, Volume 25, Issue 5, pp 3163–3178 | Cite as

Seeking the lowest phase transition temperature in a cellulosic system for textile applications

  • Sandra Cerqueira Barros
  • Maria Manuela Silva
Original Paper


Smart or intelligent polymeric materials respond to small changes in their environment with a considerable change in their physicochemical properties. Environmentally responsive hydrogels have the capability to turn from solution to gel, when a specific stimulus like temperature, pH, chemicals, ultrasounds, light, electric fields and mechanical stress, is applied. Cellulose esters thermoreversible hydrogels, like HPMC, MC and NaCMC, are very appealing once they are naturally derived from cellulose, which is the most abundant naturally occurring biopolymer on earth. Allied to this advantage it is also associated the non-toxicity, biocompatibility, biodegradability and eco-friendly properties. The transition temperature of the abovementioned cellulose derivatives is medium/high (82.5, 67.5 and 47.5 °C) that is considerable elevated for most biochemical and textile applications. Therefore, within this research it is reported a systematic study to depress the gelation temperature of the cellulosic NaCMC. Several factors may influence sol–gel transition temperature of this cellulosic but herein the focus stood on the influence of polymer concentration, of admixing inorganic salts (NaCl and enriched salt solutions), polyols (glycerol) and polyols salts (Na/CaGlyPhos) and lastly the interaction with polyelectrolytes (CH–NaGlyPhos). The aforementioned modifications were afterward registered by UV–Vis spectroscopy. For the developed stimuli sensitive hydrogels it is envisioned the application on the textile materials, more specifically in the delivery of active species (e.g., scents, moisturizers, antiperspirants)/perspiration absorption, through textile apparel. The system will be triggered by human body temperature and thus a thermogelation temperature of 28–35 °C (skin-cloths microclimate temperature) is compulsory.


LCST Sodium carboxymethyl cellulose Chitosan Glycerol phosphate disodium salt Glycerol 





Hydroxypropylmethyl cellulose


Methyl cellulose


Sodium carboxymethyl cellulose


Lower critical solution temperature


Ultraviolet–visible spectroscopy


Attenuated total reflectance Fourier transformed infrared spectroscopy


Differential scanning calorimetry


Solution that mimics human perspiration


Glycerol phosphate disodium salt


Glycerol phosphate calcium salt



The authors thankfully acknowledge the funding from the Chemistry Centre at Minho University (Pest-C/QUI/UI0686/2013, UID/QUI/0686/2016), and the Portuguese Foundation for Science and Technology (FCT) and the Human Capital Operational Program (POCH), for the Post-Doc grant assigned to Sandra Cerqueira Barros (SFRH/BPD/85399/2012). The researchers involved in this work are also grateful to the Company Devan-Micropolis, S.A., for the supply of the biopolymers hydroxypropylmethyl cellulose (HPMC), methyl cellulose (MC) and sodium carboxymethyl cellulose (NaCMC), applied within this research work.


