Porphyrins and their derivatives are abundant in nature and play an important role in plant photosynthesis. To mimic the photosynthetic reactions in plants, researchers have developed numerous porphyrin‐based nanomaterials to convert light into chemical energy. And the porous porphyrin‐based nanomaterials attract great interest in photocatalysis owing to their high surface areas, designable structure, and favorable photocatalytic behavior. In this review, we highlight the recent progress of porous porphyrin‐based nanomaterials for photocatalysis. We offer a structured description of the main classes of the porous porphyrin‐based nanomaterials which consist of metal‐organic frameworks (MOFs), covalent‐organic frameworks (COFs), amorphous porous organic polymers (APOPs), and hydrogen bonding‐organic frameworks (HOFs). Strategies to improve their photocatalytic behavior in respect of how to boost the photoexcited electron‐hole separation and increase the accessible active sites are mainly highlighted. At last, the prospects and challenges of porous porphyrin‐based nanomaterials for photocatalysis are also discussed.
Recently, supramolecular coordination complexes (SCCs) based on photosensitizers as bridging ligands have attracted great attention in cancer therapy owing to their synergistic effect between photodynamic therapy (PDT) and chemotherapy. Herein, a highly emissive supramolecular platinum triangle BTZPy-Pt based on a novel type of photosensitizer BTZPy with thermally activated delayed fluorescence (TADF) was fabricated. The BTZPy and BTZPy-Pt exhibited strong luminescence emission in the visible range with high quantum yields (quantum yields (QYs) for BTZPy and BTZPy-Pt were about 78 and 62% in ethanol solutions, respectively). Additionally, BTZPy had been proved to be an excellent photosensitizer with superior 1 O 2 generation capability (the 1 O 2 generation quantum yield reached up to ca. 95%) for PDT. By the combination of the excellent phototoxicity of BTZPy and the antitumor activity of the Pt center, the platinum triangle BTZPy-Pt demonstrated a highly efficient anticancer performance toward HeLa cells (IC 50 : 0.5 μg mL −1 ). This study not only provides a blueprint to fabricate new types of photosensitizers but also paves a way to design novel SCCs for efficient PDT.
Supramolecular self-assembly of near-infrared (NIR) dyes are believed to be a promising strategy to design effective photothermal agents for tumor photothermal therapy (PTT). However, due to the uncontrollable intermolecular interactions, accurately fine-tuning the aggregated morphology of NIR dyes through adjusting their supramolecular self-assembly is challenging. Here, based on organic-metal coordination interaction, a facile self-assembly fine-tuning strategy is proposed to adjust the aggregated morphology of heptamethine cyanine (Cy7) dyes, the well-known NIR dyes. Three hydrophilic Cy7 derivatives Cy-nCOOH (n = 1, 2, and 3) are synthesized, and then are coordinated with Cu 2+ to obtain different aggregates. Cy-1COOH/Cu aggregates form partial J-aggregates. Cy-2COOH/Cu aggregates are amorphous. Noteworthily, Cy-3COOH/Cu aggregates exhibit significant H-type aggregation. Moreover, Cy-3COOH/Cu aggregates show about threefold higher photothermal conversion efficiency and obviously enhanced photostability than Cy-1COOH/Cu and Cy-2COOH/Cu aggregates. It is demonstrated that H-aggregates with face-to-face π-π stacking greatly quench fluorescence and inhibit singlet oxygen ( 1 O 2 ) production, which lead to the improved photothermal performances. In vitro and in vivo experiments demonstrate the remarkable tumor PTT efficiency of Cy-3COOH/Cu H-aggregates. This study provides a new insight into how to precisely control molecular aggregation of organic dyes in supramolecular self-assembly for enhanced tumor phototherapy.
Photosensitizers for photodynamic
therapy (PDT) of cancer have
been widely investigated over the past decades. However, the notorious
aggregation-caused quenching (ACQ) effect limits their further biological
applications. In this work, we have designed and reported a photosensitizer
BOPHY-2TPA. The formed photosensitizer BOPHY-2TPA was a donor–acceptor–donor
(D–A–D) structure with the BOPHY as an acceptor core
and two triphenylamine (TPAs) as the electron donor units. The BOPHY-2TPA
exhibited a large Stokes shift and excellent photoinduced 1O2 generation capabilities. Besides, the twisted structure
of TPAs endowed the BOPHY-2TPA with intrinsic AIE properties, which
effectively avoided the ACQ effect. Because of these prominent features,
the BOPHY-2TPA aggregates encapsulated with biocompatible Pluronic
P123 in aqueous solution showed high PDT antitumor efficiency.
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