Abstract
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.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
Abbreviations
- CH:
-
Chitosan
- HPMC:
-
Hydroxypropylmethyl cellulose
- MC:
-
Methyl cellulose
- NaCMC:
-
Sodium carboxymethyl cellulose
- LCST:
-
Lower critical solution temperature
- UV–Vis:
-
Ultraviolet–visible spectroscopy
- ATR-FTIR:
-
Attenuated total reflectance Fourier transformed infrared spectroscopy
- DSC:
-
Differential scanning calorimetry
- SMHP:
-
Solution that mimics human perspiration
- NaGlyPhos:
-
Glycerol phosphate disodium salt
- CaGlyPhos:
-
Glycerol phosphate calcium salt
References
Aguilar MR, Elvira C, Gallardo A, Vázquez B, Román JS (2007) Smart polymers and their applications as biomaterials. http://www.oulu.fi/spareparts/ebook_topics_in_t_e_vol3/
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. https://doi.org/10.1039/c2sm25254f
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. https://doi.org/10.1016/j.addr.2013.04.016
Arvidson SA et al (2013) Interplay of phase separation and thermoreversible gelation in aqueous methylcellulose solutions. Macromolecules 46:300–309. https://doi.org/10.1021/ma3019359
Barros SC et al (2014) Thermo-sensitive chitosan-cellulose hydrogels: swelling behaviour and morphologic studies. Cellulose 21:4531–4544. https://doi.org/10.1007/s10570-014-0442-9
Barros S et al (2015) Thermal–mechanical behaviour of chitosan–cellulose derivative thermoreversible hydrogel films. Cellulose 22:1911–1929. https://doi.org/10.1007/s10570-015-0603-5
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. https://doi.org/10.1016/j.foodres.2014.09.016
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. https://doi.org/10.1016/j.clay.2016.08.026
Chan AW, Whitney RA, Neufeld RJ (2009) Semisynthesis of a controlled stimuli-responsive alginate hydrogel. Biomacromol 10:609–616. https://doi.org/10.1021/bm801316z
Chang C, Zhang L (2011) Cellulose-based hydrogels: present status and application prospects. Carbohydr Polym 84:40–53. https://doi.org/10.1016/j.carbpol.2010.12.023
Chang C, He M, Zhou J, Zhang L (2011) Swelling behaviors of pH- and salt-responsive cellulose-based hydrogels. Macromolecules 44:1642–1648. https://doi.org/10.1021/ma102801f
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. https://doi.org/10.16865/j.cnki.1000-7555.2016.11.030
Chen L, Wang T, Li K (2016b) Preparation of chitosan/hydroxypropyl methyl cellulose thermo-sensitive hydrogel. Polym Mater Sci Eng 32:156–161 + 167
Chenite A et al (2000) Novel injectable neutral solutions of chitosan form biodegradable gels in situ. Biomaterials 21:2155–2161. https://doi.org/10.1016/S0142-9612(00)00116-2
Chenite A, Buschmann M, Wang D, Chaput C, Kandani N (2001) Rheological characterisation of thermogelling chitosan/glycerol-phosphate solutions. Carbohydr Polym 46:39–47. https://doi.org/10.1016/S0144-8617(00)00281-2
Chevillard C, Axelos MAV (1997) Phase separation of aqueous solution of methylcellulose. Colloid Polym Sci 275:537–545. https://doi.org/10.1007/s003960050116
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. https://doi.org/10.1021/bm050313s
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. https://doi.org/10.1016/j.foodhyd.2005.10.015
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. https://doi.org/10.1016/j.carbpol.2005.10.013
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. https://doi.org/10.1016/j.jfoodeng.2005.01.047
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. https://doi.org/10.3144/expresspolymlett.2011.83
Corporation O (2010) OriginPro, 8.5.0 SR1 edn, Northampton
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. https://doi.org/10.1016/j.carbpol.2010.07.038
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. https://doi.org/10.1016/j.carbpol.2011.12.014
Determan MD, Cox JP, Mallapragada SK (2007) Drug release from pH-responsive thermogelling pentablock copolymers. J Biomed Mater Res Part A 81A:326–333. https://doi.org/10.1002/jbm.a.30991
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. https://doi.org/10.1016/j.carbpol.2011.07.022
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. https://doi.org/10.1016/j.ijbiomac.2013.02.002
Ford JL (1999) Thermal analysis of hydroxypropylmethylcellulose and methylcellulose: powders, gels and matrix tablets. Int J Pharm 179:209–228. https://doi.org/10.1016/S0378-5173(98)00339-1
French AD (2017) Glucose, not cellobiose, is the repeating unit of cellulose and why that is important. Cellulose 24:4605–4609. https://doi.org/10.1007/s10570-017-1450-3
Heymann E (1935) Studies on sol–gel transformations. I. The inverse sol–gel transformation of methylcellulose in water. Trans Faraday Soc 31:846–864. https://doi.org/10.1039/tf9353100846
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. https://doi.org/10.1002/jbm.a.31365
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. https://doi.org/10.5681/bi.2011.018
Jeong B, Bae YH, Kim SW (1999) Thermoreversible gelation of PEG − PLGA − PEG triblock copolymer aqueous solutions. Macromolecules 32:7064–7069. https://doi.org/10.1021/ma9908999
Jeong B, Kim SW, Bae YH (2002) Thermosensitive sol–gel reversible hydrogels. Adv Drug Deliv Rev 54:37–51. https://doi.org/10.1016/S0169-409X(01)00242-3
Joshi SC (2011) Sol–gel behavior of hydroxypropyl methylcellulose (HPMC) in ionic media including drug release. Materials 4:1861
