Fused Azulenyl Squaraine Derivatives Improve Phototheranostics in the Second Near-Infrared Window by Concentrating Excited State Energy on Non-Radiative Decay Pathways.

The second near-infrared (NIR-II) theranostics offer new opportunities for precise disease phototheranostic due to the enhanced tissue penetration and higher maximum permissible exposure of NIR-II light. However, traditional regimens lacking effective NIR-II absorption and uncontrollable excited-state energy decay pathways often result in insufficient theranostic outcomes. Herein a phototheranostic nano-agent (PS-1 NPs) based on azulenyl squaraine derivatives with a strong NIR-II absorption band centered at 1092 nm is reported, allowing almost all absorbed excitation energy to dissipate through non-radiative decay pathways, leading to high photothermal conversion efficiency (90.98 %) and strong photoacoustic response. Both in vitro and in vivo photoacoustic/photothermal therapy results demonstrate enhanced deep tissue cancer theranostic performance of PS-1 NPs. Even in the 5 mm deep-seated tumor model, PS-1 NPs demonstrated a satisfactory anti-tumor effect in photoacoustic imaging-guided photothermal therapy. Moreover, for the human extracted tooth root canal infection model, the synergistic outcomes of the photothermal effect of PS-1 NPs and 0.5 % NaClO solution resulted in therapeutic efficacy comparable to the clinical gold standard irrigation agent 5.25 % NaClO, opening up possibilities for the expansion of NIR-II theranostic agents in oral medicine.

Synchronously Manipulating Absorption and Extinction Coefficient of Semiconducting Polymers via Precise Dual-Acceptor Engineering for NIR-II Excited Photothermal Theranostics.

Integrating the ultralong excitation wavelength, high extinction coefficient, and prominent photothermal conversion ability into a single photothermal agent is an appealing yet significantly challenging task. Herein, a precise dual-acceptor engineering strategy is exploited for this attempt based on donor-acceptor (D-A) type semiconductor polymers by subtly regulating the molar proportions of the two employed electron acceptor moieties featuring different electronic affinity and π-conjugation degrees, and making full use of the active intramolecular motion-induced photothermal effect. The optimal polymer SP4 synchronously shows desirable second near-infrared (NIR-II) absorption, an extremely high extinction coefficient, and satisfactory photothermal conversion behavior. Consequently, the unprecedented performance of SP4 NPs on 1064 nm laser-excited photoacoustic imaging (PAI)-guided photothermal therapy (PTT) is demonstrated by the precise tumor diagnosis and complete tumor elimination.

Azulene-Containing Squaraines for Photoacoustic Imaging and Photothermal Therapy.

Photoacoustic imaging (PAI) guided photothermal therapy (PTT) can realize real-time diagnosis and in situ treatment of cancer at the same time. Absorption in the near-infrared (NIR) region with large molar extinction coefficient (ε) and high value of photothermal conversion efficiency (PCE) are key prerequisites for photothermal agents (PTAs) to realize dual PAI and PTT treatments. Squaraines have stable quinoid structures with strong planarity and rigidity, in favor of the NIR absorption and high ε values. On the other hand, azulene derivatives mostly have very faint fluorescence emission, which is beneficial for photothermal transformation. Herein, two azulene-containing squaraines Az-SQ-1 and Az-SQ-2 are synthesized as high-performance PTAs. In comparison with Az-SQ-1, Az-SQ-2 possesses larger εmax of 3 × 105 M-1 cm-1 at 780 nm in organic solution and higher PCE of 53.2% in the form of nanoparticles under 808 nm laser irradiation. Accordingly, Az-SQ-2 NPs present stronger photoacoustic signals (about 15.1-times the background signal) and more efficient suppression of tumor growth. Our research indicates that the introduction of azulene unit to traditional NIR dyes is a simple but effective approach to obtain outstanding PTAs in the aspect of phototheranostics.

Highly efficient photothermal nanoagent achieved by harvesting energy via excited-state intramolecular motion within nanoparticles.

The exciting applications of molecular motion are still limited and are in urgent pursuit, although some fascinating concepts such as molecular motors and molecular machines have been proposed for years. Utilizing molecular motion in a nanoplatform for practical application has been scarcely explored due to some unconquered challenges such as how to achieve effective molecular motion in the aggregate state within nanoparticles. Here, we introduce a class of near infrared-absorbing organic molecules with intramolecular motion-induced photothermy inside nanoparticles, which enables most absorbed light energy to dissipate as heat. Such a property makes the nanoparticles a superior photoacoustic imaging agent compared to widely used methylene blue and semiconducting polymer nanoparticles and allow them for high-contrast photoacoustic imaging of tumours in live mice. This study not only provides a strategy for developing advanced photothermal/photoacoustic imaging nanoagents, but also enables molecular motion in a nanoplatform to find a way for practical application.

Specific and reproducible gas sensors utilizing gas-phase chemical reaction on organic transistors.

Utilizing a textbook reaction on the surface of an organic active channel, achieves sensitive detection of HCl, NH3 and NO2, with good selectivity, excellent reproducibility, and satisfactory stability. These results reveal gas-phase reaction assisted detection as a unique and promising approach to construct practical applicable gas sensors with typical organic transistors.

A facile synthesis of linear benzene-fused bis(tetrathiafulvalene) compounds and their application for organic field-effect transistors.

Three new linear benzene-fused bis(tetrathiafulvalene) compounds (1-3) were easily synthesized by one-step phosphite-induced cross-coupling reactions; a solution processed organic field-effect transistor based on 2 shows high mobility of 0.02 cm2/Vs.

One- or two-dimensional 2,3-naphtho crown ether complexes [Na(N15C5)]2[M(SCN)4] and [K(N18C6)]2[M(SCN)4] (M = Pd, Pt) constructed by pi-pi stacking interactions.

Four novel 2,3-naphtho-15-crown-5 (N15C5) and 2,3-naphtho-18-crown-6 (N18C6) complexes [Na(N15C5)]2[Pd(SCN)4] (1), [Na(N15C5)]2[Pt(SCN)4] (2), [K(N18C6)]2[Pd(SCN)4] (3) and [K(N18C6)]2[Pt(SCN)4] (4) were synthesized and characterized by elemental analysis, FT-IR spectra and single-crystal X-ray diffraction. The structure analyses reveal that both 1 and 2 are assembled into zigzag chains by the strong intermolecular pi-pi stacking interactions between adjacent 2,3-naphthylene groups of N15C5. The molecules of complexes 3 and 4 are linked into 1D chains by the bridging K-O(ether) interactions between the adjacent [K(N18C6)]+ units and the resulting chains are constructed into a novel 2D network by inter-chain pi-pi stacking interactions between the neighboring 2,3-naphthylene moieties of N18C6. According to the supramolecular self-assemblies of complexes 1-4, two types of stacking model of naphthylene groups are given and discussed.