Abstract
The effect of adding GA to 1 % (w/v) TSX on the phase transitions was detected by tube inversion and optical changes. The size of the aggregated domains and the morphology of the GA/TSX blends in the gel states were investigated using SAXS and an optical microscope, respectively, at 25 °C. Turbidity and tube inversion determinations showed that 1TSX, 0.2GA/1TSX and 0.4GA/1TSX could not form a gel but the blends of 0.6GA/1TSX, 0.8GA/1TSX and 1GA/1TSX formed turbid gels and exhibited a thermoreversible phase transformation. Upon heating, the gel-to-sol temperatures were between 42 and 52 °C and increased with an increase of the GA concentration. Upon cooling, the sol-to-gel temperatures were between 26 and 36 °C with the lower temperatures for the lower concentrations of GA in the blends. According to SAXS analyses, molecular aggregation appeared in the blends that exhibited the gelling ability with an aggregation domain of 2.2–2.9 nm. The size of the aggregation domain increased as the GA concentration increased. Fibrillation was observed for the gels of 0.6GA/1TSX, 0.8GA/1TSX and 1GA/1TSX from the optical micrographs. Furthermore, the blends of GA/TSX caused synergistic antioxidant activity as determined by a reduction of the DPPH radicals. In addition, these GA/TSX gels exhibited a sustained release of GA by a non-Fickian mechanism. These gels may have a potential use for the topical delivery of GA.
Similar content being viewed by others
References
Bajpai AK, Shukla SK, Bhanu S, Kankane S (2008) Responsive polymers in controlled drug delivery. Prog Polym Sci 33:1088–1118
Boustta M, Colombo P-E, Lenglet S, Poujol S, Vert M (2014) Versatile UCST-based thermoresponsive hydrogels for loco-regional sustained drug delivery. J Control Release 174:1–6
Wang Q, Li S, Wang Z, Liu H, Li C (2009) Preparation and characterization of a positive thermoresponsive hydrogel for drug loading and release. J Appl Polym Sci 111:1417–1425
Saxena A, Kaloti M, Bohidar HB (2011) Rheological properties of binary and ternary protein–polysaccharide co-hydrogels and comparative release kinetics of salbutamol sulphate from their matrices. Int J Biol Macromol 48:263–270
Rawat K, Aswal VK, Bohidar HB (2012) DNA–gelatin complex coacervation, UCST and first-order phase transition of coacervate to anisotropic ion gel in 1-methyl-3-octylimidazolium chloride ionic liquid solutions. J Phys Chem B 116:14805–14816
Di Y, Ma X, Li C, Liu H, Fan X, Wang M et al (2014) A new thermosensitive poly(N-propionyl-aspartic acid/ethylene glycol) with no cytotoxicity and tunable UCST. Macromol Chem Physic 215:365–371
Tuvikene R, Truus K, Kollist A, Volobujeva O, Mellikov E, Pehk T (2008) Gel-forming structures and stages of red algal galactans of different sulfation levels. J Appl Phycol 20:527–535
Persin Z, Stana-Kleinschek K, Foster TJ, van Dam JEG, Boeriu CG, Navard P (2011) Challenges and opportunities in polysaccharides research and technology: the EPNOE views for the next decade in the areas of materials, food and health care. Carbohydr Polym 84:22–32
Nandi LG, Guerra JPTA, Bellettini IC, Machado VG, Minatti E (2013) Properties of aqueous solutions of lentinan in the absence and presence of zwitterionic surfactants. Carbohydr Polym 98:1–7
Yamashita Y, Yanagisawa M, Tokita M (2014) Sol–gel transition and phase separation in ternary system of gelatin–water–poly(ethylene glycol) oligomer. J Mol Liq 200:47–51
