Yuanning Feng

Phototherapy—which includes photothermal therapy (PTT) and photodynamic therapy (PDT)—has evoked interest as a promising cancer treatment modality on account of its noninvasiveness, spatiotemporal precision, and minimal side effects. C. Wang et al. recently reported a near‐infrared‐activated charge transfer complex‐based nanoparticle which consists of a donor (D) and an acceptor (A). Experimental results have demonstrated a potent immunotherapeutic effect of integrating programmed cell death protein 1 antibody combination therapy in preclinical models. Incorporating D–A interactions into nanosystems for photoimmunotherapy (PIT) is still a novel approach. This approach offers a multifaceted strategy for synergistic cancer PIT which holds promising potential to transform cancer treatment paradigms.

Phototherapy—which includes photothermal therapy (PTT) and photodynamic therapy (PDT)—has evoked interest as a promising cancer treatment modality on account of its noninvasiveness, spatiotemporal precision, and minimal side effects. C. Wang et al. recently reported a near‐infrared‐activated charge transfer complex‐based nanoparticle which consists of a donor (D) and an acceptor (A). Experimental results have demonstrated a potent immunotherapeutic effect of integrating programmed cell death protein 1 antibody combination therapy in preclinical models. Incorporating D–A interactions into nanosystems for photoimmunotherapy (PIT) is still a novel approach. This approach offers a multifaceted strategy for synergistic cancer PIT which holds promising potential to transform cancer treatment paradigms.

Stereoisomerism, stemming from the spatial orientation of components in molecular structures, plays a decisive role in nature. While the unconventional bonding found in mechanically interlocked molecules gives rise to unique expressions of stereochemistry, the exploration of their stereoisomers is still in its infancy. Sequence isomerism, characterized by variations in the ordering of mechanically interlocked components in catenanes and rotaxanes, mirrors the sequence variations found in biological macromolecules. Herein, we report the use of artificial molecular pumps for the precise and simple production of sequentially isomeric hetero[3]rotaxanes. Utilizing redox-driven pumping cassettes with different rings, we have synthesized two hetero[3]rotaxane isomers in high isolated yields from two [2]rotaxanes. This research represents a significant advance in sequential molecular assembly, paving the way for the development of sophisticated, functionalized, mechanically interlocked materials.

In reticular chemistry, molecular building blocks are designed to create crystalline open frameworks. A key principle of reticular chemistry is that the most symmetrical networks are the likely outcomes of reactions, particularly when highly symmetrical building blocks are involved. The strategy of synthesizing low-dimensional networks aims to reduce explicitly the symmetry of the molecular building blocks. Here we report the spontaneous formation of hydrogen-bonded fibrous structures from trigonal prismatic building blocks, which were designed to form three-dimensional crystalline networks on account of their highly symmetrical structures. Utilizing different microscopic and spectroscopic techniques, we identify the structures at the early stages of the assembly process in order to and understand the growth mechanism. The symmetrical molecular building blocks are incorporated preferentially in the longitudinal direction, giving rise to anisotropic hydrogen-bonded porous organic nanotubes. Entropy-driven anisotropic growth provides micrometer-scale unidirectional nanotubes with high porosity. By combining experimental evidence and theoretical modeling, we have obtained a deep understanding of the nucleation and growth processes. Our findings offer fundamental insight into the molecular design of tubular structures. The nanotubes evolve further in the transverse directions to provide extended higher-order fibrous structures [nano- and microfibers], ultimately leading to large-scale interconnected hydrogen-bonded fiber-like structures with twists and turns. Our work provides fundamental understanding and paves the way for innovative molecular designs in low-dimensional networks.

Harnessing flexible host cavities opens opportunities for the design of novel supramolecular architectures that accommodate nanosized guests. This research examines unprecedented gas-phase structures of Keggin-type polyoxometalate PW₁₂O₄₀ ³⁻ (WPOM) and cyclodextrins (X-CD, X = α, β, γ, δ, ε, ζ) including previously unexplored large, flexible CDs. Using ion mobility spectrometry coupled to mass spectrometry (IM-MS) in conjunction with molecular dynamics (MD) simulations, we provide first insights into the binding modes between WPOM and larger CD hosts as isolated structures. Notably, γ-CD forms two distinct structures with WPOM through binding to its primary and secondary faces. We also demonstrate that ε-CD forms a deep inclusion complex, which encapsulates WPOM within its annular inner cavity. In contrast, ζ-CD adopts a saddle-like conformation in its complex with WPOM, which resembles its free form in solution. More intriguingly, the gas-phase CD–WPOM structures are highly correlated with their counterparts in solution as characterized by nuclear magnetic resonance (NMR) spectroscopy. The strong correlation between the gas- and solution phase structures of CD–WPOM complexes highlight the power of gas-phase IM-MS for the structural characterization of supramolecular complexes with nanosized guests, which may be difficult to examine using conventional approaches.