  1. Aguilar MR, Elvira C, Gallardo A, Vázquez B, Román JS (2007) Smart polymers and their applications as biomaterials.
  2. Aliaghaie M, Mirzadeh H, Dashtimoghadam E, Taranejoo S (2012) Investigation of gelation mechanism of an injectable hydrogel based on chitosan by rheological measurements for a drug delivery application. Soft Matter 8:7128–7137. CrossRefGoogle Scholar
  3. Alvarez-Lorenzo C, Blanco-Fernandez B, Puga AM, Concheiro A (2013) Crosslinked ionic polysaccharides for stimuli-sensitive drug delivery. Adv Drug Deliv Rev 65:1148–1171. CrossRefGoogle Scholar
  4. Arvidson SA et al (2013) Interplay of phase separation and thermoreversible gelation in aqueous methylcellulose solutions. Macromolecules 46:300–309. CrossRefGoogle Scholar
  5. Barros SC et al (2014) Thermo-sensitive chitosan-cellulose hydrogels: swelling behaviour and morphologic studies. Cellulose 21:4531–4544. CrossRefGoogle Scholar
  6. Barros S et al (2015) Thermal–mechanical behaviour of chitosan–cellulose derivative thermoreversible hydrogel films. Cellulose 22:1911–1929. CrossRefGoogle Scholar
  7. Bekkour K, Sun-Waterhouse D, Wadhwa SS (2014) Rheological properties and cloud point of aqueous carboxymethyl cellulose dispersions as modified by high or low methoxyl pectin. Food Res Int 66:247–256. CrossRefGoogle Scholar
  8. Benslimane A, Bahlouli IM, Bekkour K, Hammiche D (2016) Thermal gelation properties of carboxymethyl cellulose and bentonite-carboxymethyl cellulose dispersions: Rheological considerations. Appl Clay Sci 132–133:702–710. CrossRefGoogle Scholar
  9. Chan AW, Whitney RA, Neufeld RJ (2009) Semisynthesis of a controlled stimuli-responsive alginate hydrogel. Biomacromol 10:609–616. CrossRefGoogle Scholar
  10. Chang C, Zhang L (2011) Cellulose-based hydrogels: present status and application prospects. Carbohydr Polym 84:40–53. CrossRefGoogle Scholar
  11. Chang C, He M, Zhou J, Zhang L (2011) Swelling behaviors of pH- and salt-responsive cellulose-based hydrogels. Macromolecules 44:1642–1648. CrossRefGoogle Scholar
  12. Chen L, Wang T, Li K (2016a) Preparation of chitosan/hydroxypropyl methyl cellulose thermo-sensitive hydrogel. Gaofenzi Cailiao Kexue Yu Gongcheng/Polym Mater Sci Eng 32:156–161 and 167. Google Scholar
  13. Chen L, Wang T, Li K (2016b) Preparation of chitosan/hydroxypropyl methyl cellulose thermo-sensitive hydrogel. Polym Mater Sci Eng 32:156–161 + 167CrossRefGoogle Scholar
  14. Chenite A et al (2000) Novel injectable neutral solutions of chitosan form biodegradable gels in situ. Biomaterials 21:2155–2161. CrossRefGoogle Scholar
  15. Chenite A, Buschmann M, Wang D, Chaput C, Kandani N (2001) Rheological characterisation of thermogelling chitosan/glycerol-phosphate solutions. Carbohydr Polym 46:39–47. CrossRefGoogle Scholar
  16. Chevillard C, Axelos MAV (1997) Phase separation of aqueous solution of methylcellulose. Colloid Polym Sci 275:537–545. CrossRefGoogle Scholar
  17. Cho J, Heuzey M-C, Bégin A, Carreau PJ (2005) Physical gelation of chitosan in the presence of β-glycerophosphate: the effect of temperature. Biomacromol 6:3267–3275. CrossRefGoogle Scholar
  18. Cho J, Heuzey M-C, Bégin A, Carreau PJ (2006a) Chitosan and glycerophosphate concentration dependence of solution behaviour and gel point using small amplitude oscillatory rheometry. Food Hydrocoll 20:936–945. CrossRefGoogle Scholar
  19. Cho J, Heuzey M-C, Bégin A, Carreau PJ (2006b) Effect of urea on solution behavior and heat-induced gelationof chitosan-β-glycerophosphate. Carbohydr Polym 63:507–518. CrossRefGoogle Scholar
  20. Cho J, Heuzey M-C, Bégin A, Carreau PJ (2006c) Viscoelastic properties of chitosan solutions: effect of concentration and ionic strength. J Food Eng 74:500–515. CrossRefGoogle Scholar
