Intrinsic Photothermal Effect Research Articles

Tensile Strain‐Mediated Bimetallene Nanozyme for Enhanced Photothermal Tumor Catalytic Therapy

AbstractNanozymes have demonstrated significant potential in combating malignant tumor proliferation through catalytic therapy. However, the therapeutic effect is often limited by insufficient catalytic performance. In this study, we propose the utilization of strain engineering in metallenes to fully expose the active regions due to their ultrathin nature. Here, we present the first report on a novel tensile strain‐mediated local amorphous RhRu (la‐RhRu) bimetallene with exceptional intrinsic photothermal effect and photo‐enhanced multiple enzyme‐like activities. Through geometric phase analysis, electron diffraction profile, and X‐ray diffraction, it is revealed that crystalline‐amorphous heterophase boundaries can generate approximately 2 % tensile strain in the bimetallene. The ultrathin structure and in‐plane strain of the bimetallene induce an amplified strain effect. Both experimental and theoretical evidence support the notion that tensile strain promotes multiple enzyme‐like activities. Functioning as a tumor microenvironment (TME)‐responsive nanozyme, la‐RhRu exhibits remarkable therapeutic efficacy both in vitro and in vivo. This work highlights the tremendous potential of atomic‐scale tensile strain engineering strategy in enhancing tumor catalytic therapy.

Tensile Strain-Mediated Bimetallene Nanozyme for Enhanced Photothermal Tumor Catalytic Therapy.

Nanozymes have demonstrated significant potential in combating malignant tumor proliferation through catalytic therapy. However, the therapeutic effect is often limited by insufficient catalytic performance. In this study, we propose the utilization of strain engineering in metallenes to fully expose the active regions due to their ultrathin nature. Here, we present the first report on a novel tensile strain-mediated local amorphous RhRu (la-RhRu) bimetallene with exceptional intrinsic photothermal effect and photo-enhanced multiple enzyme-like activities. Through geometric phase analysis, electron diffraction profile, and X-ray diffraction, it is revealed that crystalline-amorphous heterophase boundaries can generate approximately 2 % tensile strain in the bimetallene. The ultrathin structure and in-plane strain of the bimetallene induce an amplified strain effect. Both experimental and theoretical evidence support the notion that tensile strain promotes multiple enzyme-like activities. Functioning as a tumor microenvironment (TME)-responsive nanozyme, la-RhRu exhibits remarkable therapeutic efficacy both in vitro and in vivo. This work highlights the tremendous potential of atomic-scale tensile strain engineering strategy in enhancing tumor catalytic therapy.

Tailoring Photoweldable Shape Memory Polyurethane with Intrinsic Photothermal / Fluorescence Via Engineering Metal‐Phenolic Systems

AbstractMultifunctional shape memory polymers are significant for next‐generation intelligent systems as smart materials. However, their practical applications are limited by toughness, manufacturability, and functional integration strategies. Besides, while 4D printing is used to construct deformable devices, the limited accessible shapes and difficulty of integrating multiple materials hindered the development of multifunctional devices. Herein, metal‐phenolic coordination is used as crosslinks to tailor tough shape memory polyurethanes with intrinsic photothermal effect and/or tunable fluorescence. The reversible dissociation of metal‐phenolic complexes upon loading provides an efficient energy dissipation for the polymer network. The photothermal/fluorescent properties of target polyurethane can be effortlessly programmed by changing the coordinated metals and functional ligands. The obtained fluorescent polyurethane displays tunable fluorescence through the reversible dissociation‐association of dynamic bonds upon thermal stimulus. Moreover, relying on light‐triggered hybrid exchange reactions among various metal‐phenolic coordination bonds, heterogeneous interfaces can be merged to manufacture exquisite 3D shape‐shifting devices and integrate more advanced functions. As demonstrations, intrinsic photothermal‐responsive shape memory stent, and 3D fluorescent encryption device are produced based on photo‐welding instead of 4D printing. This study not only provides a convenient supramolecular strategy for constructing multifunctional smart materials but also demonstrates a feasible method for making personalized integrated architectures.

