Algae Extraction Controllable Delamination of Vanadium Carbide Nanosheets with Enhanced Near-Infrared Photothermal Performance

The two-dimensional (2D) vanadium carbide (V₂C) MXene has shown great potential as a photothermal agent (PTA) for photothermal therapy (PTT). However, the use of V₂C in PTT is limited by the harsh synthesis condition and low photothermal conversion efficiency (PTCE). Herein, we report a completely different green delamination method using algae extraction to intercalate and delaminate V₂AlC to produce mass V₂C nanosheets (NSs) with a high yield (90 %). The resulting V₂C NSs demonstrated good structural integrity and remarkably high absorption in near infrared (NIR) region with a PTCE as high as 48 %. Systemic in vitro and in vivo studies demonstrate that the V₂C NSs can serve as efficient PTA for photoacoustic (PA) and magnetic resonance imaging (MRI)-guided PTT of cancer. This work provides a cost-effective, environment-friendly, and high-yielding disassembly approach of MAX, opening a new avenue to develop MXenes with desirable properties for a myriad of applications.     

Organic‐Base‐Driven Intercalation and Delamination for the Production of Functionalized Titanium Carbide Nanosheets with Superior Photothermal Therapeutic Performance

The delamination of titanium carbide sheets, an intriguing class of two‐dimensional materials, has been critically dependent on the extraction of interlayer Al in acidic media, such as concentrated hydrofluoric acid (HF) or a mixture of hydrochloric acid (HCl) and a fluoride salt. Herein, we report an organic‐base‐driven intercalation and delamination of titanium carbide that takes advantage of the amphoteric nature of interlayer Al. The resulting aluminum‐oxoanion‐functionalized titanium carbide sheets manifested unusually strong optical absorption in the near‐infrared (NIR) region with a mass extinction coefficient as high as 29.1 L g^?1 cm^?1 at 808 nm. Thus, the performance of this material is comparable or even superior to that of state‐of‐the‐art photoabsorption materials, including gold‐based nanostructures, carbon‐based materials, and transition‐metal dichalcogenides. Preliminary studies show that the titanium carbide sheets serve as efficient photothermal agents against tumor cells.     

Copper Sulfide Nanoparticles with Phospholipid‐PEG Coating for In Vivo Near‐Infrared Photothermal Cancer Therapy

In this work, small sizes of hydrophobic copper sulfide nanoparticles (CuS NPs, ～3.8 nm in diameter) have been successfully prepared from the reaction of copper chloride with sodium diethyldithiocarbamate (SDEDTC) inside a heated oleylamine solution. These CuS NPs displayed strong absorption in the 700–1100 nm near‐infrared (NIR) region. By coating CuS NPs with DSPE‐PEG2000 on the surface, the as‐synthesized CuS@DSPE‐PEG NPs exhibited good water solubility, significant stability and biocompatibility, as well as excellent photothermal conversion effects upon exposure to an 808 nm laser. After intravenous administration to mice, the CuS@DSPE‐PEG NPs were found to passively target to the tumor site, and tumor tissues could be ablated efficiency under laser irradiation. In addition, CuS@DSPE‐PEG NPs do not show significant toxicity by histological and blood chemistry analysis, and can be effectively excreted via metabolism. Our results indicated that CuS@DSPE‐PEG NPs can act as an ideal photothermal agent for cancer photothermal therapy.     

Ag@TiO2 Nanoprisms with Highly Efficient Near‐Infrared Photothermal Conversion for Melanoma Therapy

Melanoma is a primary reason of death from skin cancer and associated with high lethality. Photothermal therapy (PTT) has been developed into a powerful cancer treatment technique in recent years. Here, we created a low‐cost and high‐performance PTT agent, Ag@TiO₂ NPs, which possesses a high photothermal conversion efficiency of ≈65 % and strong near‐infrared (NIR) absorption about 808 nm. Ag NPs were synthesized using a two‐step method and coated with TiO₂ to obtain Ag@TiO₂ NPs by a facile sol‐gel method. Because of the oxide, Ag@TiO₂ NPs exhibit remarkable high photothermal conversion efficiencies and biocompatibility in vivo and in vitro. Cytotoxicity and therapeutic efficiency of photothermal cytotoxicity of Ag@TiO₂ NPs were tested in B16‐F10 cells and C57BL/6J mice. Under light irradiation, the elevated temperature causes cell death in Ag NPs‐treated (100 μg mL^?1) cells in vitro (both p<0.01). In the case of subcutaneous melanoma tumor model, Ag@TiO₂ NPs (100 μg mL^?1) were injected into the tumor and irradiated with a 808 nm laser of 2 W cm^?2 for 1 minute. As a consequence, the tumor volume gradually decreased by NIR laser irradiation with only a single treatment. The results demonstrate that Ag@TiO₂ NPs are biocompatible and an attractive photothermal agent for cutaneous melanoma by local delivery.     

