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辛烯基琥珀酸酐改性甜玉米可溶性淀粉中取代酯基位置的解析

Elucidation of substituted ester group position in octenylsuccinic anhydride modified sugary maize soluble starch.

作者信息

Ye Fan, Miao Ming, Huang Chao, Lu Keyu, Jiang Bo, Zhang Tao

机构信息

State Key Laboratory of Food Science and Technology, Synergetic Innovation Center of Food Safety and Nutrition, Jiangnan University , 1800 Lihu Avenue, Wuxi, Jiangsu 214122, People's Republic of China.

出版信息

J Agric Food Chem. 2014 Dec 3;62(48):11696-705. doi: 10.1021/jf5035064. Epub 2014 Nov 18.

Abstract

The octenylsuccinic groups in esterification-modified sugary maize soluble starches with a low (0.0191) or high (0.0504) degree of substitution (DS) were investigated by amyloglucosidase hydrolysis followed by a combination of chemical and physical analysis. The results showed the zeta-potential remained at approximately the same value regardless of excessive hydrolysis. The weight-average molecular weight decreased rapidly and reached 1.22 × 10(7) and 1.60 × 10(7) g/mol after 120 min for low-DS and high-DS octenylsuccinic anhydride (OSA) modified starch, respectively. The pattern of z-average radius of gyration as well as particle size change was similar to that of Mw, and z-average radius of gyration decreased much more slowly, especially for high-DS OSA starch. Compared to native starch, two characteristic absorption peaks at 1726.76 and 1571.83 cm(-1) were observed in FT-IR spectra, and the intensity of absorption peaks increased with increasing DS. The NMR results showed that OSA starch had several additional peaks at 0.8-3.0 ppm and a shoulder at 5.56 ppm for OSA substituents, which were grafted at O-2 and O-3 positions in soluble starch. The even distribution of OSA groups in the center area of soluble starch particle has been directly shown under CLSM. Most substitutions were located near branching points of soluble starch particles for a low-DS modified starch, whereas the substituted ester groups were located near branching points as well as at the nonreducing ends in OSA starch with a high DS.

摘要

通过淀粉葡萄糖苷酶水解,然后结合化学和物理分析,研究了低取代度(0.0191)或高取代度(0.0504)的酯化改性甜玉米可溶性淀粉中的辛烯基琥珀酸基团。结果表明,无论过度水解与否,ζ电位都保持在大致相同的值。低取代度和高取代度的辛烯基琥珀酸酐(OSA)改性淀粉在水解120分钟后,重均分子量迅速下降,分别达到1.22×10⁷和1.60×10⁷ g/mol。z平均回转半径以及粒径变化的模式与重均分子量相似,并且z平均回转半径下降得慢得多,尤其是对于高取代度的OSA淀粉。与天然淀粉相比,在傅里叶变换红外光谱(FT-IR)中观察到在1726.76和1571.83 cm⁻¹处有两个特征吸收峰,并且吸收峰的强度随着取代度的增加而增加。核磁共振(NMR)结果表明,OSA淀粉在0.8 - 3.0 ppm处有几个额外的峰,在5.56 ppm处有一个肩峰代表OSA取代基,这些取代基接枝在可溶性淀粉的O-2和O-3位置。在共聚焦激光扫描显微镜(CLSM)下直接显示了OSA基团在可溶性淀粉颗粒中心区域的均匀分布。对于低取代度改性淀粉,大多数取代位于可溶性淀粉颗粒的分支点附近,而在高取代度的OSA淀粉中,取代的酯基团位于分支点附近以及非还原端。

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