Observation of Calcium-Alginate Gel with Micrometer-sized Network Structure
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Author(s)
Abstract
The micrometer-sized network structure of a calcium-alginate hydrogel, which was synthesized from sodium alginate, calcium sulfate dihydrate, trisodium phosphate 12-hydrate, glycerol, and water, was observed using an optical microscope, cryogenic-scanning electron microscope, and an energy-dispersive X-ray spectrometer. For observation with the optical microscope, the calcium-alginate hydrogel was stained with Calcein, which emits green fluorescence by binding with calcium ions. Calcium ions act as a crosslinking agent in calcium-alginate hydrogels. For observation with the cryogenic-scanning electron microscope and energy-dispersive X-ray spectrometer, the hydrogel was frozen at -130 °C in a state containing water without drying or xerogelation. The optical microscope and cryogenic-scanning electron microscope observations revealed that the calcium-alginate hydrogel had a mixed structure of regions where large-scale gel networks and domains existed, and regions where they did not exist. The scale of each region was several hundred micrometers to several millimeters. In regions of the large-scale network structure, the domains were several tens of micrometers or less in size, and were surrounded by networks that were several hundred nanometers or more thick. Fluorescence emission of Calcein as observed by the optical microscope and elemental analysis with the energy-dispersive X-ray spectrometer indicated that the large-scale network is composed of accumulated calcium-alginate networks. Energy-dispersive X-ray spectroscopy also indicated that calcium alginate exists in the large-scale domains and in regions where no large-scale network structure exists. We considered that calcium-alginate networks of molecular sizes with a well-known egg-box structure exist in the large-scale network structure and regions where no large-scale network structure exists, and that the water constituting the hydrogel is preserved in them.
Keywords
hydrogel, alginate, gel network, domain structure, cryogenic-scanning electron microscopy
Cite this paper
Minoru Aoyagi, Takahiro Ueno,
Observation of Calcium-Alginate Gel with Micrometer-sized Network Structure
, SCIREA Journal of Materials.
Volume 3, Issue 3, June 2018 | PP. 76-89.
References
[ 1 ] | Madsen, E.L.; Zagzebski, J.A.; Banjavie, R.A.; Jutila, R.E. Tissue Mimicking Materials for Ultrasound Phantoms. Med. Phys. 1978, 5, 391-394. |
[ 2 ] | Madsen, E.L.; Frank, G.R.; Dong, F. Liquid or Solid Ultrasonically Tissue-Mimicking Materials with Very Low Scatter. Ultrasound Med. Biol., 1998, 24, 535-542. |
[ 3 ] | Blechinger, J.C.; Madsen, E.L.; Frank, G.R. Tissue-Mimicking Gelatin-Agar Gels for Use in Magnetic Resonance Imaging Phantoms. Med. Phys., 1988, 15, 629-636. |
[ 4 ] | de Korte, C.L.; Cespedes, E.I.; van der Steen, A.F.; Norder, B.K.; Nijenhuis, Te. Elastic and Acoustic Properties of Vessel Mimicking Material for Elasticity Imaging. Ultrason. Imaging, 1997, 19, 112-126. |
