A Highly Water‐Soluble Aggregation‐Induced Emission Luminogen with Anion‐π⁺ Interactions for Targeted NIR Imaging of Cancer Cells and Type I Photodynamic Therapy

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(33)

Published: June 26, 2023

The low oxygen dependence of type I photosensitizers (PSs) has made them a popular choice for treating solid tumors. However, the drawbacks poor water solubility, short emission wavelength, stability, and inability to distinguish cancer cells from normal limit application most PSs in clinical therapy. Thereby, developing novel overcoming these problems is an urgent but challenging task. Herein, by utilizing distinctive structural characteristics anion-π+ interactions, highly water-soluble PS (DPBC-Br) with aggregation-induced (AIE) characteristic near-infrared (NIR) fabricated first time. DPBC-Br displays remarkable solubility (7.3 mM) outstanding photobleaching resistance, enabling efficient precise differentiation between tumor wash-free long-term tracking manner via NIR-I imaging. Additionally, superior reactive species (ROS) produced provide both specific killing vitro inhibition growth vivo, negligible systemic toxicity. This study rationally constructs PS, which higher reliability controllability compared conventional nanoparticle formulating procedures, offering great potential treatment.

Language: Английский

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Novel Dibenzofulvene‐Based NIR‐II Emission Phototheranostic Agent with an 82.6% Photothermal Conversion Efficiency for Photothermal Therapy

Advanced Functional Materials, Journal Year: 2023, Volume and Issue: 34(8)

Published: Nov. 12, 2023

Abstract Organic molecules with second near‐infrared (NIR‐II, 1000–1700 nm) emission have significant advantages over NIR‐I (600–900 dyes, and been widely used as phototheranostic agents (PTAs) fluorescent probes. However, the two biggest challenges for such reagents are improving photothermal conversion efficiency (PCE), simplifying tedious synthetic procedures. Herein, different from traditional NIR skeleton, first time, it develops novel dibenzofulvene‐based NIR‐II PTAs via D‐π‐A concept high PCEs through simple steps. The increased intramolecular charge transfer effect extended π‐conjugation effectively red‐shift their emissions to region. In addition, introduction of molecular rotors/vibrators formation π–π stacking prompt exhibit PCEs. Notably, FE‐IDMN nanoparticles (FE‐IDMN NPs) achieve an exciting PCE 82.6%, higher than most reported emission. NPs also possess good colloidal, pH, stabilities, well excellent photoacoustic response, which is further successfully applied fluorescence/photoacoustic/photothermal imaging‐guided therapy. This work provides a strategy constructing new low weight, emission, cancer

Language: Английский

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Oxidization enhances type I ROS generation of AIE-active zwitterionic photosensitizers for photodynamic killing of drug-resistant bacteria

Chemical Science, Journal Year: 2023, Volume and Issue: 14(18), P. 4863 - 4871

Published: Jan. 1, 2023

Type I photosensitizers (PSs) with an aggregation-induced emission (AIE) feature have received sustained attention for their excellent theranostic performance in the treatment of clinical diseases. However, development AIE-active type PSs strong reactive oxygen species (ROS) production capacity remains a challenge due to lack in-depth theoretical studies on aggregate behavior and rational design strategies. Herein, we proposed facile oxidization strategy enhance ROS generation efficiency PSs. Two AIE luminogens, MPD its oxidized product MPD-O were synthesized. Compared MPD, zwitterionic showed higher efficiency. The introduction electron-withdrawing atoms results formation intermolecular hydrogen bonds molecular stacking MPD-O, which endowed more tightly packed arrangement state. Theoretical calculations demonstrated that accessible intersystem crossing (ISC) channels larger spin-orbit coupling (SOC) constants provide further explanation superior evidenced effectiveness enhancing ability by strategy. Moreover, DAPD-O, cationic derivative was synthesized improve antibacterial activity showing photodynamic against methicillin-resistant S. aureus both vitro vivo. This work elucidates mechanism offers new guideline exploitation

Language: Английский

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Development of Sulfonamide‐Functionalized Charge‐Reversal AIE Photosensitizers for Precise Photodynamic Therapy in the Acidic Tumor Microenvironment

Advanced Functional Materials, Journal Year: 2023, Volume and Issue: 33(30)