Plasmonic nanobipyramids with photo-enhanced catalytic activity under near-infrared II window for effective treatment of breast cancer

Nanozyme-based catalytic therapy is an effective method for cancer treatment, but insufficient catalytic activity presents a challenge in achieving optimal therapeutic outcomes. External light can provide an innovative approach to modulate nanozyme catalytic activity. Herein, we report on plasmonic gold nanobipyramid@cuprous oxide (Au NBP@Cu2O) nanozyme for the effective phototherapy of breast cancer. In the tumor microenvironment, Cu+-mediated Fenton-like reaction catalyzes the generation of toxic hydroxyl radicals (•OH) from endogenous hydrogen peroxide to induce apoptosis. Additionally, the Au NBP@Cu2O nanostructure improves the absorption performance of Au NBPs in the near-infrared II region through near-field enhancement of equipartite exciters and achieves a high photothermal conversion efficiency value of 58%. Remarkably, the Au NBP@Cu2O nanoheterostructure can capture hot electrons induced by equipartition excitations and promote electron-hole separation under 1064 nm laser irradiation, facilitating the production of more reactive oxygen species (ROS). The mechanism behind this enhanced catalytic activity was unraveled using femtosecond transient absorption spectroscopy. Both in vitro and in vivo investigations have demonstrated the efficacious tumor therapeutic potential of Au NBP@Cu2O nanozyme, particularly under 1064 nm laser irradiation. Furthermore, the proposed therapeutic approach has been proved to effectively block tumor metastasis, providing a promising strategy for the development of multifunctional nanotherapeutics to tackle metastatic tumors. Statement of significanceA highly effective plasmonic nanozyme has been developed to improve catalytic therapy for breast cancer. When exposed to 1064 nm laser irradiation, Au NBP@Cu2O nanozyme can promote the separation of hot electrons and holes thereby facilitating the production of reactive oxygen species. Hot electrons transfer behavior is unveiled by femtosecond transient absorption spectroscopy technique. This enhanced catalytic activity, along with the intrinsic photothermal effect, effectively kills tumor cells.

Polyserotonin as a versatile coating with pH-responsive degradation for anti-tumor therapy.

Through self-polymerization of serotonin monomer, polyserotonin (PST) can coat on arbitrary surfaces with pH-responsive degradation, which was employed for nanoparticle coating and controlled drug release, achieving a robust anti-tumor effect when combined with its intrinsic photothermal effect.

Near-Infrared Laser-Triggered In Situ Dimorphic Transformation of BF2-Azadipyrromethene Nanoaggregates for Enhanced Solid Tumor Penetration.

The shape of a drug delivery system impacts its in vivo behavior such as circulation time, accumulation, and penetration. Considering the advantages of functional dyes in bioapplications, we synthesize a class of nanoaggregates based on BF2-azadipyrromethene (aza-BODIPY) dyes, which can realize long blood circulation and deep tumor penetration simultaneously in vivo through morphological transformation modulated by a near-infrared (NIR) laser. First, when the temperature increases, the wormlike nanofibers of the aza-BODIPY-1 aggregate, possessing a long blood circulation time, can be transformed into spherical nanoparticles, which are conducive to increasing the penetration in the solid tumor. Second, without any postmodification, the nanofibers exhibit an outstandingly narrow absorption band in the NIR spectral range, so that they possess ideal photothermal properties. Through 655 nm laser irradiation, the intrinsic photothermal effect causes a local temperature increase to ∼48 °C, realizing the transformation of 1-NFs to 1-NPs. Third, the morphological transformation is real-time detected by photoacoustic (PA) imaging. By monitoring the change of the PA signal at a specific wavelength, the in vivo deformation process of nanomaterials can be traced. Consequently, the in situ morphology transformation of aza-BODIPY-based nanomaterials can simultaneously realize long blood circulation and deep penetration, resulting in the enhanced antitumor outcome.

Silicone Oil Swelling Slippery Surfaces Based on Mussel-Inspired Magnetic Nanoparticles with Multiple Self-Healing Mechanisms

In this work, a novel substrate building block, magnetic Fe3O4 nanoparticles armed with dopamine molecules were developed via mussel-inspired metal-coordination bonds. Combined with glycidyl methacrylate, polydimethylsiloxane propyl ether methacrylate, and diethylenetriamine, the original silicone oil swelling slippery liquid-infused porous surfaces (SLIPS) were first prepared by reversible coordinate bonds and strong covalent bonds cross-linking process. The matrix mechanical characteristics and surface physicochemical properties were systematically investigated. Results showed that the mechanical property of copolymer matrix and surface wettability of SLIPS can be remarkably recovered, which were due to the synergistic interactions of magnetic nanoparticles' intrinsic photothermal effect, reversible Fe-catechol coordination, and diffused lubricating liquid. After irradiating with sunlamp for 2 h and sequentially healing for 10 h under ambient conditions, the crack almost disappeared under optical microscopy with 78.25% healing efficiency (HEf) of toughness, and surface slippery was completely retrieved to water droplets. The efficient self-heal of copolymer matrix (66.5% HEf after eighth cutting-healing cycle) and recovering of slipperiness (SA < 5° and 5° < SA < 17° after fourth and eighth cutting-centrifuging-healing cycles, respectively) would extend longevity of SLIPS when subjected to multiple damages. Moreover, the prepared SLIPS displayed superb self-cleaning and liquid-repellent properties to a wide range of particulate contaminants and fluids.