Synthesis of a Near‐Infrared BODIPY Dye for Bioimaging and Photothermal Therapy

The development of robust photothermal agents for near‐infrared (NIR) imaging is a great challenge. Herein, we report the design and synthesis of a new photothermal agent, based on the aza‐boron‐dipyrromethene framework (azaBDP). This compound possessed excellent photostability and high photothermal‐conversion efficiency (50 %) under NIR laser irradiation. When the photothermal properties of this compound were utilized for tumor inhibition, stable long‐term fluorescence was observed in living animals. Photothermal treatment efficiently suppressed tumor growth, as evidenced by in vitro and in vivo experiments. Furthermore, NIR emission could be detected by using an imaging system and therapeutic self‐monitoring was achieved by using NIR imaging.     

Cocrystals Strategy towards Materials for Near‐Infrared Photothermal Conversion and Imaging

A cocrystal strategy with a simple preparation process is developed to prepare novel materials for near‐infrared photothermal (PT) conversion and imaging. DBTTF and TCNB are selected as electron donor (D) and electron acceptor (A) to self‐assemble into new cocrystals through non‐covalent interactions. The strong D–A interaction leads to a narrow band gap with NIR absorption and that both the ground state and lowest‐lying excited state are charge transfer states. Under the NIR laser illumination, the temperature of the cocrystal sharply increases in a short time with high PT conversion efficiency (η=18.8 %), which is due to the active non‐radiative pathways and inhibition of radiative transition process, as revealed by femtosecond transient absorption spectroscopy. This is the first PT conversion cocrystal, which not only provides insights for the development of novel PT materials, but also paves the way of designing functional materials with appealing applications.     

Facile Fabrication of Near‐Infrared‐Responsive and Chitosan‐Functionalized Cu2Se Nanoparticles for Cancer Photothermal Therapy

Photothermal therapy has attracted much interest for use in cancer treatment in recent years. In this study, Cu₂Se nanoparticles as a novel photothermal agent modified by chitosan (CS‐Cu₂SeNPs) were successfully synthesized through a facile route at room temperature. The as‐synthesized CS‐Cu₂SeNPs exhibited good water solubility and significant stability. CS‐Cu₂SeNPs can efficiently convert near‐infrared (NIR) light into heat and exhibit excellent thermostability. In vitro experiments showed that CS‐Cu₂SeNPs had selective cellular uptake between cancer and normal cells and expressed clear anticancer activity on A375 and HeLa human cancer cells. In addition, the anticancer activity was increased to about 400 % by combination with a laser at 808 nm, which acted through induction of apoptosis with the involvement of intrinsic and extrinsic pathways. CS‐Cu₂SeNPs irradiated with a laser effectively triggered the intracellular reactive oxygen species (ROS) overproduction that promoted cell apoptosis. Therefore, the developed CS‐Cu₂SeNPs could be used as a novel phototherapeutic agent for the photothermal therapy of human cancers.     

Macrotheranostic Probe with Disease‐Activated Near‐Infrared Fluorescence,Photoacoustic, and Photothermal Signals for Imaging‐Guided Therapy

Theranostics provides opportunities for precision cancer therapy. However, theranostic probes that simultaneously turn on their diagnostic signal and pharmacological action only in respond to a targeted biomarker have been less exploited. We herein report the synthesis of a macrotheranostic probe that specifically activates its near‐infrared fluorescence (NIRF), photoacoustic (PA), and photothermal signals in the presence of a cancer‐overexpressed enzyme for imaging‐guided cancer therapy. Superior to the small‐molecule counterpart probe, the macrotheranostic probe has ideal biodistribution and renal clearance, permitting passive targeting of tumors, in situ activation of multimodal signals, and effective photothermal ablation. Our study thus provides a macromolecular approach towards activatable multimodal phototheranostics.     

