydr Polym 209:51–61PubMedCrossRefPubMedCentralGoogle Scholar
  12. Dragan ES, Lazar MM, Dinu MV (2012) Preparation and characterization of IPN composite hydrogels based on polyacrylamide and chitosan and their interaction with ionic dyes. Carbohydr Polym 88:270–281CrossRefGoogle Scholar
  13. Gao XY, Cao Y, Song XF, Zhang Z, Xiao CS, He CL, Chen XS (2013) pH and thermo-responsive poly(N-isopropylacrylamide-co-acrylic acid derivative) copolymers and hydrogels with LCST dependent on pH and alkyl side groups. J Mater Chem B 1:5578–5587CrossRefGoogle Scholar
  14. Gharekhani H, Olad A, Mirmohseni A, Bybordi A (2017) Superabsorbent hydrogel made of NaAlg-g-poly(AA-co-AAm) and rice husk ash: synthesis, characterization, and swelling kinetic studies. Carbohydr Polym 168:1–13PubMedCrossRefPubMedCentralGoogle Scholar
  15. Guo Y, Duan B, Cui L, Zhu P (2015) Construction of chitin/graphene oxide hybrid hydrogels. Cellulose 22:2035–2043CrossRefGoogle Scholar
  16. Haq MA, Su Y, Wang D (2017) Mechanical properties of PNIPAM based hydrogels: a review. Mater Sci Eng C 70:842–855CrossRefGoogle Scholar
  17. Higuchi T (1963) Mechanism of sustained action medication: theoretical analysis of rate of release of solid drugs dispersed in solid matrices. J Pharm Sci 52:1145–1149PubMedCrossRefPubMedCentralGoogle Scholar
  18. Hirokawa Y, Tanaka T (1984) Volume phase transition in a nonionic gel. J Chem Phys 81:6379–6380CrossRefGoogle Scholar
  19. Hong S, Yang QR, Yuan Y, Chen L, Song YD, Lian HL (2019) Sustainable co-solvent induced one step extraction of low molecular weight chitin with high purity from raw lobster shell. Carbohydr Polym 205:236–243PubMedCrossRefGoogle Scholar
  20. Jaiswal MK, Banerjee R, Pradhan P, Bahadur D (2010) Thermal behavior of magnetically modalized poly(n-isopropylacrylamide)-chitosan based nanohydrogel. Colloids Surf B 81:185–194CrossRefGoogle Scholar
  21. Jalababu R, Veni SS, Reddy KVNS (2018) Synthesis and characterization of dual responsive sodium alginate-g-acryloyl phenylalanine-poly n-isopropyl acrylamide smart hydrogels for the controlled release of anticancer drug. J Drug Deliv Sci Technol 44:190–204CrossRefGoogle Scholar
  22. Karimi M, Ghasemi A, Zangabad PS, Rahighi R, Moosavi Basri SM, Mirshekari H et al (2016) Smart micro/nano particles in stimulus-responsive drug/gene delivery systems. Chem Soc Rev 45:1457–1501PubMedPubMedCentralCrossRefGoogle Scholar
  23. Kim SW, Bae YH, Okano T (1992) Hydrogels: swelling, drug loading, and release. Pharm Res 9:283–290PubMedCrossRefGoogle Scholar
  24. Korsmeyer RW, Gurny R, Doelker E, Buri P, Peppas NA (1983) Mechanisms of solute release from porous hydrophilic polymers. Int J Pharm 15:25–35CrossRefGoogle Scholar
  25. Liao J, Huang H (2019a) Green magnetic hydrogels synthesis, characterization and flavourzyme immobilization based on chitin from Hericium erinaceus residue and polyvinyl alcohol. Int J Biol Macromol 138:462–472PubMedCrossRefGoogle Scholar
  26. Liao J, Huang HH (2019b) Magnetic chitin hydrogels prepared from Hericium erinaceus residues with tunable characteristics: a novel biosorbent for Cu2+ removal. Carbohydr Polym 220:191–201PubMedCrossRefGoogle Scholar
  27. Lima BV, Vidal RR, Marques ND, Maia AM, Balaban RD (2012) Temperature-induced thickening of sodium carboxymethylcellulose and poly(n-isopropylacrylamide) physical blends in aqueous solution. Polym Bull 69:1093–1101CrossRefGoogle Scholar
  28. Lin X, Ju X, Xie R, Jiang M, Wei J, Chu L (2013) Halloysite nanotube composited thermoresponsive hydrogel system for controlled-release. Chin J Chem Eng 21:991–998CrossRefGoogle Scholar
  29. Liu Z, Huang H (2016) Preparation and characterization of cellulose composite hydrogels from tea residue and carbohydrate additives. Carbohydr Polym 147:226–233PubMedCrossRefGoogle Scholar
  30. Liu J, Liu G, Liu W (2014) Preparation of water-soluble β-cyclodextrin/poly(acrylic acid)/graphene oxide nanocomposites as new adsorbents to remove cationic dyes from aqueous solutions. Chem Eng J 257:299–308CrossRefGoogle Scholar
