Yifan Zhang

A central challenge in three‐dimensional (3D) photoprinting lies in the absence of a deterministic translation from optical fields into volumetric chemical reaction fields. Here, we establish a photoprinting strategy in which light acts not merely as a trigger, but as a programmable input that defines a spatial chemical reaction field enabled by molecular spatial homogeneity and topochemical control. Within this light‐defined reaction field, topochemical reactions are spatially confined and propagated along the depth direction, generating continuous reaction gradients that deterministically translate optical projections into 3D chemical transformations. We realize this concept using a large‐area ADCA‐based single‐cocrystalline photoresist film, in which well‐defined molecular packing supports efficient cascade reactions. The resulting light‐defined spatial reaction field enables low‐power (µW), millimeter‐scale projection photoprinting, producing 3D nanostructures with a sub‐diffraction‐limited lateral resolution of 153 nm and an axial resolution of 3.5 nm. By integrating a home‐built projection system with computational modeling, arbitrary graphic inputs can be directly compiled into programmable 3D chemical reaction fields and rapidly translated into nanoarchitectures within seconds. These results establish topochemical reaction‐field‐guided projection photoprinting as a powerful strategy for rapid, high‐resolution three‐dimensional fabrication in ADCA‐based single‐cocrystalline photoresists and suggest a broader molecular‐design principle for future co‐crystalline photoprinting materials.

A central challenge in three‐dimensional (3D) photoprinting lies in the absence of a deterministic translation from optical fields into volumetric chemical reaction fields. Here, we establish a photoprinting strategy in which light acts not merely as a trigger, but as a programmable input that defines a spatial chemical reaction field enabled by molecular spatial homogeneity and topochemical control. Within this light‐defined reaction field, topochemical reactions are spatially confined and propagated along the depth direction, generating continuous reaction gradients that deterministically translate optical projections into 3D chemical transformations. We realize this concept using a large‐area ADCA‐based single‐cocrystalline photoresist film, in which well‐defined molecular packing supports efficient cascade reactions. The resulting light‐defined spatial reaction field enables low‐power (µW), millimeter‐scale projection photoprinting, producing 3D nanostructures with a sub‐diffraction‐limited lateral resolution of 153 nm and an axial resolution of 3.5 nm. By integrating a home‐built projection system with computational modeling, arbitrary graphic inputs can be directly compiled into programmable 3D chemical reaction fields and rapidly translated into nanoarchitectures within seconds. These results establish topochemical reaction‐field‐guided projection photoprinting as a powerful strategy for rapid, high‐resolution three‐dimensional fabrication in ADCA‐based single‐cocrystalline photoresists and suggest a broader molecular‐design principle for future co‐crystalline photoprinting materials.

Photosensitive topochemical polymerization, characterized by lattice-controlled reaction sites and rates, enables the production of highly crystalline and isotactic polymers, providing a powerful synthesis route for advancing high-performance lithographic technologies. However, the substantial challenge of achieving precise molecular packing and fabricating large-area single-crystal thin films required by topochemical reactions remains a major obstacle to realizing sub-diffraction, low-power lithographic technologies. In this study, we report a lattice-induced resolution enhancement method that exceeds the diffraction limit, in synergy with a dual solid-liquid interface confinement strategy, enabling efficient topochemical polymerization in both 2D and 3D lithographic applications. The directed fluid flow within the confined space effectively suppresses uncontrolled nucleation, facilitating the fabrication of large-area single-crystal thin-film photoresists with tunable thickness and aspect ratios. We demonstrate dual-mode photocarving on large-area photoresists at sub-50 nm resolution ( λ /10) using a low-power continuous-wave visible laser (4-20 μW), which operates at power levels several orders of magnitude lower than those required for two-photon lithography. The entire process is compatible with standard commercial optical microscopes using standard optical components. Our research introduces a versatile platform for achieving subdiffractional lithographic resolution with low-power light, demonstrating a fivefold enhancement in resolution under identical illumination conditions compared to reported photoresists.

Rapid and reliable detection of nanoplastics and other analytes in complex biological and environmental media is very important for public health management and environment protection but there is still a lack of effective methods. Here, we report optoelectronic-tweezer-assisted nanograspers (OET-NGP), a reconfigurable trapping system that dynamically assembles metallic nanoparticles into light-programmable grasping structures. This approach enables not only rapid analyte enrichment but also the formation of highly uniform hotspots with improved Surface-Enhanced Raman scattering (SERS) reproducibility, achieving a detection limit as low as 4.43 × 10^–8 M for Rhodamine B. More importantly, the OET-NGP platform enables in situ capture and SERS detection of nanoplastics at μg/mL level in both aqueous media and serum. These results highlight the capability and great promise of OET-NGP as a powerful sensing tool for effective nanoplastic detection with great potential for environmental monitoring and biosafety assessment.

Hydrogen‐bonded water clusters (H ₂ O) _n obscure the intrinsic reactivity of monomeric H ₂ O (n = 1) by restricting molecular reorientation. Elucidating the catalytic behavior of isolated water remains a key challenge in aqueous‐phase chemistry. Here, we address this by designing a molecular crystal that uniformly confines single water molecules in identical tetrahedral cavities. This platform, CB‐H ₂ O , exhibits exceptional activity for photocatalytic H ₂ O‐to‐H ₂ O ₂ conversion, achieving 7.03 mmol g ^{− 1} h ^{− 1} with pure water, representing an 11.6‐fold enhancement over cavity‐deficient controls and being markedly superior to existing photocatalytic systems. This performance advantage is directly attributed to the crystallographically defined monomeric water, as verified by isotopic labelling and in‐situ spectroscopy. Theoretical calculations further demonstrate that cavity confinement eliminates hydrogen‐bond reorganization penalties, substantially lowering the activation barrier for water oxidation. Our work establishes monomeric‐water catalysis as a distinct and efficient paradigm, showcasing molecular crystal engineering as a versatile approach to tailoring water‐involved reactions for sustainable catalysis.

