使用 l-丙氨酸/l-赖氨酸共聚物抑制冰再结晶,ACS Applied Polymer Materials

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使用 l-丙氨酸/l-赖氨酸共聚物抑制冰再结晶
ACS Applied Polymer Materials ( IF 4.4 ) Pub Date : 2022-03-30 , DOI: 10.1021/acsapm.2c00174
Soyeon Park ₁ , Zhengyu Piao ₁ , Jin Kyung Park ₁ , Hyun Jung Lee ₁ , Byeongmoon Jeong ₁

Affiliation

最近，据报道聚（l-丙氨酸-co - l-赖氨酸）（PAK）表现出与聚（乙烯醇）相当的冰重结晶抑制（IRI）活性，聚（乙烯醇）在合成聚合物（ ACS）中具有最高的IRI活性。Macro Lett. 2021, 10, 1436–1442)。作为研究的继续，我们合成了一系列 PAK 共聚物，通过改变 (1) l-丙氨酸/ l-赖氨酸 (A/K ) 0/100、50/50、60/40 和 70/30 之间的比率和 (2) 在 A/K 的固定 50/50 比率下，PAK 的分子量在 4、9 和 15 kDa 之间。作为疏水性lPAK 的丙氨酸成分从 0% 增加到 70%，相对于磷酸盐缓冲液的平均最大粒径 (MLGS) 在 1.0 mg/mL 时从 74% 降低到 11%。随着 PAK 的分子量从 4 kDa 增加到 15 kDa，MLGS 在 1.0 mg/mL 时从 32% 下降到 15%。冰成核温度随着疏水性l的降低而降低-丙氨酸组成和PAK的分子量增加。PAK 的热滞后 (TH) 在 1.0 mg/mL 时约为 0.05 °C，随着分子量从 4 kDa 增加到 15 kDa，则增加到 0.2 °C。冰淇淋的冰晶大小与 IRI 活性呈相似趋势。为了了解 PAK 的 IRI 效应的潜在化学性质，进行了圆二色光谱、动态冰成形研究和傅里叶变换红外光谱。这些研究表明，α-螺旋度、疏水/亲水平衡、PAK 的分子量以及聚合物与冰晶之间相互作用的程度与 IRI 活性有关，这延伸到冰成核抑制、冰形成的 TH、冰成型、甚至冰淇淋的冰晶大小。

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Ice Recrystallization Inhibition Using l-Alanine/l-Lysine Copolymers

Recently, poly(l-alanine-co-l-lysine) (PAK) was reported to exhibit an ice recrystallization inhibition (IRI) activity comparable to that of poly(vinyl alcohol), which has the highest IRI activity among synthetic polymers (ACS Macro Lett.2021,10, 1436–1442). As a continuation of the study, we synthesized a series of PAK copolymers to investigate the structure–property relationship of PAK on the IRI activity and its mechanism by varying the (1) composition of the l-alanine/l-lysine (A/K) ratio among 0/100, 50/50, 60/40, and 70/30 and (2) molecular weight of PAK among 4, 9, and 15 kDa at a fixed 50/50 ratio of A/K. As the hydrophobic l-alanine composition of PAK increased from 0 to 70%, the mean largest grain size (MLGS) relative to phosphate-buffered saline decreased from 74 to 11% at 1.0 mg/mL. As the molecular weight of PAK increased from 4 to 15 kDa, the MLGS decreased from 32 to 15% at 1.0 mg/mL. The ice nucleation temperature decreased as the hydrophobic l-alanine composition and the molecular weight of PAK increased. The thermal hysteresis (TH) of PAK was about 0.05 °C at 1.0 mg/mL and increased to 0.2 °C as the molecular weight increased from 4 to 15 kDa. The ice crystal size of ice cream showed a similar trend to IRI activity. To understand the underlying chemistry of the IRI effect of PAK, circular dichroism spectroscopy, a dynamic ice shaping study, and Fourier-transform infrared spectroscopy were carried out. These studies suggest that the α-helicity, hydrophobic/hydrophilic balance, molecular weight of PAK, and extent of interactions between polymers and ice crystals are related to the IRI activity, which extends to ice nucleation inhibition, TH of ice formation, ice shaping, and even the ice crystal size of ice cream.

更新日期：2022-03-30

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