Exogenous Electron Generation Techniques for Biomedical Applications: Bridging Fundamentals and Clinical Practice

Biomaterials, Journal Year: 2025, Volume and Issue: 317, P. 123083 - 123083

Published: Jan. 5, 2025

Language: Английский

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Development of Transiently Strainable Benzocycloheptenes for Catalyst-Free, Visible-Light-Mediated [3 + 2]-Cycloadditions

Bioconjugate Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 4, 2025

Dynamic photogeneration of ephemeral and reactive species is enabling for chemical reactions, providing spatial temporal control. A previous study from our group established the ability 6,7-dihydro-5H-benzo[7]annulene, benzocycloheptene (BC7), to convert photochemical energy into ring strain, rapid cycloaddition alkyl azides with reversibly formed transient trans-isomer, affording versatile nonaromatic triazolines. Despite conceptual advances study, some challenges remained: fragility triazoline products, low regioselectivity cycloaddition, a need an iridium-based photosensitizer organic-based solvents, lack convenient linchpin functional handles. Herein, we communicate development second generation BC7 molecules that overcome issues first generation. method fragile products stable triazoles was developed. The alkene component polarized carbonyl group, dramatically improving while simultaneously red-shifting absorbance cycloalkene visible region, which expected facilitate direct excitation eliminate photocatalysts. However, experiments indicated involved passage through triplet manifold, complicating strategy. This successfully by attaching bromine atom directly moiety, accelerated singlet-to-triplet intersystem crossing heavy effect. Further exploration identified sites substitution can increase water solubility provide handle loading tools probes.

Language: Английский

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Bioorthogonal Reaction of β-Chloroacroleins with meta-Aminothiophenol to Develop Near-Infrared Fluorogenic Probes for Simultaneous Two-color Imaging

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 11, 2025

Highly fluorogenic probe based bioorthogonal chemistry has become a promising tool in biomedical applications. However, the majority of probes are designed by introducing partner as fluorescence quencher into classical fluorophores, and these exhibit deteriorating fluorogenicity emission wavelength shifts toward near-infrared (NIR) region, greatly limiting their applications vivo. Herein, we report novel reaction involving β-chloroacroleins (β-CAs) meta-aminothiophenol (m-AT1), whose increases more than 500-fold upon situ generating fluorophores. β-CAs stable under physiological conditions react rapidly (β-CA9, k2 = 2.2 × 102 M–1 s–1, H2O) chemoselectively with m-AT1 presence biological nucleophiles, delightfully, proceeds swiftly even solvent-free conditions. Furthermore, manipulating conjugate length enables to be fine-tuned from 627 778 nm. These allow simultaneous labeling multiple cellular organelles without washing steps, two-color tumor visualization is achieved living mice. We believe this study not only provides new insights for development NIR superior turn-on behaviors but also presents CA-AT widespread potential research.

Language: Английский

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Regulating the Isomerization Geometry and Energy State of Covalent Organic Frameworks for Enhanced Oxygen Reduction Activity

Advanced Materials, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 19, 2025

Abstract Embedding isomer entities onto crystalline frameworks with precisely defined spatial distributions represents a promising approach to enhancing the efficiency of oxygen reduction reaction (ORR) in fuel cells. However, accurately constructing covalent organic (COFs) regulate energy state effectively remains significant challenge. Herein, an innovative geometric isomerization strategy aimed at minimizing rotational barrier (ΔE), average local ionization (ALIE), and Gibbs free (ΔG) for ORR within COFs is proposed. Based on this strategy, isomeric Py‐COF‐αα 2,2‐substitution, Py‐COF‐ββ 3,3‐substitution, Py‐COF‐αβ 2,3‐substitution mainchain have been obtained. The electronic states intermediate adsorption capabilities are finely tuned through modification, yielding controllable chemical activity. Notably, lower ΔE between thiophenes achieves remarkable performance, evidenced by half‐wave potential 0.77 V vs reversible hydrogen electrode (RHE), surpassing most reported metal‐free electrocatalysts. Combined theoretical prediction situ Raman spectra, it revealed that increased dipole moment non‐uniform charge distribution caused endows pentacyclic‐carbon (thiophene β‐position) far from sulfur atoms efficient catalytic This work has opened up novel paradigm underscores pivotal role regulation facilitating catalysis.

Language: Английский

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Multifunctional Light Emitters for Theranostics

Engineering materials, Journal Year: 2025, Volume and Issue: unknown, P. 297 - 329

Published: Jan. 1, 2025

Language: Английский

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Near-infrared BODIPY-based theranostic agents for photothermal and combinatory therapy of cancers, where do we stand in year 2025

Coordination Chemistry Reviews, Journal Year: 2025, Volume and Issue: 541, P. 216781 - 216781

Published: May 21, 2025

Language: Английский

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Diverse reactivity of maleimides in polymer science and beyond

Polymer International, Journal Year: 2024, Volume and Issue: 74(4), P. 296 - 306

Published: Nov. 5, 2024

Abstract Maleimides are remarkably versatile functional groups, capable of participating in homo‐ and copolymerizations, Diels–Alder (photo)cycloadditions, Michael additions, other reactions. Their reactivity has afforded materials ranging from polyimides with high upper service temperatures to hydrogels for regenerative medicine applications. Moreover, maleimides have proven be an enabling chemistry pharmaceutical development bioconjugation via straightforward modification cysteine residues. To exert spatiotemporal control over reactions maleimides, multiple approaches been developed photocage nucleophiles, dienes, dipoles. Additionally, further substitution the maleimide alkene (e.g. monohalo‐, dihalo‐, thio‐, amino‐ methyl‐maleimides, among substituents) confers tunable dynamicity, as well responsive mechanical optical properties. In this mini‐review, we highlight diverse functionality underscoring their notable impact polymer science. This moiety related heterocycles will play important role future innovations chemistry, biomedical, research. © 2024 The Author(s). Polymer International published by John Wiley & Sons Ltd on behalf Society Chemical Industry.

Language: Английский

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Photoredox/Iron Dual-Catalysis-Enabled [4 + 2] Cyclization of Acyl Nitrene with Alkynes

Organic Letters, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 13, 2024

In this work, the annulation of acyl nitrene with alkynes is reported under photoredox/iron dual-catalysis for synthesis a series isoquninalin-2-ones. The reaction featured high regioselectivity and good generality. particular, resulting isoquinalin-2-ones could be structurally elaborated into several biologically interesting scaffolds. Mechanism investigation suggests that was ascribed to formal [4 + 2] cyclization. It believed represents an initial example preparing isoquinolin-1-ones from ferric peroxyl-catalyzed insertion.

Language: Английский

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Principles and recent developments in visible-light photoclick chemistry

Royal Society of Chemistry eBooks, Journal Year: 2024, Volume and Issue: unknown, P. 343 - 372

Published: Dec. 18, 2024

Photoclick reactions are photochemical transformations that either behave like ground state click or gate them through light-activation. To be compatible with future applications in the material sciences and biology, an increasing number of visible-light responsive variations being developed. These latest developments have been discussed present chapter, together systems can operated multiple wavelengths at same time.

Language: Английский

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