*Article* **Local Variations in Carbohydrates and Matrix Lignin in Mechanically Graded Bamboo Culms**

**Kexia Jin 1,3 , Zhe Ling 2, Zhi Jin 4, Jianfeng Ma 1, Shumin Yang <sup>1</sup> , Xinge Liu 1,\* and Zehui Jiang 1,\***


**Abstract:** The mechanical performance of bamboo is highly dependent on its structural arrangement and the properties of biomacromolecules within the cell wall. The relationship between carbohydrates topochemistry and gradient micromechanics of multilayered fiber along the diametric direction was visualized by combined microscopic techniques. Along the radius of bamboo culms, the concentration of xylan within the fiber sheath increased, while that of cellulose and lignin decreased gradually. At cellular level, although the consecutive broad layer (Bl) of fiber revealed a relatively uniform cellulose orientation and concentration, the outer Bl with higher lignification level has higher elastic modulus (19.59–20.31 GPa) than that of the inner Bl close to the lumen area (17.07–19.99 GPa). Comparatively, the cell corner displayed the highest lignification level, while its hardness and modulus were lower than that of fiber Bl, indicating the cellulose skeleton is the prerequisite of cell wall mechanics. The obtained cytological information is helpful to understand the origin of the anisotropic mechanical properties of bamboo.

**Keywords:** multilayered bamboo fiber; topochemistry; microscopic imaging; gradient micromechanics