Two‐Dimensional Nanomaterials for Photothermal Therapy

Two‐dimensional (2D) nanomaterials are currently explored as novel photothermal agents because of their ultrathin structure, high specific surface area, and unique optoelectronic properties. In addition to single photothermal therapy (PTT), 2D nanomaterials have demonstrated significant potential in PTT‐based synergistic therapies. In this Minireview, we summarize the recent progress in 2D nanomaterials for enhanced photothermal cancer therapy over the last five years. Their unique optical properties, typical synthesis methods, and surface modification are also covered. Emphasis is placed on their PTT and PTT‐synergized chemotherapy, photodynamic therapy, and immunotherapy. The major challenges of 2D photothermal agents are addressed and the promising prospects are also presented.     

Deep‐Level Defect Enhanced Photothermal Performance of Bismuth Sulfide–Gold Heterojunction Nanorods for Photothermal Therapy of Cancer Guided by Computed Tomography Imaging

Bismuth sulfide (Bi₂S₃) nanomaterials are emerging as a promising theranostic platform for computed tomography imaging and photothermal therapy of cancer. Herein, the photothermal properties of Bi₂S₃ nanorods (NRs) were unveiled to intensely correlate to their intrinsic deep‐level defects (DLDs) that potentially could work as electron–hole nonradiative recombination centers to promote phonon production, ultimately leading to photothermal performance. Bi₂S₃‐Au heterojunction NRs were designed to hold more significant DLD properties, exhibiting more potent photothermal performance than Bi₂S₃ NRs. Under 808 nm laser irradiation, Bi₂S₃‐Au NRs could trigger higher cellular heat shock protein 70 expression and more apoptotic cells than Bi₂S₃ NRs, and caused severe cell death and tumor growth inhibition, showing great potential for photothermal therapy of cancer guided by computed tomography imaging.     

Near‐Infrared Croconaine Rotaxanes and Doped Nanoparticles for Enhanced Aqueous Photothermal Heating

The photothermal effect is the generation of heat by molecules or particles upon high‐energy laser irradiation, and near‐infrared absorbers such as gold nanoparticles and organic dyes have a range of potential photothermal applications. The favourable photothermal properties of thiophene‐functionalised croconaine dyes were recently discovered. The synthesis and properties of novel croconaine rotaxane and pseudorotaxane architectures capable of efficient photothermal performance in both organic and aqueous environments are reported. The versatility of this dye‐encapsulation strategy was demonstrated by the preparation of two organic croconaine rotaxanes using different synthetic methods: the formation of an aqueous pseudorotaxane association complex, and the synthesis of water‐soluble, croconaine‐doped silicated micelle nanoparticles. All of these near‐infrared‐absorbing systems exhibit excellent photothermal behaviour, with pseudorotaxane and rotaxane formation vital for effective aqueous heat generation. Dye encapsulation provides steric protection to enhance the stability of a water‐sensitive croconaine dye, while rotaxane‐doped nanoparticles avoid detrimental band broadening caused by chromophore coupling.     

Platelet‐Facilitated Photothermal Therapy of Head and Neck Squamous Cell Carcinoma

Here, we present a platelet‐facilitated photothermal tumor therapy (PLT‐PTT) strategy, in which PLTs act as carriers for targeted delivery of photothermal agents to tumor tissues and enhance the PTT effect. Gold nanorods (AuNRs) were first loaded into PLTs by electroporation and the resulting AuNR‐loaded PLTs (PLT‐AuNRs) inherited long blood circulation and cancer targeting characteristics from PLTs and good photothermal property from AuNRs. Using a gene‐knockout mouse model, we demonstrate that the administration of PLT‐AuNRs and localizing laser irradiation could effectively inhibit the growth of head and neck squamous cell carcinoma (HNSCC). In addition, we found that the PTT treatment augmented PLT‐AuNRs targeting to the tumor sites and in turn, improved the PTT effects in a feedback manner, demonstrating the unique self‐reinforcing characteristic of PLT‐PTT in cancer therapy.     

