Lihan Rong

Lanthanide-based nanomaterials have attracted increasing attention as photothermal agents for cancer therapy. However, achieving high photothermal conversion efficiency while maintaining good biocompatibility remains a significant challenge. In this work, lanthanide coordination nanocrystals with a silver ragwort-like architecture were constructed through the coordination of La[Formula: see text] ions with an amino ligand, 1,5-diaminonaphthalene, forming a La–amine coordination platform (LN5). Through crystal phase modulation via ultrasonic treatment and heterometal co-doping with Eu[Formula: see text] and Gd[Formula: see text] ions, two types of coordination nanocrystals, LN5(I) and LN5Eu[Formula: see text]Gd[Formula: see text], were successfully engineered with controlled particle sizes of approximately 15[Formula: see text]±[Formula: see text]5[Formula: see text]nm and 20[Formula: see text]±[Formula: see text]5[Formula: see text]nm, respectively. The heterometal doping strategy not only regulated the crystallographic evolution of the coordination framework but also altered the energy dissipation pathways, leading to distinct optical and photothermal properties. LN5(I) exhibited yellow fluorescence emission centered at approximately 569[Formula: see text]nm, whereas LN5Eu[Formula: see text]Gd[Formula: see text] displayed a purple emission band within the range of 350–450[Formula: see text]nm, enabling potential dual-modal imaging capabilities. Importantly, both coordination nanocrystals demonstrated remarkable photothermal conversion efficiencies under 808[Formula: see text]nm near-infrared (NIR) irradiation, reaching 63.9% for LN5 and 67.1% for LN5Eu[Formula: see text]Gd[Formula: see text]. In vitro photothermal experiments revealed that the temperature of the nanocrystal dispersion increased to above 60[Formula: see text]C within 10[Formula: see text]min of NIR irradiation. In vivo thermal imaging further confirmed that the tumor-site temperature rapidly exceeded 50[Formula: see text]C under the same irradiation conditions, leading to effective thermal ablation of tumor tissues. Comprehensive biosafety assessments indicated low cytotoxicity and minimal immune interference. In vivo antitumor studies demonstrated significant tumor growth suppression, particularly in the LN5Eu[Formula: see text]Gd[Formula: see text] combined with laser irradiation group. Overall, this work establishes amino-ligand-coordinated lanthanide nanocrystals as promising photothermal theranostic platforms, integrating efficient photothermal therapy with fluorescence imaging capabilities for potential applications in cancer nanomedicine.

The scalable fabrication of hydrogels with high toughness and low hysteresis is critically hindered by oxygen inhibition, which typically produces brittle, highly crosslinked (HC) networks. This study presents an oxygen-tolerant photoinduced electron transfer–reversible addition–fragmentation chain transfer (PET-RAFT) strategy for synthesizing highly entangled (HE) polyacrylamide hydrogels under open-vessel conditions. By optimizing the water-to-monomer ratio (W = 3.9) and introducing lithium chloride (LiCl) for spatial confinement, we achieved a fundamental shift in mechanical performance. The optimized HE hydrogel exhibited a fracture energy of 1.39 MJ/m³ and a fracture strain of ~900%, starkly contrasting the brittle failure of the HC control (W = 20, C = 10⁻²) at ~50% strain. This represents an order-of-magnitude improvement in deformability. Furthermore, the incorporation of 15 wt% LiCl amplified the HE hydrogel’s fracture energy to 2.17 MJ/m³ while maintaining its low hysteresis. This method enables the rapid, scalable production of robust, transparent thin films that exhibit dual passive cooling via radiative emission (>89% emissivity) and evaporation, rapid self-healing, and reliable strain sensing at temperatures as low as −20 °C. The synergy of entanglement design and confinement engineering establishes a versatile platform for manufacturing multifunctional hydrogels that vastly outperform their crosslink-dominated predecessors.

Fe³⁺-incorporated hydrogels are particularly valuable for wearable devices due to their tunable mechanical properties and ionic conductivity. However, conventional immersion-based fabrication fundamentally limits hydrogel performance because of heterogeneous ion distribution, ionic leaching, and scalability limitations. To overcome these challenges, we report a novel one-pot strategy where controlled amounts of Fe³⁺ are directly added to polyacrylamide-sodium acrylate (PAM-SA) precursor solutions, ensuring homogeneous ion distribution. Combining this with Photoinduced Electron/Energy Transfer Reversible Addition–Fragmentation Chain Transfer (PET-RAFT) polymerization enables efficient hydrogel fabrication under open-vessel conditions, improving its scalability. Fe³⁺ concentration achieves unprecedented modulation of mechanical properties: Young’s modulus (10 to 150 kPa), toughness (0.26 to 2.3 MJ/m³), and strain at break (800% to 2500%). The hydrogels also exhibit excellent compressibility (90% strain recovery), energy dissipation (>90% dissipation efficiency at optimal Fe³⁺ levels), and universal adhesion to diverse surfaces (plastic, metal, PTFE, and cardboard). Finally, these Fe³⁺-incorporated hydrogels demonstrated high effectiveness as strain sensors for monitoring finger/elbow movements, with gauge factors dependent on composition. This work provides a scalable, oxygen-tolerant route to tunable hydrogels for advanced wearable devices.

Patterned surfaces with distinct regularity and structured arrangements have attracted great interest due to their extensive promising applications. Although colloidal patterning has conventionally been used to create such surfaces, herein, we introduce a novel 3D patterned poly(N-isopropylacrylamide) (PNIPAM) surface, synthesized by using a combination of colloidal templating and surface-initiated photoinduced electron transfer-reversible addition-fragmentation chain transfer (SI-PET-RAFT) polymerization. In order to investigate the temperature-driven 3D morphological variations at a lower critical solution temperature (LCST) of ∼32 °C, multifaceted characterization techniques were employed. Atomic force microscopy confirmed the morphological transformations at 20 and 40 °C, while water contact angle measurements, upon heating, revealed distinct trends, offering insights into the correlation between surface wettability and topography adaptations. Moreover, quartz crystal microbalance with dissipation monitoring and electrochemical measurements were employed to detect the topographical adjustments of the unique hollow capsule structure within the LCST. Tests using different sizes of PSNPs shed light on the size-selective capture-release potential of the patterned PNIPAM, accentuating its biomimetic open-close behavior. Notably, our approach negates the necessity for expensive proteins, harnessing temperature adjustments to facilitate the noninvasive and efficient reversible capture and release of nanostructures. This advancement hopes to pave the way for future innovative cellular analysis platforms.

Recently, photoinduced electron/energy transfer reversible addition–fragmentation chain transfer (PET‐RAFT) polymerization has been developed and gaining wide acceptance. PET‐RAFT polymerization uses visible light to initiate the reaction and is compatible with ambient conditions and green solvents. It also maintains the ability to produce well‐defined polymers and possesses high potential as an alternative to the conventional RAFT technique. This review aims to summarize the fundamentals of PET‐RAFT polymerization, highlight two of the most commonly studied applications of PET‐RAFT process (i.e. flow chemistry and surface‐initiated polymerization), and explore perspectives and new possibilities of the technique. © 2022 Society of Industrial Chemistry.