Hydrogen‐bonded water clusters (H ₂ O) _n obscure the intrinsic reactivity of monomeric H ₂ O (n = 1) by restricting molecular reorientation. Elucidating the catalytic behavior of isolated water remains a key challenge in aqueous‐phase chemistry. Here, we address this by designing a molecular crystal that uniformly confines single water molecules in identical tetrahedral cavities. This platform, CB‐H ₂ O , exhibits exceptional activity for photocatalytic H ₂ O‐to‐H ₂ O ₂ conversion, achieving 7.03 mmol g ^{− 1} h ^{− 1} with pure water, representing an 11.6‐fold enhancement over cavity‐deficient controls and being markedly superior to existing photocatalytic systems. This performance advantage is directly attributed to the crystallographically defined monomeric water, as verified by isotopic labelling and in‐situ spectroscopy. Theoretical calculations further demonstrate that cavity confinement eliminates hydrogen‐bond reorganization penalties, substantially lowering the activation barrier for water oxidation. Our work establishes monomeric‐water catalysis as a distinct and efficient paradigm, showcasing molecular crystal engineering as a versatile approach to tailoring water‐involved reactions for sustainable catalysis.

The ability to produce uniform micellar nanoparticles with controlled dimension and spatially controlled functionality is a key challenge in nanoscience. Living crystallization‐driven self‐assembly (CDSA) of block copolymers (BCP) has emerged as an effective approach to generate uniform size‐tunable core‐shell micellar nanoparticles; however, most core‐shell micelles generated via CDSA consist of a continuous crystalline core from BCPs with the same core‐forming block. Herein, we perform insightful studies of heteroepitaxial CDSA process from chemical distinct core‐forming poly(ferrocenyldimethylgermane) (PFDMG) and poly(ferrocenyldimethylsilane) (PFDMS) based BCPs to produce segmented block comicelles. The heteroepitaxial growth process produced micelles with kinetically trapped crystalline cores that are thermodynamically less stable than the materials formed via spontaneous nucleation. This was rationalized by determining the previously unknown core lattice of PFDMG micelles, self‐assembly experiments, and theoretical lattice energy calculations, providing an insight into the energetic penalty associated with heteroepitaxial growth. These methods for determining the theoretical core lattice energies in these BCP systems could provide a way to screen BCP candidates that can undergo heteroepitaxial growth. Furthermore, by using our newfound understanding of these micelle systems, we achieved the formation of micelles with crystalline cores that undergo self‐sorting, driven by self‐seeding from fragmented triblock comicellar structures.

The ability to produce uniform micellar nanoparticles with controlled dimension and spatially controlled functionality is a key challenge in nanoscience. Living crystallization‐driven self‐assembly (CDSA) of block copolymers (BCP) has emerged as an effective approach to generate uniform size‐tunable core‐shell micellar nanoparticles; however, most core‐shell micelles generated via CDSA consist of a continuous crystalline core from BCPs with the same core‐forming block. Herein, we perform insightful studies of heteroepitaxial CDSA process from chemical distinct core‐forming poly(ferrocenyldimethylgermane) (PFDMG) and poly(ferrocenyldimethylsilane) (PFDMS) based BCPs to produce segmented block comicelles. The heteroepitaxial growth process produced micelles with kinetically trapped crystalline cores that are thermodynamically less stable than the materials formed via spontaneous nucleation. This was rationalized by determining the previously unknown core lattice of PFDMG micelles, self‐assembly experiments, and theoretical lattice energy calculations, providing an insight into the energetic penalty associated with heteroepitaxial growth. These methods for determining the theoretical core lattice energies in these BCP systems could provide a way to screen BCP candidates that can undergo heteroepitaxial growth. Furthermore, by using our newfound understanding of these micelle systems, we achieved the formation of micelles with crystalline cores that undergo self‐sorting, driven by self‐seeding from fragmented triblock comicellar structures.

The overuse of antibiotics in China and the resulting rise in antibiotic resistance pose an urgent need for effective antibiotic degradation in water. Developing artificial systems that mimic the catalytic efficiency of natural photoactive enzymes for this purpose remains a critical challenge. Despite decades of research, there is a notable scarcity of precisely designed scaffolds that can replicate the structural and functional efficiency of natural enzymes for waterborne antibiotic degradation, particularly at the nano‐ to micrometer scale. In this study, we present a core‐corona type fiber‐like micellar system designed for photothermal‐assisted β‐lactam antibiotic degradation (PAD) in water. This system integrates photothermal molecular chromophores (zinc porphyrin) and ionic copper degradation catalysts in close proximity within grafted solvophilic coronal chains on the surface of fiber‐like crystalline scaffold. By employing a living crystallization‐driven self‐assembly (CDSA) strategy, we fine‐tune the composition, dimensions, and antibiotic degradation performance of the PAD nanofibers. The tailored colloidal stable PAD nanofibers achieve a penicillin G degradation rate of 0.35 min⁻¹ per micromole of copper under simulated sunlight irradiation (AM 1.5) in deionized water, offering a promising platform for sustainable environmental remediation.