Near-Infrared Light-Driving Organic Photothermal Agents with an 88.9% Photothermal Conversion Efficiency for Image-Guided Synergistic Phototherapy.

Photothermal agents (PTAs) with desirable near-infrared (NIR) absorption and excellent photothermal conversion efficiency (PCE) are ideal candidates for cancer treatment. However, numerous PTAs still require high-intensity and long-duration laser irradiation to completely ablate the tumor during the photothermal therapy (PTT) process, resulting in light damage to healthy skin and tissue as well as limiting their biomedical applications. Integrating intense NIR absorption and high PCE into a single small-molecule PTA is an important prerequisite for realizing efficient PTT, but is a serious challenge. Herein, a series of donor-acceptor type PTAs (CC1 to NC4) are designed through a molecular engineering strategy. Theoretical calculations and experimental results show that the NIR absorption and photothermal effect from CC1 to NC4 are significantly enhanced as expected. Notably, NC4 nanoparticles exhibit intense NIR absorption, superhigh PCE of up to 88.9% for PTT, photoacoustic imaging and photothermal imaging, and effective reactive oxygen species generation for photodynamic therapy (PDT). The superior PTT/PDT synergistic phototherapeutic efficacy is well demonstrated by the complete elimination of tumor in vivo upon one-time, low-intensity, and short-duration laser irradiation (808 nm, 330 mW cm-2, and 3 min). This work provides a valuable guideline for rational design of PTAs for cancer phototherapy.

Acceptor-donor-acceptor type organic photothermal agents with enhanced NIR absorption and photothermal conversion effect for cancer photothermal therapy.

Numerous photothermal agents (PTAs) require high-intensity and long-duration laser excitation for photothermal therapy (PTT), resulting in light damage to healthy skin and tissue as well as limiting their biomedical applications. Integrating desirable near-infrared (NIR) absorption and high photothermal conversion efficiency (PCE) into a single small-molecule PTA is an important prerequisite for realizing efficient PTT, but is a serious challenge. Herein, through molecular engineering strategy, an acceptor-donor-acceptor (A-D-A) type PTA (ADA3) was readily developed for 808 nm laser-driving photothermal imaging and PTT of tumor. Theoretical calculations and experiment results show molecular engineering strategy is significant in regulating the structure and energy gap of PTAs, so as to effectively induce a narrow band gap for NIR absorption and further optimize photothermal properties. ADA3 possesses molar extinction coefficient of 3.1 × 104 M-1 cm-1 at 808 nm, followed being assembled into nanoparticles, ADA3-NPs show high PCE of 80.3%. In vivo experiments indicate that ADA3-NPs have excellent antitumor capability under one-time, low-intensity and short-duration (808 nm, 330 mW/cm2, 3 min) laser irradiation. Therefore, this work definitely exemplifies the enormous potential of molecular engineering strategy and provides an effective method for developing small-molecule PTAs.

Graphene-based terahertz metamirror with wavefront reconfiguration.

As an emerging material, graphene has been widely applied in the field of active metasurface. Recently, researchers employed graphene to achieve dynamical control of electromagnetic wavefront. In this work, graphene-based reflective metasurface is presented to realize dynamical wavefront reconfiguration for terahertz wave. Using a hybrid structure of cross-shaped graphene and metal patch, the designed metasurface has 360° phase modulation capability. Its wavefront is reconfigurable and can realize multiple functions. In order to verify this, three examples are designed to demonstrate the phenomenon of wavefront reconstruction. They are gradient metasurface, vortex beam generator, and focusing mirror, respectively. First of all, Fermi level of graphene is used to reconstruct the reflected wavefront of gradient metasurface, and then realize switching between positive and negative reflections. Secondly, a vortex beam generator is implemented, and it can reconstruct the mode number of orbital angular momentum through Fermi level. Finally, a reflective lens is proposed and verified, whose focus can appear or disappear with the tuning of Fermi level. The proposed functions have potential applications in the fields of terahertz switching, communication, and focusing.

Bifunctional terahertz modulator for beam steering and broadband absorption based on a hybrid structure of graphene and vanadium dioxide.

A bifunctional metamaterial is proposed based on a hybrid graphene and vanadium dioxide (VO2) configuration, which can realize a dynamic switch between beam steering and broadband absorption. The structure consists of a VO2 square, graphene patch, topas spacer, VO2 film, topas spacer, and metal substrate. When VO2 is in the metallic state, the structure serves as a coding metamaterial. By engineering different sizes of the top VO2 square and adjusting the Fermi energy level of graphene, the incident wave is scattered in different patterns. When VO2 is in the dielectric state, the structure serves as a broadband absorber. By changing the Fermi energy level of graphene from 0.0 eV to 0.9 eV, absorptance can be gradually changed and working bandwidth widens. There is an absorption band with near 100% absorptance from 0.9 THz to 1.35 THz when the Fermi energy level is 0.73 eV. And the designed broadband absorber is polarization-insensitive within the incident angle of 50°. Our work may show great potential in applications such as terahertz switching and modulation.