Luminescent and Photofunctional Transition Metal Complexes: From Molecular Design to Diagnostic and Therapeutic Applications

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(32), P. 14420 - 14440

Published: Aug. 4, 2022

There has been emerging interest in the exploitation of photophysical and photochemical properties transition metal complexes for diagnostic therapeutic applications. In this Perspective, we highlight major recent advances development luminescent photofunctional complexes, particular, those rhenium(I), ruthenium(II), osmium(II), iridium(III), platinum(II), as bioimaging reagents phototherapeutic agents, with a focus on molecular design strategies that harness modulate interesting behavior complexes. We also discuss current challenges future outlook both fundamental research clinical

Language: Английский

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Near-infrared-II photoacoustic imaging and photo-triggered synergistic treatment of thrombosis via fibrin-specific homopolymer nanoparticles

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Oct. 28, 2023

Abstract The formation of an occlusive thrombus in the blood vessel is main culprit for numerous life-threatening cardiovascular diseases that represent leading cause morbidity and mortality worldwide. Herein, we develop a polymer nanoplatform integrates long-wavelength second near-infrared (NIR-II) photoacoustic imaging-based thrombosis detection antithrombotic activity. We design synthesize semiconducting homopolymer with strong absorption NIR-II region molecular motion boosts photothermal conversion signal. dope thermosensitive nitric oxide donor to formulate nanoplatform, on which fibrin-specific ligand functionalized ensure selective targeting. show light harvesting capability, bright signal active accumulation ability, nanoprobes are able sensitively selectively delineate thrombi. find also displays rapid efficient clot removal activity nearly complete flow restoration both carotid models low extremity arterial under trigger by integrating thrombus-localized effect on-demand release. This offers versatile approach diagnosis treatment caused various thrombotic disorders.

Language: Английский

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Small molecular cyanine dyes for phototheranostics

Coordination Chemistry Reviews, Journal Year: 2024, Volume and Issue: 516, P. 215986 - 215986

Published: June 2, 2024

Language: Английский

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A Nanographene‐Porphyrin Hybrid for Near‐Infrared‐Ii Phototheranostics

Advanced Science, Journal Year: 2024, Volume and Issue: 11(18)

Published: March 2, 2024

Abstract Photoacoustic imaging (PAI)‐guided photothermal therapy (PTT) in the second near‐infrared (NIR‐II, 1000–1700 nm) window has been attracting attention as a promising cancer theranostic platform. Here, it is reported that π‐extended porphyrins fused with one or two nanographene units (NGP‐1 and NGP‐2) can serve new class of NIR‐responsive organic agents, displaying absorption extending to ≈1000 ≈1400 nm NIR‐I NIR‐II windows, respectively. NGP‐1 NGP‐2 are dispersed water through encapsulation into self‐assembled nanoparticles (NPs), achieving high conversion efficiency 60% 69%, respectively, under 808 1064 laser irradiation. Moreover, NIR‐II‐active NGP‐2‐NPs demonstrated photoacoustic responses, along photostability biocompatibility, enabling PAI efficient PTT vivo.

Language: Английский

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Molecular Design Principles to Elongate the Metal-to-Ligand Charge Transfer Excited-State Lifetimes of Square-Planar Nickel(II) Complexes

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(48), P. 21948 - 21960

Published: Nov. 23, 2022

Square-planar NiII complexes and their electronically excited states play key roles in cross-coupling catalysis could offer new opportunities to complement well-known isoelectronic PtII luminophores. Metal-to-ligand charge transfer (MLCT) deactivation pathways are particularly relevant these contexts. We sought extend the lifetimes of 3MLCT square-planar by creating coordination environments that seemed well adapted 3d8 valence electron configuration. Using a rigid tridentate chelate ligand, which central cyclometalated phenyl unit is flanked two coordinating N-heterocyclic carbenes, along with monodentate isocyanide very strong ligand field created. Bulky substituents at backbone furthermore protect center from nucleophilic attack axial directions. UV-Vis transient absorption spectroscopies reveal upon excitation into 1MLCT bands ultrafast intersystem crossing state, latter relaxes onward metal-centered triplet state (3MC). A torsional motion NiII-carbon bond elongation facilitate relaxation 3MC state. The lifetime gets longer increasing strength improved steric protection, thereby revealing clear design guidelines for enhanced photophysical properties. longest reached solution room temperature 48 ps, factor 5-10 compared previously investigated complexes. Our study contributes making first-row transition metal partially filled d-orbitals more amenable applications photophysics photochemistry.