[ 5 ] | Surry, K.J.M.; Austin, H.J.B.; Fenster, A.; Peters, T.M. Poly(Vinyl Alcohol) Cryogel Phantoms for Use in Ultrasound and MR Imaging. Phys. Med. Biol., 2004, 49, 5529-5546. |
[ 6 ] | Culjat, M.O.; Goldenberg, D.; Tewari, P.; Singh, R.S. A Review of Tissue Substitutes for Ultrasound Imaging. Ultrasound Med. Biol., 2010, 36, 861-873. |
[ 7 ] | Cannon, L.M.; Fagan, A.J.; Browne, J.E. Novel Tissue Mimicking Materials for High Frequency Breast Ultrasound Phantoms. Ultrasound Med. Biol., 2011, 37, 122-135. |
[ 8 ] | Browne, J.E.; Ramnarine, K.V.; Watson, A.J.; Hoskins, P.R. Assessment of the Acoustic Properties of Common Tissue-Mimicking Test Phantoms. Ultrasound Med. Biol., 2003, 29, 1053-1060. |
[ 9 ] | Madsen, E.L.; Frank, G.R.; Dong. F. Liquid or Solid Ultrasonically Tissue-Mimicking Materials with Very Low Scatter. Ultrasound Med. Biol., 1998, 24, 535-542. |
[ 10 ] | Aoyagi, M.; Hiraguri, T. Ultrasound Phantom Using Sodium Alginate as a Gelling Agent. Journal of Ultrasound in Medicine, 2017, 36, 2345-2353. DOI: 10.1002/jum.14252. |
[ 11 ] | Fields, S.; Dunn, F. Correlation of Echographic Visualizability of Tissue with Biological Composition and Physiological State. J. Acoust. Soc. Am., 1973, 3, 809-812. |
[ 12 ] | Wells, P.N.T. Biomedical Ultrasonics, Academic Press, London, 1977. |
[ 13 ] | Chivers, R.C.; Parry, R.J. Ultrasonic Velocity and Attenuation in Mammalian Tissues. J. Acoust. Soc. Am., 1978, 63, 940-953. |
[ 14 ] | Gammell, P.M.; Le Croissette, D.H.; Heyser, R.C. Temperature and Frequency Dependence of Ultrasonic Attenuation in Selected Tissues. Ultrasound Med. Biol., 1979, 5, 269-277. |
[ 15 ] | Goss, S.A.; Johnston, R.L.; Dunn, F. Comprehensive Compilation of Empirical Ultrasonic Properties of Mammalian Tissues. J. Acoust. Soc. Am., 1980, 68, 93-108. |
[ 16 ] | Burlew, M.M.; Madsen, E.L.; Zagzebski, J.A.; Banjavic, R.A.; Sum, S.W. A New Ultrasound Tissue- Equivalent Material. Radiology, 1980, 134, 517-520. |
[ 17 ] | International commission on radiation units and measurements. ICRU Report 61: Tissue Substitutes, Phantoms and Computational Modelling in Medical Ultrasound, ICRU Publications: Bethesda, MD 1998. |
[ 18 ] | Mast, T.D. Empirical Relationships between Acoustic Parameters in Human Soft Tissues Acoust. Res. Lett. Online, 2000, 1, 37-42. |
[ 19 ] | Haug, A.; Larsen, B.; Smidsrod, O. A Study of the Constitution of Alginic Acid by Partial Acid Hydrolysis. Acta Chem. Scand., 1966, 20, 183-190. |
[ 20 ] | Haug, A.; Myklestad, S.; Larsen, B.; Smidsrød, O. Correlation between Chemical Structure and Physical Properties of Alginates. Acta Chem. Scand., 1967, 21, 768-778. |
[ 21 ] | Rees, D.A. Conformation, and Mechanism in the Formation of Polysaccharide Gels and Networks. Chem. Adv. Carbohydr. Structure, Biochem., 1969, 24, 267-332. |
[ 22 ] | Penman, A.; Sanderson, G.R. A Method for the Determination of Uronic Acid Sequence in Alginates. Carbohydr. Res., 1972, 25, 273-282. |
[ 23 ] | Smidsrod, O.; Haug, A. Dependence upon the Gel-Sol State of the Ion-Exchange Properties of Alginates. Acta Chem. Scand., 1972, 26, 2063-2074. |
