Locked Nucleic Acid Modification for Base‐Stacking Engineering of Self‐Assembled DNA Crystals

J Jielin Chen (State Key Laboratory of Synergistic Chem-Bio Synthesis, School of Chemistry and Chemical Engineering, New Cornerstone Science Laboratory, Frontiers Science Center for Transformative Molecules, Zhang Jiang Institute for Advanced Study and National Center for Translational Medicine, Shanghai Jiao Tong University) M Mingqiang Li (State Key Laboratory of Synergistic Chem-Bio Synthesis, State Key Laboratory of Micro-Nano Engineering Science, School of Chemistry and Chemical Engineering, New Cornerstone Science Laboratory, Frontiers Science Center for Transformative Molecules, Zhangjiang Institute for Advanced Study, and National Center for Translational Medicine) Z Ziyu Li Y Yuqing Tang (State Key Laboratory of Synergistic Chem-Bio Synthesis, School of Chemistry and Chemical Engineering, Frontiers Science Center for Transformative Molecules, Institute of Translational Medicine, Shanghai Jiao Tong University) H Hanwei Zhang J Jianing Cheng Z Zheze Dai (State Key Laboratory of Synergistic Chem-Bio Synthesis, School of Chemistry and Chemical Engineering, Frontiers Science Center for Transformative Molecules, Institute of Translational Medicine, Shanghai Jiao Tong University) X Xiaolei Zuo (Institute of Molecular Medicine, Shanghai Key Laboratory for Nucleic Acids Chemistry and Nanomedicine, Renji Hospital, School of Medicine) Q Qian Li F Fei Wang S Sisi Jia (Zhangjiang Laboratory) H Hui Lv (Institute of Materiobiology, College of Sciences) C Chunhai Fan (State Key Laboratory of Synergistic Chem-Bio Synthesis, School of Chemistry and Chemical Engineering, New Cornerstone Science Laboratory, Frontiers Science Center for Transformative Molecules, Zhang Jiang Institute for Advanced Study and National Center for Translational Medicine) X Xiaoguo Liu (State Key Laboratory of Synergistic Chem-Bio Synthesis, School of Chemistry and Chemical Engineering, New Cornerstone Science Laboratory, Frontiers Science Center for Transformative Molecules, Zhangjiang Institute for Advanced Study and National Center for Translational Medicine)

Abstract

Abstract DNA hybridization and assembly processes are governed by the concerted effects of Watson–Crick pairing and base‐stacking interactions. While sequence engineering and chemical modifications have been extensively exploited to regulate DNA hybridization processes and complex structural assembly of DNA, here we demonstrate the use of locked nucleic acid (LNA) modifications to finely tune base‐stacking interactions, which are yet to be explored in DNA assembly processes, to program the growth of self‐assembled DNA crystals. We find that sticky‐end LNA modifications decrease base‐pair spacing and enhance base‐stacking energy, which synergistically improves interstrand affinity and accelerates hybridization rate constants, as revealed by strand displacement kinetics, molecular dynamics simulations, and small‐angle X‐ray scattering analysis. This LNA‐based base‐stacking engineering strategy can finely tune base‐stacking energy landscapes to drive anisotropic growth and morphological control in self‐assembled DNA crystal. We further establish a quantitative framework for probing structure–energy relationships in base‐stacking interactions, which not only paves the way for better control of structural DNA nanotechnology but also provides mechanistic insights for developing dynamic DNA nanosystems.

Article Details

Volume / Issue Vol. 64, Issue 39
Published September 22, 2025
ISSN 1433-7851
Publisher Wiley

Journal Info

Angewandte Chemie International Edition

Wiley

ISSN: 1433-7851 Physical Sciences

Authors (14)

J

Jielin Chen

State Key Laboratory of Synergistic Chem-Bio Synthesis, School of Chemistry and Chemical Engineering, New Cornerstone Science Laboratory, Frontiers Science Center for Transformative Molecules, Zhang Jiang Institute for Advanced Study and National Center for Translational Medicine, Shanghai Jiao Tong University

M

Mingqiang Li

State Key Laboratory of Synergistic Chem-Bio Synthesis, State Key Laboratory of Micro-Nano Engineering Science, School of Chemistry and Chemical Engineering, New Cornerstone Science Laboratory, Frontiers Science Center for Transformative Molecules, Zhangjiang Institute for Advanced Study, and National Center for Translational Medicine

Z

Ziyu Li

Y

Yuqing Tang

State Key Laboratory of Synergistic Chem-Bio Synthesis, School of Chemistry and Chemical Engineering, Frontiers Science Center for Transformative Molecules, Institute of Translational Medicine, Shanghai Jiao Tong University

H

Hanwei Zhang

J

Jianing Cheng

Z

Zheze Dai

State Key Laboratory of Synergistic Chem-Bio Synthesis, School of Chemistry and Chemical Engineering, Frontiers Science Center for Transformative Molecules, Institute of Translational Medicine, Shanghai Jiao Tong University

X

Xiaolei Zuo

Institute of Molecular Medicine, Shanghai Key Laboratory for Nucleic Acids Chemistry and Nanomedicine, Renji Hospital, School of Medicine

Q

Qian Li

F

Fei Wang

S

Sisi Jia

Zhangjiang Laboratory

H

Hui Lv

Institute of Materiobiology, College of Sciences

C

Chunhai Fan

State Key Laboratory of Synergistic Chem-Bio Synthesis, School of Chemistry and Chemical Engineering, New Cornerstone Science Laboratory, Frontiers Science Center for Transformative Molecules, Zhang Jiang Institute for Advanced Study and National Center for Translational Medicine

X

Xiaoguo Liu

State Key Laboratory of Synergistic Chem-Bio Synthesis, School of Chemistry and Chemical Engineering, New Cornerstone Science Laboratory, Frontiers Science Center for Transformative Molecules, Zhangjiang Institute for Advanced Study and National Center for Translational Medicine