  21. Constantin M, Cristea M, Ascenzi P, Fundueanu G (2011) Lower critical solution temperature versus volume phase transition temperature in thermoresponsive drug delivery systems. Express Polym Lett 5:839–848. CrossRefGoogle Scholar
  22. Corporation O (2010) OriginPro, 8.5.0 SR1 edn, NorthamptonGoogle Scholar
  23. Dang QF, Yan JQ, Li JJ, Cheng XJ, Liu CS, Chen XG (2011) Controlled gelation temperature, pore diameter and degradation of a highly porous chitosan-based hydrogel. Carbohydr Polym 83:171–178. CrossRefGoogle Scholar
  24. Dang QF, Yan JQ, Lin H, Chen XG, Liu CS, Ji QX, Li JJ (2012) Design and evaluation of a highly porous thermosensitive hydrogel with low gelation temperature as a 3D culture system for Penaeus chinensis lymphoid cells. Carbohydr Polym 88:361–368. CrossRefGoogle Scholar
  25. Determan MD, Cox JP, Mallapragada SK (2007) Drug release from pH-responsive thermogelling pentablock copolymers. J Biomed Mater Res Part A 81A:326–333. CrossRefGoogle Scholar
  26. Dhar N, Akhlaghi SP, Tam KC (2012) Biodegradable and biocompatible polyampholyte microgels derived from chitosan, carboxymethyl cellulose and modified methyl cellulose. Carbohydr Polym 87:101–109. CrossRefGoogle Scholar
  27. Douglas TEL et al (2013) Acceleration of gelation and promotion of mineralization of chitosan hydrogels by alkaline phosphatase. Int J Biol Macromol 56:122–132. CrossRefGoogle Scholar
  28. Ford JL (1999) Thermal analysis of hydroxypropylmethylcellulose and methylcellulose: powders, gels and matrix tablets. Int J Pharm 179:209–228. CrossRefGoogle Scholar
  29. French AD (2017) Glucose, not cellobiose, is the repeating unit of cellulose and why that is important. Cellulose 24:4605–4609. CrossRefGoogle Scholar
  30. Heymann E (1935) Studies on sol–gel transformations. I. The inverse sol–gel transformation of methylcellulose in water. Trans Faraday Soc 31:846–864. CrossRefGoogle Scholar
  31. Hoemann CD et al (2007) Cytocompatible gel formation of chitosan-glycerol phosphate solutions supplemented with hydroxyl ethyl cellulose is due to the presence of glyoxal. J Biomed Mater Res Part A 83A:521–529. CrossRefGoogle Scholar
  32. Jafari B, Rafie F, Davaran S (2011) Preparation and characterization of a novel smart polymeric hydrogel for drug delivery of insulin. BioImpacts: BI 1:135–143. Google Scholar
  33. Jeong B, Bae YH, Kim SW (1999) Thermoreversible gelation of PEG − PLGA − PEG triblock copolymer aqueous solutions. Macromolecules 32:7064–7069. CrossRefGoogle Scholar
  34. Jeong B, Kim SW, Bae YH (2002) Thermosensitive sol–gel reversible hydrogels. Adv Drug Deliv Rev 54:37–51. CrossRefGoogle Scholar
  35. Joshi SC (2011) Sol–gel behavior of hydroxypropyl methylcellulose (HPMC) in ionic media including drug release. Materials 4:1861CrossRefGoogle Scholar
  36. Joshi HN, Wilson TD (1993) Calorimetric studies of dissolution of hydroxypropyl methylcellulose E5 (HPMC E5) in water. J Pharm Sci 82:1033–1038. CrossRefGoogle Scholar
  37. Karolewicz B (2016) A review of polymers as multifunctional excipients in drug dosage form technology. Saudi Pharm J 24:525–536. CrossRefGoogle Scholar
  38. Khodaverdi E, Ganji F, Tafaghodi M, Sadoogh M (2013) Effects of formulation properties on sol–gel behavior of chitosan/glycerolphosphate hydrogel. Iran Polym J (Engl Ed) 22:785–790. CrossRefGoogle Scholar
  39. Klouda L, Mikos AG (2008) Thermoresponsive hydrogels in biomedical applications. Eur J Pharm Biopharm 68:34–45. CrossRefGoogle Scholar
  40. Knill CJ, Kennedy JF, Latif Y, Ellwood DC (2002) Effect of metal ions on the rheological flow profiles of hyaluronate solutions. In: Kennedy JFGOP, Williams PA, Hascall VC (eds) Hyaluronan, vol 1: Chemical, Biochemical and Biological Aspects. Woodhead Publishing, Cambridge, pp 175–180. CrossRefGoogle Scholar