[ 24 ] | Smidsrod, O.; Haug, A.; Whittington, S.G. The molecular basis for some physical properties of polyuronides. Acta Chem. Scand., 1972, 26, 2563-2566. |
[ 25 ] | Atkins, E.D.; Nieduszynski, I.A.; Mackie, W.; Parker, K.D.; Smolko, E.E. Structural Components of Alginic Acid. I. The Crystalline Structure of Poly-β-D-Mannuronic Acid. Results of X-ray Diffraction and Polarized Infrared Studies. Biopolymers, 1973, 12, 1865-1878. |
[ 26 ] | Atkins, E.D.T.; Nieduszynski, I.A.; Mackie, W.; Parker, K.D.; Smolko, E.E. Structural Components of Alginic Acid. II. The Crystalline Structure of Poly-α-L Guluronic Acid. Results of X-ray Diffraction and Polarized Infrared Studies. Biopolymers, 1973, 12, 1879-1887. |
[ 27 ] | Grant, G.T.; Morris, E.R.; Rees, D.A.; Smith, P.J.C.; Thom, D. Biological Interactions Between Polysaccharides and Divalent Cations: The Egg-Box model. FEBS Lett., 1973, 32, 195-198. |
[ 28 ] | Haug, A.; Larsen, B.; Smidsrod, O. Uronic Acid Sequence in Alginate from Different Sources. Carbohydr. Res., 1974, 32, 217-225. |
[ 29 ] | Morris, E.R.; Rees, D.A.; Thom, D. Characterization of Alginate Composition and Block-Structure by Circular Dichroism. Carbohyd. Res., 1980, 81, 305-314. |
[ 30 ] | Grasdalen, H.; Larsen, B.; Smidsrod, O. 13C-N.M.R. Studies of Monomeric Composition and Sequence in Alginate. Carbohydr. Res., 1981, 89, 179-191. |
[ 31 ] | Augst, A.D.; Kong, J.K.; Mooney, D.J. Alginate Hydrogels as Biomaterials. Macromol. Biosci., 2006, 6, 623-633. |
[ 32 ] | Adrian, M.; Dubochet, J.; Lepault, J.; McDowall, A.W. Cryo-Electron Microscopy of Viruses. Nature, 1984, 308, 32-36. |
[ 33 ] | Rahbani, J.; Behzad, A.R.; Khashab, N.M. Characterization of Internal Structure of Hydrated Agar and Gelatin Matrices by Cryo-SEM. Electrophoresis, 2013, 34, 405-408. |
[ 34 ] | Marmorat, C.; Arinstein, A.; Koifman, N.; Talmon, Y.; Zussman, E.; Rafailovich, M. Cryo-Imaging of Hydrogels Supermolecular Structure. Sci. Rep. 2016, 6, Article number: 25495, DOI: 10.1038/srep25495. |
[ 35 ] | E. Zorebski, Excess Volumes and Adiabatic Compressibilities of Binary Mixtures of. Cyclohexanol+Glycerol at 298.15 K. Mol. Quantum Acoust., 2002, 23, 463-472. |
[ 36 ] | Strohm, E.; Kolios, M. Sound Velocity and Attenuation Measurement of Perfluorocarbon Liquids Using Photoacoustic Methods. Proceedings of 2011 IEEE International Ultrasonics Symposium (IUS 2011), Florida, USA, Oct 18-21, 2011; 2368-2371; P6Aa-5. |
[ 37 ] | Ashby, R.O.; Roberts. M. A Micro Determination of Calcium in Blood Serum. J. Lab. & Clin. Med., 1957, 49, 958-961. |
[ 38 ] | Korbl, J.; Vyder. F. Metallochromic Indicators. IV. A Note on the Preparation and Properties of Calcein. Collect. Czech. Chem. Commun., 1958, 23, 622-627. |
[ 39 ] | Demertzis, M.A. Fluorimetric Determination of Calcium in Serum with Calcein: Complexation of Calcein with Calcium and Alkali Metals. Anal. Chim. Acta, 1988, 209, 303-308. |
[ 40 ] | Muller-Ackermann, E.; Panne, U.; Niessner. R. A Fibre Optic Sensor Array for the Fluorimetric Detection of Heavy Metals. Anal. Methods Instrum., 1995, 2, 182-189. |