Joshi HN, Wilson TD (1993) Calorimetric studies of dissolution of hydroxypropyl methylcellulose E5 (HPMC E5) in water. J Pharm Sci 82:1033–1038. https://doi.org/10.1002/jps.2600821011
Karolewicz B (2016) A review of polymers as multifunctional excipients in drug dosage form technology. Saudi Pharm J 24:525–536. https://doi.org/10.1016/j.jsps.2015.02.025
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. https://doi.org/10.1007/s13726-013-0177-8
Klouda L, Mikos AG (2008) Thermoresponsive hydrogels in biomedical applications. Eur J Pharm Biopharm 68:34–45. https://doi.org/10.1016/j.ejpb.2007.02.025
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. https://doi.org/10.1533/9781845693121.173
Kwon J, Choi J (2013) Clothing insulation and temperature, layer and mass of clothing under comfortable environmental conditions. J Physiol Anthropol 32:11. https://doi.org/10.1186/1880-6805-32-11
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. https://doi.org/10.1021/la020029b
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. https://doi.org/10.1021/bm049813w
Liu SQ, Joshi SC, Lam YC, Tam KC (2008) Thermoreversible gelation of hydroxypropylmethylcellulose in simulated body fluids. Carbohydr Polym 72:133–143. https://doi.org/10.1016/j.carbpol.2007.07.040
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. https://doi.org/10.1016/j.jmbbm.2009.07.001
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. https://doi.org/10.1002/app.28840
Nishimura H, Donkai N, Miyamoto T (1997) Temperature-responsive hydrogels from cellulose. Macromol Symp 120:303–313. https://doi.org/10.1002/masy.19971200130
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. https://doi.org/10.1006/jcis.1999.6628
Parkova I, Vilumsone A (2011) Microclimate of smart garment. Mater Sci Text Cloth Technol 6:99–104
Patel A, Mequanint K (2011) Hydrogel biomaterials. Biomed Eng Front Chall. https://doi.org/10.5772/24856
Roy I, Gupta MN (2003) Smart polymeric materials: emerging biochemical applications. Chem Biol 10:1161–1171. https://doi.org/10.1016/j.chembiol.2003.12.004
Ruel-Gariépy E, Leroux J-C (2004) In situ-forming hydrogels—review of temperature-sensitive systems. Eur J Pharm Biopharm 58:409–426. https://doi.org/10.1016/j.ejpb.2004.03.019
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. https://doi.org/10.1016/S0378-5173(00)00428-2
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. https://doi.org/10.1016/j.polymer.2005.11.067
Sannino A et al (2000) Cellulose-based hydrogels as body water retainers. J Mater Sci Mater Med 11:247–253. https://doi.org/10.1023/a:1008980629714
Sannino A, Demitri C, Madaghiele M (2009) Biodegradable cellulose-based hydrogels: design and applications. Materials 2:353–373. https://doi.org/10.3390/ma2020353
Sarkar N (1979) Thermal gelation properties of methyl and hydroxypropyl methylcellulose. J Appl Polym Sci 24:1073–1087. https://doi.org/10.1002/app.1979.070240420
Schittek B et al (2001) Dermcidin: a novel human antibiotic peptide secreted by sweat glands. Nat Immunol 2:1133–1137. http://www.nature.com/ni/journal/v2/n12/suppinfo/ni732_S1.html
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. https://doi.org/10.1016/j.jcis.2008.08.056
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. https://doi.org/10.1021/la401993q
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. https://doi.org/10.1517/17425247.2014.867326
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. https://doi.org/10.1016/j.carbpol.2010.06.003
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. https://doi.org/10.3390/jfb2030173
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. https://doi.org/10.1111/ijfs.12039
Van Nieuwenhove I et al (2016) Gelatin- and starch-based hydrogels. Part A: hydrogel development, characterization and coating. Carbohydr Polym 152:129–139. https://doi.org/10.1016/j.carbpol.2016.06.098
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. https://doi.org/10.1016/j.polymer.2005.12.049
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. https://doi.org/10.1016/j.colsurfb.2010.08.047
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. https://doi.org/10.1016/j.ijbiomac.2016.09.038
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. https://doi.org/10.1038/srep24112
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. https://doi.org/10.2147/ijn.s47665
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. https://doi.org/10.1002/app.24393
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. https://doi.org/10.1016/j.carbpol.2005.08.041
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:35–42
Zhang XH, Li J, Wang YY (2012) Effects of clothing ventilation openings on thermoregulatory responses during exercise. Indian J Fibre Text 37:162–171. https://doi.org/10.1109/ICBECS.2010.5462337
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. https://doi.org/10.1016/j.carbpol.2014.09.094
Acknowledgments
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.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Barros, S.C., Silva, M.M. Seeking the lowest phase transition temperature in a cellulosic system for textile applications. Cellulose 25, 3163–3178 (2018). https://doi.org/10.1007/s10570-018-1763-x
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10570-018-1763-x