Chivero P, Gohtani S, Ikeda S, Nakamura A (2014) The structure of soy soluble polysaccharide in aqueous solution. Food Hydrocolloids 35:279–286
Kara S, Arda E, Pekcan Ö (2005) Molecular recognition during sol–gel and gel–sol transition of kappa–iota carrageenan mixtures. Phase Transit 78:915–926
Hirun N, Rugmai S, Sangfai T, Tantishaiyakul V (2012) SAXS and ATR-FTIR studies on EBT–TSX mixtures in their sol–gel phases. Int J Biol Macromol 51:423–430
Xu Y, Li L (2005) Thermoreversible and salt-sensitive turbidity of methylcellulose in aqueous solution. Polymer 46:7410–7417
Khutoryanskiy VV, Nurkeeva ZS, Mun GA, Dubolazov AV (2004) Effect of temperature on aggregation/dissociation behavior of interpolymer complexes stabilized by hydrogen bonds. J Appl Polym Sci 93:1946–1950
Dai H, Chen Q, Qin H, Guan Y, Shen D, Hua Y et al (2006) A temperature-responsive copolymer hydrogel in controlled drug delivery. Macromolecules 39:6584–6589
Agulhon P, Robitzer M, David L, Quignard F (2012) Structural regime identification in ionotropic alginate gels: influence of the cation nature and alginate structure. Biomacromolecules 13:215–220
Moschakis T, Lazaridou A, Biliaderis CG (2012) Using particle tracking to probe the local dynamics of barley β-glucan solutions upon gelation. J Colloid Interface Sci 375:50–59
Casettari L, Cespi M, Palmieri GF, Bonacucina G (2013) Characterization of the interaction between chitosan and inorganic sodium phosphates by means of rheological and optical microscopy studies. Carbohydr Polym 91:597–602
Inoue M, Suzuki R, Koide T, Sakaguchi N, Ogihara Y, Yabu Y (1994) Antioxidant, gallic acid, induces apoptosis in HL-60RG cells. Biochem Bioph Res Commun 204:898–904
Ji BC, Hsu WH, Yang JS, Hsia TC, Lu CC, Chiang JH et al (2009) Gallic acid induces apoptosis via caspase-3 and mitochondrion-dependent pathways in vitro and suppresses lung xenograft tumor growth in vivo. J Agric Food Chem 57:7596–7604
Priscilla DH, Prince PSM (2009) Cardioprotective effect of gallic acid on cardiac troponin-T, cardiac marker enzymes, lipid peroxidation products and antioxidants in experimentally induced myocardial infarction in Wistar rats. Chem Biol Interact 179:118–124
Tavano L, Muzzalupo R, Picci N, de Cindio B (2014) Co-encapsulation of antioxidants into niosomal carriers: gastrointestinal release studies for nutraceutical applications. Colloid Surface B 114:82–88
Subramanian V, Venkatesan B, Tumala A, Vellaichamy E (2014) Topical application of Gallic acid suppresses the 7,12-DMBA/Croton oil induced two-step skin carcinogenesis by modulating anti-oxidants and MMP-2/MMP-9 in Swiss albino mice. Food Chem Toxicol 66:44–55
Chen L, Remondetto GE, Subirade M (2006) Food protein-based materials as nutraceutical delivery systems. Trends Food Sci Tech 17:272–283
Wang Y, Liu J, Chen F, Zhao G (2013) Effects of molecular structure of polyphenols on their noncovalent interactions with oat β-glucan. J Agric Food Chem 61:4533–4538
Hirun N, Bao H, Li L, Deen GR, Tantishaiyakul V (2012) Micro-DSC, rheological and NMR investigations of the gelation of gallic acid and xyloglucan. Soft Matter 8:7258–7268
Hirun N, Tantishaiyakul V, Pichayakorn W (2010) Effect of Eriochrome Black T on the gelatinization of xyloglucan investigated using rheological measurement and release behavior of Eriochrome Black T from xyloglucan gel matrices. Int J Pharm 388:196–201
Hirun N, Sangfai T, Tantishaiyakul V (2015) Characterization of freeze-dried gallic acid/xyloglucan. Drug Dev Ind Pharm 41:194–200