  31. Liu H, Yang Q, Zhang L, Zhuo R, Jiang X (2016) Synthesis of carboxymethyl chitin in aqueous solution and its thermo- and ph-sensitive behaviors. Carbohydr Polym 137:600–607PubMedCrossRefPubMedCentralGoogle Scholar
  32. Liu CM, Guo XJ, Liang RH, Liu W, Chen J (2017a) Alkylated pectin: molecular characterization, conformational change and gel property. Food Hydrocolloids 69:341–349CrossRefGoogle Scholar
  33. Liu Z, Li D, Dai H, Huang H (2017b) Preparation and characterization of papain embedded in magnetic cellulose hydrogels prepared from tea residue. J Mol Liq 232:449–456CrossRefGoogle Scholar
  34. Lv JH, Sun B, Jin J, Jiang W (2019) Mechanical and slow-released property of poly(acrylamide) hydrogel reinforced by diatomite. Mater Sci Eng C 99:315–321CrossRefGoogle Scholar
  35. Ma J, Xu Y, Fan B, Liang B (2007) Preparation and characterization of sodium carboxymethylcellulose/poly(n-isopropylacrylamide)/clay semi-ipn nanocomposite hydrogels. Eur Polym J 43:2221–2228CrossRefGoogle Scholar
  36. Munoz G, Valencia C, Valderruten N, Ruiz-Durantez E, Zuluaga F (2015) Extraction of chitosan from Aspergillus niger mycelium and synthesis of hydrogels for controlled release of betahistine. React Funct Polym 91–92:1–10CrossRefGoogle Scholar
  37. Pan YF, Wang JC, Cai PX, Xiao HN (2018) Dual-responsive IPN hydrogel based on sugarcane bagasse cellulose as drug carrier. Int J Biol Macromol 118:132–140PubMedCrossRefPubMedCentralGoogle Scholar
  38. Roland CM (2013) Interpenetrating Polymer Networks (IPN): structure and mechanical behavior. In: Kobayashi S, Müllen K (eds) Encyclopedia of polymeric nanomaterials. Springer, BerlinGoogle Scholar
  39. Sun XF, Zeng Q, Wang H, Hao Y (2019) Preparation and swelling behavior of ph/temperature responsive semi-IPN hydrogel based on carboxymethyl xylan and poly(n-isopropyl acrylamide). Cellulose 26:1909–1922CrossRefGoogle Scholar
  40. Wei QB, Luo YL, Fu F, Zhang YQ, Ma RX (2013) Synthesis, characterization, and swelling kinetics of pH-responsive and temperature-responsive carboxymethyl chitosan/polyacrylamide hydrogels. J Appl Polym Sci 129:806–814CrossRefGoogle Scholar
  41. Wei W, Qi X, Liu Y, Li J, Hu X, Zuo G, Zhang J, Dong W (2015) Synthesis and characterization of a novel pH-thermo dual responsive hydrogel based on salecan and poly (N, N-diethylacrylamide-co-methacrylic acid). Colloids Surf B 136:1182–1192CrossRefGoogle Scholar
  42. Wu T, Zivanovic S, Draughon FA, Sams CE (2004) Chitin and chitosan-value-added products from mushroom waste. J Agric Food Chem 52:7905–7910PubMedCrossRefGoogle Scholar
  43. Yang X, Nisar T, Liang D, Hou Y, Guo Y (2018) Low methoxyl pectin gelation under alkaline conditions and its rheological properties: using NaOH as a pH regulator. Food Hydrocolloids 79:560–571CrossRefGoogle Scholar
  44. Yen MT, Mau JL (2007) Selected physical properties of chitin prepared from shiitake stipes. LWT Food Sci Technol 40:558–563CrossRefGoogle Scholar
  45. Yuan Y, Wang L, Mu RJ, Gong J, Wang Y, Li Y et al (2018) Effects of konjac glucomannan on the structure, properties, and drug release characteristics of agarose hydrogels. Carbohydr Polym 190:196–203PubMedCrossRefGoogle Scholar
  46. Zhang X, Yang P, Dai Y, Ma P, Li X, Cheng Z et al (2013) Drug delivery: multifunctional up-converting nanocomposites with smart polymer brushes gated mesopores for cell imaging and thermo/pH dual-responsive drug controlled release. Adv Funct Mater 23:4062CrossRefGoogle Scholar
  47. Zhang L, Wang L, Guo B, Ma PX (2014) Cytocompatible injectable carboxymethyl chitosan/N-isopropylacrylamide hydrogels for localized drug delivery. Carbohydr Polym 103:110–118PubMedCrossRefGoogle Scholar
  48. Zhuo RX, Li W (2003) Preparation and characterization of macroporous poly(-isopropylacrylamide) hydrogels for the controlled release of proteins. J Polym Sci A Polym Chem 41:152–159CrossRefGoogle Scholar

Copyright information

© Springer Nature B.V. 2019

Authors and Affiliations

  1. 1.School of Food Science and EngineeringSouth China University of TechnologyGuangzhouChina

Personalised recommendations