Fused Isoindigo Ribbons with Absorption Bands Reaching Near‐Infrared

Through fusing isoindigo (IID) units at 6,7;6′,7′‐positions, a series of new near‐infrared (NIR) absorbing and stable ribbon‐like conjugated molecules, namely nIIDs in which n represents the number of IID units, have been synthesized. The optical band gaps of the molecules are lowered from 2.03 eV of 1IID to 1.12 eV of 6IID with the increase of the conjugation length. 3IID, 4IID, and 6IID have strong absorption in the NIR region and exhibit photothermal conversion efficiencies of greater than 50 % under laser irradiation at λ=808 nm.     

Magnetic Nanohybrids Loaded with Bimetal Core–Shell–Shell Nanorods for Bacteria Capture,Separation, and Near‐Infrared Photothermal Treatment

A novel antimicrobial nanohybrid based on near‐infrared (NIR) photothermal conversion is designed for bacteria capture, separation, and sterilization (killing). Positively charged magnetic reduced graphene oxide with modification by polyethylenimine (rGO–Fe₃O₄–PEI) is prepared and then loaded with core–shell–shell Au–Ag–Au nanorods to construct the nanohybrid rGO–Fe₃O₄–Au–Ag–Au. NIR laser irradiation melts the outer Au shell and exposes the inner Ag shell, which facilitates controlled release of the silver shell. The nanohybrids combine physical photothermal sterilization as a result of the outer Au shell with the antibacterial effect of the inner Ag shell. In addition, the nanohybrid exhibits high heat conductivity because of the rGO and rapid magnetic‐separation capability that is attributable to Fe₃O₄. The nanohybrid provides a significant improvement of bactericidal efficiency with respect to bare Au–Ag–Au nanorods and facilitates the isolation of bacteria from sample matrixes. A concentration of 25 μg mL^?1 of nanohybrid causes 100 % capture and separation of Escherichia coli O157:H7 (1×10⁸ cfu mL^?1) from an aqueous medium in 10 min. In addition, it causes a 22 °C temperature rise for the surrounding solution under NIR irradiation (785 nm, 50 mW cm^?2) for 10 min. With magnetic separation, 30 μg mL^?1 of nanohybrid results in a 100 % killing rate for E. coli O157:H7 cells. The facile bacteria separation and photothermal sterilization is potentially feasible for environmental and/or clinical treatment.     

Electrospun Silk Fibroin/Polylactic-co-glycolic Acid/Black Phosphorus Nanosheets Nanofibrous Membrane with Photothermal Therapy Potential for Cancer

Photothermal therapy is a promising treating method for cancers since it is safe and easily controllable. Black phosphorus (BP) nanosheets have drawn tremendous attention as a novel biodegradable thermotherapy material, owing to their excellent biocompatibility and photothermal properties. In this study, silk fibroin (SF) was used to exfoliate BP with long-term stability and good solution-processability. Then, the prepared BP@SF was introduced into fibrous membranes by electrospinning, together with SF and polylactic-co-glycolic acid (PLGA). The SF/PLGA/BP@SF membranes had relatively smooth and even fibers and the maximum stress was 2.92 MPa. Most importantly, the SF/PLGA/BP@SF membranes exhibited excellent photothermal properties, which could be controlled by the BP@SF content and near infrared (NIR) light power. The temperature of SF/PLGA/BP@SF composite membrane was increased by 15.26 °C under NIR (808 nm, 2.5 W/cm²) irradiation for 10 min. The photothermal property of SF/PLGA/BP@SF membranes significantly killed the HepG2 cancer cells in vitro, indicating its good potential for application in local treatment of cancer.     

Near‐Infrared‐Activated Nanocalorifiers in Microcapsules: Vapor Bubble Generation for In Vivo Enhanced Cancer Therapy

Photothermal therapy based on gold nanostructures has been widely investigated as a state‐of‐the‐art noninvasive therapy approach. Because single nanoparticles cannot harvest sufficient energy, self‐assemblies of small plasmonic particles into large aggregates are required for enhanced photothermal performance. Self‐assembled gold nanorods in lipid bilayer‐modified microcapsules are shown to localize at tumor sites, generate vapor bubbles under near‐infrared light exposure, and subsequently damage tumor tissues. The polyelectrolyte multilayer enables dense packing of gold nanorods during the assembly process, which leads to the formation of vapor bubbles around the excited capsules. The resulting vapor bubbles achieve a high efficiency of suppressing tumor growth compared to single gold nanorods. In vivo experiments demonstrated the ability of soft‐polymer multilayer microcapsules to cross the biological barriers of the body and localize at target tissues.