Published: May 1, 2023

Abstract Tumor‐targeted photodynamic therapy (PDT) is desirable as it can achieve efficient killing of tumor cells with no or less harm to normal cells. Herein, a facile molecular engineering strategy developed for photosensitizers (PSs) aggregation induced emission (AIE) characteristics and responsive properties the acidic microenvironment (TME). By marriage pH‐sensitive sulfonamide moieties AIE PSs, two near‐infrared luminogens called DBP‐SPy DBP‐SPh are designed synthesized. Both form negatively charged nanoaggregates in aqueous medium at physiological pH. The undergo surface charge conversion become positive pH close signature TME, while show such property. endowed response TME enables enhanced cellular uptake = 6.8. contrast, its much sacrificed 7.4. As result, under white light irradiation, demonstrate considerable therapeutic effect on cancer vitro excellent growth inhibition vivo. Hence, this study not only provides an TME‐responsive PS precise PDT, but also inspires new design strategies AIE‐based theragnostic systems targeting characteristics.

Language: Английский

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A planar electronic acceptor motif contributing to NIR-II AIEgen with combined imaging and therapeutic applications

Chemical Science, Journal Year: 2024, Volume and Issue: 15(18), P. 6777 - 6788

Published: Jan. 1, 2024

Designing molecules with donor-acceptor-donor (D-A-D) architecture plays an important role in obtaining second near-infrared region (NIR-II, 1000-1700 nm) fluorescent dyes for biomedical applications; however, this always comes a challenge due to very limited electronic acceptors. On the other hand, endow NIR-II combined therapeutic applications, trivial molecular design is indispensable. Herein, we propose pyrazine-based planar acceptor strong electron affinity, which can be used develop dyes. By structurally attaching two classical triphenylamine donors it, basic D-A-D module, namely Py-NIR, generated. The planarity of crucial induce distinct emission peaking at ∼1100 nm. unique construction cause twisted and flexible conformation by repulsive effect between donors, essential aggregation-induced (AIE) property. tuned intramolecular motions D-A pair brought lead remarkable photothermal conversion efficiency 56.1% type I photosensitization favorable hydroxyl radical (OH˙) formation. Note that no additional measures are adopted design, providing ideal platform realize probes synergetic functions based on such acceptor. Besides, nanoparticles Py-NIR exhibit excellent fluorescence imaging towards orthotopic 4T1 breast tumors living mice high sensitivity contrast. Combined photoacoustic caused thermal effect, imaging-guided photoablation well performed. Our work has created new opportunity accelerating applications.

Language: Английский

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J‐Aggregate Promoting NIR‐II Emission for Fluorescence/ Photoacoustic Imaging‐Guided Phototherapy

Advanced Healthcare Materials, Journal Year: 2024, Volume and Issue: unknown

Published: April 25, 2024

Abstract J‐aggregate is a promising strategy to enhance second near‐infrared window (NIR‐II) emission, while the controlled synthesis of J‐aggregated NIR‐II dyes huge challenge because lack molecular design principle. Herein, bulk spiro[fluorene‐9,9′‐xanthene] functionalized benzobisthiadiazole‐based (named BSFX‐BBT and OSFX‐BBT) are synthesized with different alkyl chains. The weak repulsion interaction between donor acceptor units S…N secondary interactions make adopt co‐planar conformation display peak absorption >880 nm in solution. Importantly, can form desiring condensed state, femtosecond transient spectra reveal that excited states radiative states, facilitate stimulated emission. Consequently, nanoparticles (NPs) emission at 1124 high relative quantum yield 0.81%. efficient good photothermal effect, biocompatibility NPs demonstrate antitumor efficacy via fluorescence/photoacoustic imaging‐guided phototherapy. paradigm illustrates tuning aggregate dye spiro‐functionalized an effective approach photo‐theranostic performance.

