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Effects of carboxylated ε-poly-L-lysine on crystallization of ice

Dmitry Vorontsov 1Gen Sazaki 2Suong-Hyu Hyon 3Kazuaki Matsumura 4Yoshinori Furukawa 2

1. Nizhny Novgorod State University, Nizhny Novgorod 603950, Russian Federation
2. Institute of Low Temperature Science, Hokkaido University (ILTS), N19-W8, Kita-ku, Sapporo 060-0819, Japan
3. Center for Fiber and Textile Science, Kyoto Institute of Technology, Kyoto 606-8585, Japan
4. Japan Advanced Institute of Science and Technology, Ishikawa 923-1292, Japan

Abstract

   The use of some biological agents gives a potential to control the crystallization processes of ice. Living organisms (polar fish, insects) produce anti-freeze proteins to survive in subfreezing environments. Some agents are used in medicine for preservation and transplantation of cells and tissues [1]. Carboxylated ε-poly-L-lysine (PLL) is a new cryoprotector which shows lower cytotoxicity [2].
    In this study we have investigated the effects of carboxylated ε-poly-L-lysine as an impurity on crystallization of ice in supercooled water. Seed crystals of ice of hexagonal modification (space group P63/mmc) were created in a glass capillary and then were grown up in a growth cell filled with supercooled water with PLL concentrations 0-150 mg/ml H2O. The accuracy of temperature control in the growth chamber was within ±0.02 °C. Measurements of growth rates R were performed by optical microscopy at supercoolings ΔT from 0 to 1.5°C. Images of growing crystal were captured at every fixed time interval by a video-system and processed by specially developed software. Ice crystal has a disk-like shape at small supercoolings (0.2-0.3°C) where the top and bottom planes are basal faces {0001}. Further increase in supercooling leads to formation of dendrites with branches parallel to the {0001} faces. The change to dendritic growth in the presence of PLL impurity occurs at lower supercoolings than in pure deionized water. An increase in PLL concentration inhibits growth rate of the faces of ice crystals at fixed supercooling. Growth rate sharply increases when supercooling reaches a certain critical value. Depression of melting point of ice has not been detected in water with PLL additions. Blocking effect of impurity is explained on the basis of Gibbs-Thomson law and under the assumption of Langmuir's dynamics of PLL adsorption. Retardation of ice growth in the presence of PLL occurs due to following factors: blocking of the surface by molecules of impurity and increase in the viscosity of solution with PLL addition. We used Punin's model for non-equilibrium adsorption [3] as a basis for theoretical description of the shape of kinetic curves R(ΔT) at different PLL concentrations. Calculated values for the growth rate correspond with the results of our experiments.

1. K. Matsumura, J.Y. Bae, S.H. Hyon. Cell Transplantation. 2010. V. 19. P. 691-699.
2. K. Matsumura, S.H. Hyon. Biomaterials. 2009. V. 30. P. 4842-4849.
3. Yu.O. Punin, O.I. Artamonova. Kristallographiya. 1989. V. 34. P. 1262-1266.

 

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Related papers

Presentation: Poster at 17th International Conference on Crystal Growth and Epitaxy - ICCGE-17, General Session 1, by Dmitry Vorontsov
See On-line Journal of 17th International Conference on Crystal Growth and Epitaxy - ICCGE-17

Submitted: 2013-03-27 09:38
Revised:   2013-03-27 11:08