The size and weight fraction of crystals of pure ice or dimethylsulfoxide
(DMSO) in poly(vinyl alcohol) (PVA) gel prepared from a mixed solvent of DMSO/water
were determined from melting peaks observed by differential scanning
calorimetry (DSC). The depression of the melting point with respect to the equilibrium
melting point and the melting enthalpy gave the crystal size and weight
fraction, respectively. The sizes were in the range of a few nm to tens of nm,
depending on the composition ratio of the mixed solvent (DMSO/water) and the
polymer concentration. Based on the weight fraction, the critical condition at
which the whole solvent became non-freezable was estimated, and it was found to
depend on both the PVA concentration and the DMSO/water ratio. When the solvent
was pure water, the critical PVA concentration was as high as 86.4 wt%, while
for pure DMSO solvent it was 50.1 wt%.
Higuchi, A. and Iijima, T. (1985) DSC Investigation of the States of Water in Poly (Vinyl Alcohol) Membranes. Polymer, 26, 1207-1211. http://dx.doi.org/10.1016/0032-3861(85)90254-X
[3]
Peppas, N.A. and Merrill, E.W. (1976) PVA Hydrogels: Reinforcement of Radiation-Crosslinked Networks by Crystallization. Journal of Polymer Science Part A: Polymer Chemistry, 14, 441-457. http://dx.doi.org/10.1002/pol.1976.170140215
[4]
Willcox, P.J., Howie, D.W., Shimidt-Rohr, K., Hoagland, D.A., Gido, S.P., Pudjijanto, S., Kleiner, L.W. and Venkatraman, S.J. (1999) Microstructure of Poly(Vinyl Alcohol) Hydrogels Produced by Freeze/Thaw Cycling. Journal of Polymer Science Part B, 37, 3438-3454. http://dx.doi.org/10.1002/(SICI)1099-0488(19991215)37:24<3438::AID-POLB6>3.0.CO;2-9
[5]
Ricciawdi, R., Auriemma, F., De Rosa, C. and Laupretre, F. (2004) X-Ray Diffraction Analysis of Poly(Vinyl Alcohol) Hydrogels, Obtained by Freezing and Thawing Techniques. Macromolecules, 37, 1921-1927. http://dx.doi.org/10.1021/ma035663q
[6]
Ricciardi, R., Auriemma, F., Gaillet, C., De Rosa, C. and Laupretre, F. (2004) Investigation of the Crystallinity of Freeze/Thaw Poly(Vinyl Alcohol) Hydrogels by Different Techniques. Macromolecules, 37, 9510-9516. http://dx.doi.org/10.1021/ma048418v
[7]
Ricciardi, R., Mangiapia, G., Lo Celso, F., Paduano, L., Triolo, R., Auriemma, F., De Rosa, C. and Laupretre, F. (2005) Evolution of PVA Gels Prepared without Crosslinking Agents as a Cell Adhesive Surface. Chemistry of Materials, 17, 1183-1189. http://dx.doi.org/10.1021/cm048632y
[8]
Auriemma, F., De Rosa, C., Ricciardi, R., Lo Celso, F., Triolo, R. and Pipich, V. (2008) Time-Resolving Analysis of Cryotropic Gelation of Water/Poly(Vinyl Alcohol) Solutions via Small-Angle Neutron Scattering. Journal of Physical Chemistry B, 112, 816-823. http://dx.doi.org/10.1021/jp0763984
[9]
Nakaoki, T. and Yamashita, H. (2008) Coagulation Dimension of Freezable Bound Solvent in Isotactic Polypropylene/o-Dichlorobenzene Gel. Journal of Molecular Structure, 875, 282-287. http://dx.doi.org/10.1016/j.molstruc.2007.04.040
[10]
Nakano, T. and Nakaoki, T. (2011) Coagulation Size of Freezable Water in Poly(Vinyl Alcohol) Hydrogels Formed by Different Freeze/Thaw Cycle Periods. Polymer Journal, 43, 875-880. http://dx.doi.org/10.1038/pj.2011.92
[11]
Ishikiriyama, K., Todoki, M. and Motomura, K. (1995) Pore Size Distribution (PSD) Measurements of Silica Gels by Means of Differential Scanning Calorimetry: I. Optimization for Determination of PSD. Journal of Colloid and Interface Science, 171, 92-103. http://dx.doi.org/10.1006/jcis.1995.1154
[12]
Ishikiriyama, K. and Todoki, M. (1995) Pore Size Distribution Measurements of Silica Gels by Means of Differential Scanning Calorimetry: II. Thermoporosimetry. Journal of Colloid and Interface Science, 171, 103-111. http://dx.doi.org/10.1006/jcis.1995.1155
[13]
Cowie, J.M.G. and Toporowski, P.M. (1961) Association in the Binary Liquid System Dimethyl Sulphoxide-Water. Canadian Journal of Chemistry, 39, 2240-2243. http://dx.doi.org/10.1139/v61-296
[14]
Kanaya, T., Ohkura, M., Kaji, K., Furusaka, M. and Misawa, M. (1994) Structure of Poly(vinyl alcohol) Gels Studied by Wide- and Small-Angle Neutron Scattering. Macromolecules, 27, 5609-5615. http://dx.doi.org/10.1021/ma00098a014
[15]
