Structure-function relationship of the GH168 fucanase reveals an unusual enzyme recognition mechanism for sulfated polysaccharide

Guangning Chen, Jingjing Shen, Xinyu Li, Menghui Sun, Sheng Dong, Ying Sun, Achiraya Khamleng, Xuanwei Mei, Yuying Zhang, Guanchen Liu, Fangyi Chen, Xiao Song, Kaimeng Liu, Yingang Feng, Changhu Xue () and Yaoguang Chang ()
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Guangning Chen: Ocean University of China
Jingjing Shen: Ocean University of China
Xinyu Li: Ocean University of China
Menghui Sun: Ocean University of China
Sheng Dong: Chinese Academy of Sciences
Ying Sun: BGI Research
Achiraya Khamleng: Ocean University of China
Xuanwei Mei: Ocean University of China
Yuying Zhang: Ocean University of China
Guanchen Liu: Ocean University of China
Fangyi Chen: Ocean University of China
Xiao Song: Ocean University of China
Kaimeng Liu: Ocean University of China
Yingang Feng: Chinese Academy of Sciences
Changhu Xue: Ocean University of China
Yaoguang Chang: Ocean University of China

Nature Communications, 2025, vol. 16, issue 1, 1-14

Abstract: Abstract Sulfated fucan is one of the most recalcitrant polysaccharides. The molecular mechanism underlying the endo-1,3-fucanase, which plays a critical role in the breakdown of sulfated fucan, remains unexplained. Here, we conduct a comprehensive structure-function relationship investigation on the endo-1,3-fucanases within a family space—GH168. The family can be divided into four subfamilies according to phylogenetic relationship and functional similarities. Subfamily I, Ⅱ and Ⅳ preferentially recognize Fucp2(OSO3−), Fucp2,4(OSO3−) and Fucp units at the +1 subsite, respectively, while consistently recognizing the Fucp2(OSO3−) unit at the −1 subsite. Remarkably, two-thirds of the interacting residues are dedicated to the recognition of sulfate groups along the glycoside chains. This mechanism is distinct from the direct recognition of the sugar backbone employed by neutral polysaccharide hydrolases. These findings unveil a critical enzyme recognition mechanism for sulfate polysaccharides and promote the application of endo-1,3-fucanases in the structural analysis and oligosaccharide production of sulfated fucan.

Date: 2025
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DOI: 10.1038/s41467-025-63891-4

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