  41. Kwon J, Choi J (2013) Clothing insulation and temperature, layer and mass of clothing under comfortable environmental conditions. J Physiol Anthropol 32:11. CrossRefGoogle Scholar
  42. Li L, Shan H, Yue CY, Lam YC, Tam KC, Hu X (2002) Thermally induced association and dissociation of methylcellulose in aqueous solutions. Langmuir 18:7291–7298. CrossRefGoogle Scholar
  43. Liang H-F, Hong M-H, Ho R-M, Chung C-K, Lin Y-H, Chen C-H, Sung H-W (2004) Novel method using a temperature-sensitive polymer (methylcellulose) to thermally gel aqueous alginate as a pH-sensitive hydrogel. Biomacromol 5:1917–1925. CrossRefGoogle Scholar
  44. Liu SQ, Joshi SC, Lam YC, Tam KC (2008) Thermoreversible gelation of hydroxypropylmethylcellulose in simulated body fluids. Carbohydr Polym 72:133–143. CrossRefGoogle Scholar
  45. Liu Y, Geever LM, Kennedy JE, Higginbotham CL, Cahill PA, McGuinness GB (2010) Thermal behavior and mechanical properties of physically crosslinked PVA/Gelatin hydrogels. J Mech Behav Biomed Mater 3:203–209. CrossRefGoogle Scholar
  46. Mohammad MF, Ali AO (2008) Lower critical solution temperature determination of smart, thermosensitive N-isopropylacrylamide-alt-2-hydroxyethyl methacrylate copolymers: Kinetics and physical properties. J Appl Polym Sci 110:2815–2825. CrossRefGoogle Scholar
  47. Nishimura H, Donkai N, Miyamoto T (1997) Temperature-responsive hydrogels from cellulose. Macromol Symp 120:303–313. CrossRefGoogle Scholar
  48. Pandit N, Trygstad T, Croy S, Bohorquez M, Koch C (2000) Effect of salts on the micellization, clouding, and solubilization behavior of pluronic F127 solutions. J Colloid Interf Sci 222:213–220. CrossRefGoogle Scholar
  49. Parkova I, Vilumsone A (2011) Microclimate of smart garment. Mater Sci Text Cloth Technol 6:99–104Google Scholar
  50. Patel A, Mequanint K (2011) Hydrogel biomaterials. Biomed Eng Front Chall. Google Scholar
  51. Roy I, Gupta MN (2003) Smart polymeric materials: emerging biochemical applications. Chem Biol 10:1161–1171. CrossRefGoogle Scholar
  52. Ruel-Gariépy E, Leroux J-C (2004) In situ-forming hydrogels—review of temperature-sensitive systems. Eur J Pharm Biopharm 58:409–426. CrossRefGoogle Scholar
  53. Ruel-Gariépy E, Chenite A, Chaput C, Guirguis S, Leroux JC (2000) Characterization of thermosensitive chitosan gels for the sustained delivery of drugs. Int J Pharm 203:89–98. CrossRefGoogle Scholar
  54. Sammon C, Bajwa G, Timmins P, Melia CD (2006) The application of attenuated total reflectance Fourier transform infrared spectroscopy to monitor the concentration and state of water in solutions of a thermally responsive cellulose ether during gelation. Polymer 47:577–584. CrossRefGoogle Scholar
  55. Sannino A et al (2000) Cellulose-based hydrogels as body water retainers. J Mater Sci Mater Med 11:247–253. CrossRefGoogle Scholar
  56. Sannino A, Demitri C, Madaghiele M (2009) Biodegradable cellulose-based hydrogels: design and applications. Materials 2:353–373. CrossRefGoogle Scholar
  57. Sarkar N (1979) Thermal gelation properties of methyl and hydroxypropyl methylcellulose. J Appl Polym Sci 24:1073–1087. CrossRefGoogle Scholar
  58. Schittek B et al (2001) Dermcidin: a novel human antibiotic peptide secreted by sweat glands. Nat Immunol 2:1133–1137.
  59. Silva SMC, Pinto FV, Antunes FE, Miguel MG, Sousa JJS, Pais AACC (2008) Aggregation and gelation in hydroxypropylmethyl cellulose aqueous solutions. J Colloid Interf Sci 327:333–340. CrossRefGoogle Scholar