Takeshita, H., Kanaya, T., Nishida, K. and Kaji, K. (1999) Gelation Process and Phase Separation of PVA Solutions As Studied by a Light Scattering Technique. Macromolecules, 32, 7815-7819. http://dx.doi.org/10.1021/ma990565j
[16]
Takahashi, N., Kanaya, T., Nishida, K. and Kaji, K. (2003) Effects of Cononsolvency on Gelation of Poly(vinyl alcohol) in Mixed Solvents of Dimethyl Sulfoxide and Water. Polymer, 44, 4075-4078. http://dx.doi.org/10.1016/S0032-3861(03)00390-2
[17]
Takahashi, N., Kanaya, T., Nishida, K. and Kaji, K. (2007) Gelation-Induced Phase Separation of Poly(vinyl alcohol) in Mixed Solvents of Dimethyl Sulfoxide and Water. Macromolecules, 40, 8750-8755. http://dx.doi.org/10.1021/ma071256t
[18]
Rasmussen, D.H. and MacKenzie, A.P. (1968) Phase Diagram for the System Water-Dimethylsulphoxide. Nature, 220, 1315-1317. http://dx.doi.org/10.1038/2201315a0
[19]
Vaisman, I.I. and Berkowitz, M.L. (1992) Local Structural Order and Molecular Associations in Water-DMSO Mixtures. Molecular Dynamics Study. Journal of the American Chemical Society, 114, 7889-7896. http://dx.doi.org/10.1021/ja00046a038
[20]
Luzar, A., Soper, A.K. and Chandler, D. (1993) Combined Neutron Diffraction and Computer Simulation Study of Liquid Dimethyl Sulphoxide. The Journal of Chemical Physics, 99, 6836-6847. http://dx.doi.org/10.1063/1.465828
[21]
Luzar, A. and Chandler, D. (1993) Structure and Hydrogen Bond Dynamics of Water-Dimethyl Sulfoxide Mixtures by Computer Simulations. The Journal of Chemical Physics, 98, 8160-8173. http://dx.doi.org/10.1063/1.464521
[22]
Kirchner, B., Searles, D.J., Dyson, A.J., Vogt, P.S. and Huber, H. (2000) Disproving the Iceberg Effect? A Study of the Deuteron Quadrupole Coupling Constant of Water in a Mixture with Dimethyl Sulfoxide via Computer Simulations. Journal of the American Chemical Society, 122, 5379-5383. http://dx.doi.org/10.1021/ja994526z
[23]
Liu, H., Mueller-Plathe, F. and van Gunsteren, W.F. (1995) A Force Field for Liquid Dimethyl Sulfoxide and Physical Properties of Liquid Dimethyl Sulfoxide Calculated Using Molecular Dynamics Simulation. Journal of the American Chemical Society, 117, 4363-4366. http://dx.doi.org/10.1021/ja00120a018
[24]
Borin, I.A. and Skaf, M.S. (1999) Molecular Association between Water and Dimethyl Sulfoxide in Solution: A Molecular Dynamics Simulation Study. The Journal of Chemical Physics, 110, 6412-6420. http://dx.doi.org/10.1063/1.478544
[25]
Vishnyakov, A., Lyubartsev, A.P. and Laaksonen, A. (2001) Molecular Dynamics Simulations of Dimethyl Sulfoxide and Dimethyl Sulfoxide-Water Mixture. The Journal of Physical Chemistry A, 105, 1702-1710. http://dx.doi.org/10.1021/jp0007336
[26]
Strader, M.L. and Feller, S.E. (2002) A Flexible All-Atom Model of Dimethyl Sulfoxide for Molecular Dynamics Simulations. The Journal of Physical Chemistry A, 106, 1074-1080. http://dx.doi.org/10.1021/jp013658n
[27]
Kirchner, B. and Reiher, M. (2002) The Secret of Dimethyl Sulfox-ide-Water Mixtures. A Quantum Chemical Study of 1DMSO-nWater Clusters. Journal of the American Chemical Society, 124, 6206-6215. http://dx.doi.org/10.1021/ja017703g
[28]
Eggenberger, R., Gerber, S., Huber, H. and Searles, D. (1991) Ab initio Calculation of the Second Virial Coefficient of Neon and the Potential Energy Curve of Ne2. Chemical Physics, 156, 395-401. http://dx.doi.org/10.1016/0301-0104(91)89008-X
[29]
Kelton, K.F. (1991) Crystal Nucleation in Liquids and Glasses. Solid State Physics, 45, 75-177. http://dx.doi.org/10.1016/s0081-1947(08)60144-7
[30]
ten Wolde, R.P. and Frenkel, D. (1997) Enhancement of Protein Crystal Nucleation by Critical Density Fluctuations. Science, 277, 1975-1978. http://dx.doi.org/10.1126/science.277.5334.1975
[31]
Randall, M. (1930) International Critical Tables V-VII. McGraw-Hill, New York.
[32]
Clever, H.L. and Westrum Jr., E.F. (1970) Dimethyl Sulfoxide and Dimethyl Sulfone. Heat Capacities, Enthalpies of Fusion, and Thermodynamic Properties. The Journal of Physical Chemistry, 74, 1309-1317. http://dx.doi.org/10.1021/j100701a027
[33]
Jasper, J.J. (1972) The Surface Tension of Pure Liquid Compounds. Journal of Physical and Chemical Reference Data, 1, 841. http://dx.doi.org/10.1063/1.3253106
[34]
Hu, S., Horii, F. and Odani, H. (1989) 1H NMR Study of the Solvation and Gelation in a Poly(vinyl alcohol)/DMSO- d6/H2 0 System. Bulletin of the Institute for Chemical Research, Kyoto University, 67, 239-248.