Language: Английский

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Acceptor Engineering Produces Ultrafast Nonradiative Decay in NIR-II Aza-BODIPY Nanoparticles for Efficient Osteosarcoma Photothermal Therapy via Concurrent Apoptosis and Pyroptosis

Research, Journal Year: 2023, Volume and Issue: 6

Published: Jan. 1, 2023

Small-molecule photothermal agents (PTAs) with intense second near-infrared (NIR-II, 1,000 to 1,700 nm) absorption and high conversion efficiencies (PCEs) are promising candidates for treating deep-seated tumors such as osteosarcoma. To date, the development of small-molecule NIR-II PTAs has largely relied on fabricating donor-acceptor-donor (D-A-D/D') structures limited success been achieved. Herein, through acceptor engineering, a donor-acceptor-acceptor (D-A-A')-structured aza-boron-dipyrromethene (aza-BODIPY) PTA (SW8) was readily developed 1,064-nm laser-mediated phototheranostic treatment Changing donor groups produced remarkable red-shifts maximums from first (NIR-I) regions (~808 ones (~1,064 aza-BODIPYs (SW1 SW8). Furthermore, SW8 self-assembled into nanoparticles (SW8@NPs) an ultrahigh PCE (75%, 1,064 nm). This primarily originated additional nonradiative decay pathway, which showed 100-fold enhanced rate compared that shown by conventional pathways internal vibrational relaxation. Eventually, SW8@NPs performed highly efficient therapy osteosarcoma via concurrent apoptosis pyroptosis. work not only illustrates remote approach spatiotemporal control but also provides new strategy building high-performance PTAs.

Language: Английский

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Nickel(II) Analogues of Phosphorescent Platinum(II) Complexes with Picosecond Excited‐State Decay

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(46)

Published: Sept. 21, 2023

Square-planar NiII complexes are interesting as cheaper and more sustainable alternatives to PtII luminophores widely used in lighting photocatalysis. We investigated the excited-state behavior of two complexes, which isostructural with luminescent complexes. The initially excited singlet metal-to-ligand charge transfer (1 MLCT) states decay metal-centered (3 MC) within less than 1 picosecond, followed by non-radiative relaxation 3 MC electronic ground state 9-21 ps. This contrasts population an emissive triplet ligand-centered LC) upon excitation analogues. Structural distortions responsible for this discrepant lead dark far lower energy LC compounds. Our findings suggest that if these structural could be restricted rigid coordination environments stronger ligand fields, four-coordinate decelerated such or MLCT become accessible. These insights relevant make fit photophysical photochemical applications relied on until now.

Language: Английский

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Tandem Proton Transfer in Carboxylated Supramolecular Polymer for Highly Efficient Overall Photosynthesis of Hydrogen Peroxide

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(38)

Published: July 3, 2024

Proton supply is as critical O

Language: Английский

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Tandem Proton Transfer in Carboxylated Supramolecular Polymer for Highly Efficient Overall Photosynthesis of Hydrogen Peroxide

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(38)

Published: July 3, 2024

Abstract Proton supply is as critical O 2 activation for artificial photosynthesis of hydrogen peroxide (H ) via two‐electron oxygen reduction reaction (2e − ORR). However, proton release water dissociation frequently hindered because the sluggish oxidation (WOR), extremely limiting efficiency photocatalytic H production. To tackle this challenge, carboxyl‐enriched supramolecular polymer (perylene tetracarboxylic acid—PTCA) elaborately prepared by molecular self‐assembly overall . Interestingly, interconversion between carboxyl Brønsted acid and its conjugated base realizes rapid circulation. Through efficient tandem transfer process, spatial effect greatly enhanced with reduced barrier. This significantly facilitates 2e ORR to synthesize in meanwhile promotes 4e WOR evolve Consequently, as‐developed PTCA exhibits a remarkable yield 185.6 μM h −1 pure air atmosphere under visible light illumination. More impressively, an appreciable 78.6 can be well maintained anaerobic system owing situ generation WOR. Our study presents novel concept constructing pathway enable

Language: Английский

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Near-Infrared II Agent with Excellent Overall Performance for Imaging-Guided Photothermal Thrombolysis

ACS Nano, Journal Year: 2024, Volume and Issue: 18(36), P. 25144 - 25154

Published: Aug. 27, 2024

Near-infrared II (NIR-II) imaging and photothermal therapy hold tremendous potential in precision diagnosis treatment within biological organisms. However, a significant challenge is the shortage of NIR-II fluorescent probes with both high conversion coefficient (PCE) fluorescence quantum yield (Φ

Language: Английский

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