Thermal-Responsive Gel-Based Overheat Limiter Enabled Intelligent Photothermal Therapy.

Uncontrolled and excessive photothermal heating in photothermal therapy (PTT) inevitably causes thermal damage to surrounding normal tissues, severely limiting the universality and safety of PTT. To address this issue, an intelligent cooling thermal-responsive (ICTR) gel containing poly(N-isopropylacrylamide-co-acrylamide) (P(NIPAM-AM))microgel is applied onto the skin to realize intelligent PTT, which can avoid excessive heating and accidental injury. The high near-infrared (NIR) light transmittance (> 95%) of the ICTR gel ensures effective light delivery at low temperatures, while the refractive index of the P(NIPAM-AM) microgel increases remarkably when the temperature exceeds a predetermined threshold, resulting in progressively enhanced light scattering and weakened photothermal conversion. In animal studies, the negative feedback regulation of ICTR gel on light transmittance and photothermal heating allows the photothermal temperature in the lesion site to be stabilized within the effective therapeutic range (45 °C) while ensuring that the skin surface temperature does not exceed 35 °C. Compared with the severe skin thermal damage found in the histological staining of mice skin receiving conventional PTT, the mice skin receiving the ICTR gel-enabled intelligent PTT remains in good condition. This study establishes an intelligent and universal paradigm for PTT thermal regulation, which is of great significance for achieving safe and effective PTT.

Superhydrophilic 2D Covalent Organic Frameworks as Broadband Absorbers for Efficient Solar Steam Generation.

The intrinsic hydrophobicity and limited light absorption especially in the near-infrared (NIR) region of porous organic polymers are two bottlenecks impeding their applications in solar steam generation (SSG). Herein, we develop a 1,4,5,8-tetrakis(phenylamino)anthracene-9,10-dione (TPAD)-based covalent organic framework (COF) (TPAD-COF) featuring both superhydrophilicity and broad light absorption covering from the entire UV/Vis to NIR regions for SSG. TPAD-COF serving as a highly efficient photothermal conversion material without any additives displays an excellent water evaporation of 1.42 kg m-2 h-1 and achieves a high energy conversion efficiency of 94 % under 1 sun irradiation. Further extension of the light absorption range of the TPAD-based COF is realized through post-synthetic modification by chelating BF2 moieties. Systematic control experiments and analysis confirm that the hydrophilicity of photothermal conversion materials plays a more dominant role in the current TPAD-based COFs for SSG.

Skin Thermal Management for Subcutaneous Photoelectric Conversion Reaching 500 mW.

Despite possessing higher tissue transmittance and maximum permissible exposure power density for skin relative to other electromagnetic waves, second near-infrared light (1000-1350 nm) is scarcely applicable to subcutaneous photoelectric conversion, owing to the companion photothermal effect. Here, skin thermal management is conceived to utmostly utilize the photothermal effect of a photovoltaic cell, which not only improves the photoelectric conversion efficiency but also eliminates skin hyperthermia. In vivo, the output power can be higher than 500 mW with a photoelectric conversion efficiency of 9.4%. This output power is promising to recharge all the clinically applied implantable devices via wireless power transmission, that is, clinical pacemakers (6-200 µW), drug pumps (0.5-2 mW), cochlear (5-40 mW), and wireless endo-photo cameras (≈100 mW).

Subcutaneous power supply by NIR-II light.

Implantable medical devices are wished to be recharged via contactless power transfer technologies without interventional operations. Superior to subcutaneous power supply by visible light or electromagnetic wave, second near-infrared (NIR-II) light is predicted to possess 60 times subcutaneous power transmission but hard to be utilized. Here we report a photo-thermal-electric converter via the combination of photothermal conversion and thermoelectric conversion. It is able to generate an output power as high as 195 mW under the coverage of excised tissues, presenting advantages of non-invasion, high output power, negligible biological damage, and deep tissue penetration. As an in vivo demonstration, the output power of a packaged converter in the abdominal cavity of a rabbit reaches 20 mW under NIR-II light irradiation through the rabbit skin with a thickness of 8.5 mm. This value is high enough to recharge an implanted high-power-consumption wireless camera and transfer video signal out of body in real-time.

Visualizing thermal distribution through hydrogel confined ionic system.

Effective thermal regulation has shown great impacts on tremendous aspects of our life and manufacture. However, the invisible nature of thermal field brings us inconvenience or even security hazard. Herein, we present a method to visualize thermal distribution with the aid of a thermally active material. An ionic liquid with lower critical solution temperature is mixed within hydrogel to demonstrate a hydrogel confined ionic system (HCIS). This particular system turns turbid as the temperature exceeds an established temperature threshold, which is adjustable through applying different concentrations of HCl or NaCl. The system offers straightforward images of the spatial thermal distribution whether simple or sophisticated, which is fully in line with computational simulation. The system is further demonstrated with great promise for the application in fire warning to lower the threat induced by electrical failure. The HCIS opens a practical avenue to visualize thermal distribution and improve our thermal regulation efficiency.

Coupling molecular rigidity and flexibility on fused backbones for NIR-II photothermal conversion.

Great attention is being increasingly paid to photothermal conversion in the near-infrared (NIR)-II window (1000-1350 nm), where deeper tissue penetration is favored. To date, only a limited number of organic photothermal polymers and relevant theory have been exploited to direct the molecular design of polymers with highly efficient photothermal conversion, specifically in the NIR-II window. This work proposes a fused backbone structure locked via an intramolecular hydrogen bonding interaction and double bond, which favors molecular planarity and rigidity in the ground state and molecular flexibility in the excited state. Following this proposal, a particular class of NIR-II photothermal polymers are prepared. Their remarkable photothermal conversion efficiency is in good agreement with our strategy of coupling polymeric rigidity and flexibility, which accounts for the improved light absorption on going from the ground state to the excited state and nonradiative emission on going from the excited state to the ground state. It is envisioned that such a concept of coupling polymeric rigidity and flexibility will offer great inspiration for developing NIR-II photothermal polymers with the use of other chromophores.