4.7 Article

Poly(L-Ala-co-L-Lys) Exhibits Excellent Ice Recrystallization Inhibition Activity

Journal

ACS MACRO LETTERS
Volume 10, Issue 11, Pages 1436-1442

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acsmacrolett.1c00584

Keywords

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Funding

  1. National Research Foundation of Korea - Korean Government [2020R1A2C2007101, 2017R1A5A1015365]
  2. Korea Basic Science Institute (National Research Facilities and Equipment Center) - Ministry of Education [2020R1A6C 101B194]

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This study found that poly(L-alanine-co-L-lysine) (PAK) exhibits IRI activity similar to poly(vinyl alcohol) and generates cubic-to-spherical shaped ice crystals, showing superior performance. In contrast, poly(L-alanine-co-L-aspartic acid) (PAD) and poly(ethylene glycol) (PEG) with similar molecular weights did not provide significant IRI activity. FTIR and circular dichroism spectroscopies indicated that PAK forms alpha-helices, while PAD forms random coils in water. Additionally, dynamic ice shaping study suggested strong interaction between PAK and ice crystals, while PAD and PEG only weakly interact.
The control of ice recrystallization is very important in cryo-technological fields such as the food industry, biopharmaceuticals, and cell storage. Ice recrystallization inhibition (IRI) compounds are therefore designed to limit the growth of ice crystals, decrease the crystal size, and control the crystal shape. To improve the IRI activity of cryo-systems, various synthetic polymers such as biomimetic polypeptides from polar fish, facially amphiphilic polymers, polyampholytes, poly(vinyl alcohol) derivatives, and block copolymers with hydrophilic-hydrophobic balance have been developed. Except for graphene oxide, poly(vinyl alcohol) has thus far exhibited the best performance among these polymers. Herein, poly(L-alanine-co-L-lysine) (PAK) was shown to exhibit a similar IRI activity to that of poly(vinyl alcohol). Moreover, in contrast to the needle-shaped ice crystals generated by the aqueous PVA solution, the PAK solution was shown to generate cubic-to-spherical shaped ice crystals. Furthermore, neither poly(L-alanine-co-L-aspartic acid) (PAD) nor poly(ethylene glycol) (PEG) with a similar molecular weight provided any significant IRI activity. Examination by FTIR and circular dichroism spectroscopies indicated that the PAK forms alpha-helices, whereas the PAD forms random coils in water. Further, a dynamic ice shaping study suggested that PAK strongly interacts with ice crystals, whereas PAD and PEG only weakly interact. These results suggest that PAK is an important compound with superior IRI activity and that this activity is dependent upon the functional groups and secondary structure of the polypeptides.

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