High-Resolution Atomic Force Microscopy of Native Valonia Cellulose I Microcrystals

We have studied the surface of native Valonia cellulose I microcrystals under propanol and waterby atomic force microscopy (AFM). Ultra-high-resolution images of the surface are presented, as well as lower resolution morphological observations of whole crystals. The pitch of 0.52 nm along the molecule due to the asymmetrical glucose unit and the intermolecular spacing of approximately 0.6 nm are clearly resolved in both imaging environments. The relationship between the crystalline bulk and the surface are discussed, with particular attention being paid to previous crystallographic studies. We also show that the glucose units along the cellulose chains are not topographically equivalent due to the twofold screw symmetry and accordingly present strong evidence of triclinic character by direct surface imaging, rather than by taking average measurements in reciprocal space. The crystallographic distinction between monoclinic and triclinic structure is a displacement of the cellulose chains by a quarter of the c axis period, resulting in either a stagger or a diagonal shifting, respectively, of the cellobiose unit along the chain axis by 0.26 nm. This structural identification (in real space) represents, as far as we are aware, the highest resolution AFM imaging of a biological specimen to date. This study opens up the future possibility of identifying the localized triclinic or monoclinic nature of the Valonia cellulose surface with AFM.