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To further explore the factors that resist hemicelluloses degradation and release, the chemical composition and molecular weight (MW) in both the interior and exterior portions of the hydrothermally pretreated bamboo substrates were characterized. The chemical composition analysis showed that pretreatment made the lignin tend to accumulate on the exterior surface of the bamboo chips; and therefore gave rise to a large difference of lignin content between exterior and interior. Along with the degradation of hemicelluloses, the difference of hemicelluloses content in both the exterior and interior part became small. On the contrary, the hemicelluloses from the both exterior and interior portions had an invariable MW in the early stage of pretreatment; whereas, the difference of hemicelluloses MW between the exterior and interior part increased with the pretreatment continue, indicating low MW of hemicelluloses in the interior portion. Long time pretreatment promoted increasingly lignin covering on the surface of the chips; the lignin coatings might act as a hydrophobic layer blocking the access of the degraded hemicelluloses. [ABSTRACT FROM AUTHOR]