Behera B, Patil V, Sagiri SS, Pal K, Ray SS (2012) Span-60-based organogels as probable matrices for transdermal/topical delivery systems. J Appl Polym Sci 125:852–863
Glatter O, Kratky O (1982) Small angle X-ray scattering. Academic Press, London
Soontaranon S, Rugmai S (2012) Small angle X-ray scattering at Siam photon laboratory. Chin J Phys 50:204–210
Neo YP, Ray S, Jin J, Gizdavic-Nikolaidis M, Nieuwoudt MK, Liu D et al (2013) Encapsulation of food grade antioxidant in natural biopolymer by electrospinning technique: a physicochemical study based on zein–gallic acid system. Food Chem 136:1013–1021
Giri A, Bhowmick M, Pal S, Bandyopadhyay A (2011) Polymer hydrogel from carboxymethyl guar gum and carbon nanotube for sustained trans-dermal release of diclofenac sodium. Int J Biol Macromol 49:885–893
Ghouchi Eskandar N, Simovic S, Prestidge C (2009) Nanoparticle coated submicron emulsions: sustained in vitro release and improved dermal delivery of all-trans-retinol. Pharm Res 26:1764–1775
Bansil R, Gupta MK (1980) Effect of varying crosslinking density on polyacrylamide gels. Ferroelectrics 30:63–71
Slootmaekers D, Mandel M, Reynaers H (1991) Dynamic light scattering by κ- and λ-carrageenan solutions. Int J Biol Macromol 13:17–25
Chen Y, Hu Z, Lang JC (1998) Turbidity investigation of the sol–gel transition in carrageenan gels under physiologic conditions. J Appl Polym Sci 68:29–35
Seuyep D, Szopinski D, Luinstra GA, Theato P (2014) Post-polymerization modification of reactive polymers derived from vinylcyclopropane: a poly(vinylcyclopropane) derivative with physical gelation and UCST behaviour in ethanol–water mixtures. Polym Chem 5:5823–5828
Wang ZY, White JW, Konno M, Saito S, Nozawa T (1995) A small-angle x-ray scattering study of alginate solution and its sol–gel transition by addition of divalent cations. Biopolymers 35:227–238
Yuguchi Y, Urakawa H, Kajiwara K (2002) The effect of potassium salt on the structural characteristics of gellan gum gel. Food Hydrocolloids 16:191–195
Tada T, Matsumoto T, Masuda T (1998) Structure of molecular association of curdlan at dilute regime in alkaline aqueous systems. Chem Phys 228:157–166
Ishii D, Tatsumi D, Matsumoto T, Murata K, Hayashi H, Yoshitani H (2006) Investigation of the structure of cellulose in LiCl/DMAc solution and its gelation behavior by small-angle X-ray scattering measurements. Macromol Biosci 6:293–300
Yoshida K, Fukushima Y, Yamaguchi T (2014) A study of alcohol and temperature effects on aggregation of β-lactoglobulin by viscosity and small-angle X-ray scattering measurements. J Mol Liq 189:1–8
Kondo T, Sawatari C (1996) A Fourier transform infra-red spectroscopic analysis of the character of hydrogen bonds in amorphous cellulose. Polymer 37:393–399
Ikkai F, Shibayama M, Kashihara H, Nomura S (1997) SAXS and dynamic viscoelastic studies on segmented polyurethaneurea solutions. Polymer 38:769–774
Michon C, Vigouroux F, Boulenguer P, Cuvelier G, Launay B (2000) Gelatin/iota-carrageenan interactions in non-gelling conditions. Food Hydrocolloid 14:203–208
Weiβ G, Knoch A, Laicher A, Stanislaus F, Daniels R (1995) Simple coacervation of hydroxypropyl methylcellulose phthalate (HPMCP) I. Temperature and pH dependency of coacervate formation. Int J Pharm 124:87–96
Mori T, Nakashima M, Fukuda Y, Minagawa K, Tanaka M, Maeda Y (2006) Soluble–insoluble–soluble transitions of aqueous poly(N-vinylacetamide-co-acrylic acid) solutions. Langmuir 22:4336–4342
