Knez Daniel, Petschacher Patrick, Wiltsche Helmar, Putaux Jean-Luc, Nishiyama Yoshiharu, Ogawa Yu, Kothleitner Gerald, Nypelö Tiina, Spirk Stefan
Institute of Electron Microscopy and Nanoanalysis, Graz University of Technology, Graz, 8010, Austria.
Institute of Bioproducts and Paper Technology, Graz University of Technology, Graz, 8010, Austria.
Small. 2025 Jun;21(25):e2500351. doi: 10.1002/smll.202500351. Epub 2025 May 2.
Cellulose, a pivotal component of plant cell walls, is a widely studied biologically derived material with vast potential for numerous applications. However, visualizing the arrangement of individual cellulose molecules within hierarchical structures with electron microscopy has proven challenging due to the material's low contrast and high beam sensitivity. In this study, a novel approach is introduced that combines labeling of cellulose functional groups with high-contrast cesium counter cations (Cs) in conjunction with atomic resolution scanning transmission electron microscopy (STEM) in annular dark-field (ADF) mode at cryogenic temperatures. This technique allows for the identification of individual sulfate groups attached to cellulose chains within cellulose nanocrystal hierarchies at Ångström resolution. Systematic comparison of experimentally obtained interatomic Cs distances with simulations potentially enables the localization of the labeled functional groups at the macromolecular level. The method has the potential to elucidate the polymer chain arrangements in nanoscale soft materials.
纤维素是植物细胞壁的关键组成部分,是一种被广泛研究的生物衍生材料,在众多应用中具有巨大潜力。然而,由于该材料对比度低且对电子束敏感,利用电子显微镜观察纤维素分子在层级结构中的排列已被证明具有挑战性。在本研究中,引入了一种新方法,该方法将纤维素官能团标记与高对比度铯抗衡阳离子(Cs)相结合,并在低温下以环形暗场(ADF)模式结合原子分辨率扫描透射电子显微镜(STEM)。这项技术能够在埃分辨率下识别纤维素纳米晶体层级结构中附着在纤维素链上的单个硫酸根。将实验获得的原子间铯距离与模拟结果进行系统比较,有可能在大分子水平上定位标记的官能团。该方法有潜力阐明纳米级软材料中的聚合物链排列。