journal article·2020-08-25

Selectively Scissoring Hydrogen-Bonded Cytosine Dimer Structures Catalyzed by Water Molecules

Lei Xie, Huijun Jiang, Donglin Li, Mengxi Liu, Yuanqi Ding, Yufang Liu, Xin Li, Xuechao Li, Haiming Zhang, Zhonghuai Hou, Yi Luo, Lifeng Chi, Xiaohui Qiu, Wei Xu

ACS Nano· Volume 14· Issue 8
Publisher page

Abstract

A single-molecule-level understanding of the activity of solvating water molecules in hydrogen-bonded assemblies would provide insights into the properties of the first hydration shells. Herein, we investigate the solvation of one of the DNA bases, cytosine, whose glassy-state network formed on Au(111) contains diverse types of hydrogen-bonded dimer configurations with hierarchical strengths. Upon water exposure, a global structural transformation from interwoven chain segments to extended chains was identified by scanning tunneling microscopy and atomic force microscopy. Density functional theory calculation and coarse-grained molecular dynamics simulation indicate that water molecules selectively break the weak-hydrogen-bonded dimers at T-junctions, while the stable ones within chains remain intact. The resulting hydrated chain segments further self-assemble into molecular chains by forming strong hydrogen bonds and spontaneously releasing water molecules. Such an intriguing transformation cannot be realized by thermal annealing, indicating the dynamic nature of water molecules in the regulation of hydrogen bonds in a catalytic manner.
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Research context

OpenAlex topics: Surface Chemistry and Catalysis · Molecular Junctions and Nanostructures · Advanced Chemical Physics Studies

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

Affiliations

Interdisciplinary Materials Research Center, College of Materials Science and Engineering, Tongji University, Shanghai 201804, China

Hefei National Laboratory for Physical Sciences at the Microscale & Department of Chemical Physics, iChEM, University of Science and Technology of China, Hefei, Anhui 230026, China

CAS Key Laboratory of Standardization and Measurement for Nanotechnology, CAS Center for Excellence in Nanoscience, National Center for Nanoscience and Technology, Beijing 100190, China

College of Physics and Materials Science, Henan Normal University, Xinxiang 453007, China

University of Chinese Academy of Sciences, Beijing 100049, China

Institute of Functional Nano & Soft Materials (FUNSOM), Jiangsu Key Laboratory for Carbon-Based Functional Materials and Devices, Joint International Research Laboratory of Carbon-Based Functional Materials and Devices, Soochow University, Suzhou 215123, China

Funding

Ministry of Education of the People's Republic of China · Ministry of Science and Technology of the People's Republic of China · National Natural Science Foundation of China · Chinese Academy of Sciences · Convestro-Tongji Innovation Academy Fund

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