  60. Supper S, Anton N, Seidel N, Riemenschnitter M, Schoch C, Vandamme T (2013) Rheological study of chitosan/polyol-phosphate systems: influence of the polyol part on the thermo-induced gelation mechanism. Langmuir 29:10229–10237. CrossRefGoogle Scholar
  61. Supper S, Anton N, Seidel N, Riemenschnitter M, Curdy C, Vandamme T (2014) Thermosensitive chitosan/glycerophosphate-based hydrogel and its derivatives in pharmaceutical and biomedical applications. Expert Opin Drug Deliv 11:249–267. CrossRefGoogle Scholar
  62. Tang Y, Wang X, Li Y, Lei M, Du Y, Kennedy JF, Knill CJ (2010) Production and characterisation of novel injectable chitosan/methylcellulose/salt blend hydrogels with potential application as tissue engineering scaffolds. Carbohydr Polym 82:833–841. CrossRefGoogle Scholar
  63. Taylor DK, Jayes FL, House AJ, Ochieng MA (2011) Temperature-responsive biocompatible copolymers incorporating hyperbranched polyglycerols for adjustable functionality. J Funct Biomater 2:173–194. CrossRefGoogle Scholar
  64. Tong Q, Xiao Q, Lim L-T (2013) Effects of glycerol, sorbitol, xylitol and fructose plasticisers on mechanical and moisture barrier properties of pullulan–alginate–carboxymethylcellulose blend films. Int J Food Sci Technol 48:870–878. CrossRefGoogle Scholar
  65. Van Nieuwenhove I et al (2016) Gelatin- and starch-based hydrogels. Part A: hydrogel development, characterization and coating. Carbohydr Polym 152:129–139. CrossRefGoogle Scholar
  66. Wang Q, Li L, Liu E, Xu Y, Liu J (2006) Effects of SDS on the sol–gel transition of methylcellulose in water. Polymer 47:1372–1378. CrossRefGoogle Scholar
  67. Wang X, Sang L, Luo D, Li X (2011) From collagen–chitosan blends to three-dimensional scaffolds: the influences of chitosan on collagen nanofibrillar structure and mechanical property. Colloid Surf B Biointerfaces 82:233–240. CrossRefGoogle Scholar
  68. Wang T, Chen L, Shen T, Wu D (2016a) Preparation and properties of a novel thermo-sensitive hydrogel based on chitosan/hydroxypropyl methylcellulose/glycerol. Int J Biol Macromol Part A 93:775–782. CrossRefGoogle Scholar
  69. Wang W et al (2016b) Dual-functional transdermal drug delivery system with controllable drug loading based on thermosensitive poloxamer hydrogel for atopic dermatitis treatment. Sci Rep 6:24112. CrossRefGoogle Scholar
  70. Wu Y, Yao J, Zhou J, Dahmani FZ (2013) Enhanced and sustained topical ocular delivery of cyclosporine A in thermosensitive hyaluronic acid-based in situ forming microgels. Int J Nanomed 8:3587–3601. Google Scholar
  71. Xu XM, Song YM, Ping QN, Wang Y, Liu XY (2006) Effect of ionic strength on the temperature-dependent behavior of hydroxypropyl methylcellulose solution and matrix tablet. J Appl Polym Sci 102:4066–4074. CrossRefGoogle Scholar
  72. Yin J, Luo K, Chen X, Khutoryanskiy VV (2006) Miscibility studies of the blends of chitosan with some cellulose ethers. Carbohydr Polym 63:238–244. CrossRefGoogle Scholar
  73. Zarzycki R, Modrzejewska Z, Owczarz P, Wojtasz-Pająk A (2008) New chitisan structures in the form of the thermosensitive gels. Prog Chem Appl Chitin Deriv XIII:35–42Google Scholar
  74. Zhang XH, Li J, Wang YY (2012) Effects of clothing ventilation openings on thermoregulatory responses during exercise. Indian J Fibre Text 37:162–171. Google Scholar
  75. Zhou HY, Jiang LJ, Cao PP, Li JB, Chen XG (2015) Glycerophosphate-based chitosan thermosensitive hydrogels and their biomedical applications. Carbohydr Polym 117:524–536. CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media B.V., part of Springer Nature 2018

Authors and Affiliations

  1. 1.Centro de QuímicaUniversidade do MinhoBragaPortugal
  2. 2.Departamento de QuímicaUniversidade do MinhoBragaPortugal

Personalised recommendations