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琥珀酰聚糖在氯化钠水溶液中的热致构象变化

Thermally induced conformation change of succinoglycan in aqueous sodium chloride.

作者信息

Nakanishi Tomoko, Norisuye Takashi

机构信息

Department of Macromolecular Science, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan.

出版信息

Biomacromolecules. 2003 May-Jun;4(3):736-42. doi: 10.1021/bm020132f.

Abstract

Static and dynamic light scattering, viscosity, and optical rotation measurements have been made at eight different temperatures between 25 and 75 degrees C on two succinoglycan samples (sodium salt) with weight-average molecular weights M(w) of 7.14 x 10(5) and 3.54 x 10(5) (at 25 degrees C) in 0.01 M aqueous NaCl to investigate the thermally induced order-disorder conformation change of the polysaccharide. Additionally, viscometry and polarimetry have been performed for a sodium salt sample (M(w) = 4.55 x 10(5) at 25 degrees C) whose M(w), z-average radius of gyration <S(2)>(z)(1/2), and hydrodynamic radius R(H) in the aqueous salt had been determined previously. As the temperature increases, M(w), <S(2)>(z)(1/2), R(H), and the intrinsic viscosity for every sample sharply decrease around 55 degrees C where the specific rotation at 300 nm sigmoidally increases. In particular, M(w) at 25 degrees C (i.e., in the ordered helical state) is twice as large as that at 75 degrees C (i.e., in the disordered state). These findings substantiate that the ordered structure is composed of two chains and hence is a double helix. Data analysis shows that this helix at 25 degrees C is characterized by an unperturbed wormlike chain with a helix pitch of about 2 nm (per repeating unit) and a persistence length of about 50 nm and that upon heating, it dissociates directly (i.e., in all-or-none fashion) to disordered chains of a similar contour length but with a much smaller persistence length of about 10 nm. The temperature dependence of the light scattering second viral coefficient is discussed in relation to the association of disordered chains in the cooling process.

摘要

在25至75摄氏度之间的八个不同温度下,对两个琥珀酰聚糖样品(钠盐)进行了静态和动态光散射、粘度及旋光测量,这两个样品在25摄氏度时的重均分子量M(w)分别为7.14×10(5)和3.54×10(5),溶剂为0.01M的NaCl水溶液,目的是研究多糖热诱导的有序-无序构象变化。此外,还对一个钠盐样品(25摄氏度时M(w)=4.55×10(5))进行了粘度测定和旋光测定,该样品在盐水溶液中的M(w)、z-平均回转半径<S(2)>(z)(1/2)和流体力学半径R(H)此前已测定。随着温度升高,每个样品的M(w)、<S(2)>(z)(1/2)、R(H)和特性粘度在55摄氏度左右急剧下降,此时300nm处的比旋度呈S形增加。特别是,25摄氏度(即处于有序螺旋状态)时的M(w)是75摄氏度(即处于无序状态)时的两倍。这些发现证实有序结构由两条链组成,因此是双螺旋结构。数据分析表明,25摄氏度时的这种螺旋结构的特征是未受干扰的蠕虫状链,螺旋间距约为2nm(每个重复单元),持续长度约为50nm,加热时,它直接解离(即全或无方式)为轮廓长度相似但持续长度小得多(约10nm)的无序链。结合冷却过程中无序链的缔合讨论了光散射第二维里系数的温度依赖性。

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