Muster TH, Vincent B (2003) Particle formation and gelling behaviour of anionic oligoesters in aqueous solution. Colloid Surf A 228:181–187
Dahan E, Sundararajan PR (2013) Thermoreversible physical gels of poly(dimethylsiloxane) without cross-links or functionalization. Langmuir 29:8452–8458
Gabriele A, Spyropoulos F, Norton IT (2009) Kinetic study of fluid gel formation and viscoelastic response with kappa-carrageenan. Food Hydrocolloid 23:2054–2061
Kalashnikov VN, Tsiklauri MG (1996) Supermolecular structures and flow birefringence in polymer solutions. Colloid Polym Sci 274:1119–1128
Audsley A, Fursey A (1965) Examination of a polysaccharide flocculant and flocculated kaolinite by electron microscopy. Nature 208:753–754
Kalashnikov VN, Tsiklauri MG (1990) Super-molecular structure of dilute solutions of high molecular weight polymers which lead to reduced turbulent friction. J Eng Phys 58:40–45
Keller A (1995) Aspects of polymer gels. Faraday Discuss 101:1–49
Mengome LE, Voxeur A, Akue JP, Lerouge P (2014) Screening of antioxidant activities of polysaccharides extracts from endemic plants in Gabon. Bioact Carbohydr Diet Fibre 3:77–88
Wu Z, Ming J, Gao R, Wang Y, Liang Q, Yu H et al (2011) Characterization and antioxidant activity of the complex of tea polyphenols and oat β-glucan. J Agr Food Chem 59:10737–10746
Olga G, Styliani C, Ioannis RG (2015) Coencapsulation of ferulic and gallic acid in hp-b-cyclodextrin. Food Chem 185:33–40
Cappelli C, Mennucci B, Monti S (2005) Environmental effects on the spectroscopic properties of gallic acid: a combined classical and quantum mechanical study. J Phys Chem A 109:1933–1943
Hirun N, Dokmaisrijan S, Tantishaiyakul V (2012) Experimental FTIR and theoretical studies of gallic acid–acetonitrile clusters. Spectrochim Acta A Mol Biomol Spectrosc 86:93–100
Garcia X, Escribano E, Domenech J, Queralt J, Freixes J (2011) In vitro characterization and in vivo analgesic and anti-allodynic activity of PLGA-bupivacaine nanoparticles. J Nanopart Res 13:2213–2223
Simoes SM, Veiga F, Ribeiro AC, Figueiras AR, Taboada P, Concheiro A et al (2014) Supramolecular gels of poly-α-cyclodextrin and PEO-based copolymers for controlled drug release. Eur J Pharm Biopharm 87:579–588
Ansari M, Kazemipour M, Aklamli M (2006) The study of drug permeation through natural membranes. Int J Pharm 327:6–11
François NJ, Rojas AM, Daraio ME (2005) Rheological and drug-release behaviour of a scleroglucan gel matrix at different drug loadings. Polym Int 54:1613–1619
Peppas NA, Khare AR (1993) Preparation, structure and diffusional behavior of hydrogels in controlled release. Adv Drug Deliver Rev 11:1–35
Acknowledgments
This work was supported by the Nanotechnology Center (NANOTEC), NSTDA, Ministry of Science and Technology, Thailand, through its program of Center of Excellence Network. In addition, we would like to thank the BL1.3W beamline staff of the Synchrotron Light Research Institute for their support in the SAXS experiments and for treatment of the data. Thanks also to Dr. Brian Hodgson for assistance with the English.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Hirun, N., Tantishaiyakul, V., Sangfai, T. et al. Nano-structure, phase transition and morphology of gallic acid and xyloglucan hydrogel. Polym. Bull. 73, 2211–2226 (2016). https://doi.org/10.1007/s00289-016-1604-8
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00289-016-1604-8