Language: Английский

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A Cyanine with 83.2% Photothermal Conversion Efficiency and Absorption Wavelengths over 1200 nm for Photothermal Therapy

Advanced Healthcare Materials, Journal Year: 2024, Volume and Issue: 13(20)

Published: May 23, 2024

Abstract Developing small‐molecule photothermal agents (PTAs) with good near‐infrared‐II (NIR‐II) response for deeper tissue penetration and minimizing damage to healthy tissues has attracted much attention in therapy (PTT). However, concentrating ultra‐long excitation wavelengths high conversion efficiencies (PCEs) into a single organic small molecule is still challenging due the lack of suitable molecular structures. Here, six polymethine cyanine molecules based on structure indocyanine green are synthesized by increasing conjugated two‐terminal indole salts number rigid methine units, incorporating longer alkyl side chains salts. Ultimately, IC‐1224 obtained an absorption wavelength more than 1200 nm, which PCE up 83.2% NIR‐II window exhibits excellent PTT tumor ablation performance. This provides high‐performance NIR‐II‐responsive PTA, offers further possibilities application biomedical fields.

Language: Английский

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White-light activatable organic NIR-II luminescence nanomaterials for imaging-guided surgery

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: July 11, 2024

Abstract While second near-infrared (NIR-II) fluorescence imaging is a promising tool for real-time surveillance of surgical operations, the previously reported organic NIR-II luminescent materials in vivo are predominantly activated by expensive lasers or X-ray with high power and poor illumination homogeneity, which significantly limits their clinical applications. Here we report white-light activatable agent taking advantages strong intramolecular/intermolecular D-A interactions conjugated Y6CT molecules nanoparticles (Y6CT-NPs), brightness as 13315.1, over two times that brightest laser-activated contrast agents thus far. Upon activation, Y6CT-NPs can achieve not only hepatic ischemia reperfusion, but also monitoring kidney transplantation surgery. During surgery, identification renal vasculature, post-reconstruction assessment allograft vascular integrity, blood supply analysis ureter be vividly depicted using signal-to-noise ratios upon laparoscopic LED activation. Our work provides efficient molecular design guidelines towards highlights an opportunity precision theranostics.

Language: Английский

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Light‐up the white light emission in microscale with a superior deep‐blue AIE fiber as wave‐guiding source

Aggregate, Journal Year: 2023, Volume and Issue: 5(2)

Published: Nov. 1, 2023

Abstract The development of high‐performance organic blue light‐emitting emitters is in urgent to act as an excitation source contribute the white light generation. On other hand, investigation on optical waveguides have been received increasing attentions because they can manipulate propagation accurately microscale boost optoelectronic and energy conversion applications. In this work, we facilely prepared a deep‐blue aggregation‐induced emission (AIE) dye, namely TPP‐4OMe, which shows high luminescent efficiency, narrow band good stability aggregate state. TPP‐4OMe be fabricated AIE microfibers readily with definite morphology composition. Based microfibers, active waveguide transmit signals achieved very low loss coefficient ( α ) 6.7 × 10 −3 dB μm −1 . Meanwhile, full‐visible broadband low‐loss passive well performed these has never observed pure crystals. More interestingly, excellent properties enable them wave‐guiding source, resulting distinct emission. present work not only provides materials but also bridges realize efficient accelerate practical

Language: Английский

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Easy but Efficient: Facile Approach to Molecule with Theoretically Justified Donor–Acceptor Structure for Effective Photothermal Conversion and Intravenous Photothermal Therapy

Advanced Science, Journal Year: 2024, Volume and Issue: 11(24)

Published: March 13, 2024

Abstract To accelerate the pace in field of photothermal therapy (PTT), it is urged to develop easily accessible agents (PTAs) showing high conversion efficiency (PCE). As a proof‐of‐concept, hereby conventional strategy presented prepare donor–acceptor (D–A) structured PTAs through cycloaddition‐retroelectrocyclization ( CA–RE ) reaction, and resultant give PCE upon near‐infrared (NIR) irradiation. By joint experimental‐theoretical study, these exhibit prominent D–A structure with strong intramolecular charge transfer (ICT) characteristics significantly twisting between D A units which account for PCEs. Among them, DMA‐TCNQ exhibits strongest absorption NIR range as well highest 91.3% irradiation by 760‐nm LED lamp (1.2 W cm −2 ). In vitro vivo experimental results revealed that low dark toxicity phototoxicity after IR along nude mice tumor inhibition up 81.0% intravenous therapy. The findings demonstrate reaction convenient approach obtain twisted effective PTT probably promote progress cancer therapies.

Language: Английский

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