近日，华南理工大学王宇团队研究了解聚三联体：对映选择性手性分子组装的催化框架。2025年12月23日出版的《美国化学会志》发表了这项成果。

手性分子组装是开发生命启发功能材料的前沿领域，然而针对其对映选择性催化的预测框架至今尚未建立。

研究组提出“催化组装三要素”——一个以手性超分子笼为模型系统验证的催化对映选择性组装机制范式。通过结合原位表征、从头计算与机器学习，他们阐明了催化剂如何必须协同调控附着、手性控制与解离三个过程以引导组装路径。动力学与结构分析表明，手性二胺催化剂（如环己二胺）通过模板化瞬态中间体来实现对映选择性，其中形变诱导的亲和力变化驱动了催化剂的适时释放。

基于计算得出的三要素量化指标（ΔE_att、ΔE_ctl 与 ΔE_det），我们建立了一个预测框架，并经由贝叶斯聚类与实验测试验证。该框架在不同分子类别中实现了预测与实测催化剂效能的完全吻合。此框架桥接了酶协同性与超分子组装，为可编程手性传递和自适应手性材料的催化剂设计开辟了新路径。

附：英文原文

Title: Catassembly Triad: A Catalytic Framework for Enantioselective Chiral Molecular Assembly

Author: Zhihao Li, Xuehai Huang, Yansong Jiang, Wei Zeng, Ding Zou, Xue Dong, Liulin Yang, Xiaoyu Cao, Zhongqun Tian, Yu Wang

Issue&Volume: December 23, 2025

Abstract: Chiral molecular assembly represents a frontier in creating life-inspired functional materials; yet, a predictive framework for its enantioselective catalysis remains elusive. Here, we introduce the Catassembly Triad – a mechanistic paradigm for catalytic enantioselective assembly, demonstrated using chiral supramolecular cages as a model system. Combining in situ characterization, ab initio calculations, and machine learning, we resolve how catalysts must harmonize attachment, chiral control, and detachment to direct assembly pathways. Kinetic and structural analyses reveal that chiral diamine catalysts (e.g., cyclohexanediamine) enforce enantioselectivity by templating transient intermediates with deformation-induced affinity changes driving timely catalyst release. We establish a predictive framework based on quantitative triad metrics (ΔEatt, ΔEctl, and ΔEdet) from calculations, validated by Bayesian clustering and experimental testing. The framework achieves a perfect concordance between predicted and observed catalyst efficacy across diverse molecular classes. This framework bridges enzymatic cooperativity and supramolecular assembly, enabling programmable chirality transfer and unlocking catalyst design for adaptive chiral materials.

DOI: 10.1021/jacs.5c16840

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.5c16840