D−π–A Fluorophores with Strong Solvatochromism for Single-Molecule Ratiometric Thermometers

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

Published: March 5, 2025

Fluorescence thermometry has emerged as a significant area of research in the field remote temperature sensing with high accuracy. However, development noninvasive and reliable small organic fluorescence thermometers (FTs) remains challenging. In this study, we developed high-sensitivity, high-resolution ratiometric FT solvatochromic dye analyzed its response mechanism. π-Extended fluorene-based D-π-A-type dyes (FπAc, FπF, FπVC) were synthesized characterized. A shift >200 nm was observed between n-hexane tetrahydrofuran (THF) for both FπF FπVC, emission THF reaching red region (701 nm, 828 nm). This substantial accompanied by concurrent decrease quantum yield is attributable to accelerated internal conversion. The spectra FπVC diethyl ether exhibited blue shifts increased intensities polarity at temperatures. Our observations revealed an absolute sensitivity 21%/°C relative 3.0%/°C maximum. These results represent highest resolution reported single fluorophore FTs dispersed solution. positive coefficient intensity attributed control nonradiative decay pathway solvatochromism. responsiveness could be detected living HeLa cells confocal microscopy. Using proposed strategy develop FTs, plan build library that will cover various environments interest simple complex systems.

Language: Английский

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Phenothiazine-Indole Acetonitrile Based Ratiometric Chemosensor for S2− Ions: Applications To Environmental Samples and Living Cells

Journal of Fluorescence, Journal Year: 2025, Volume and Issue: unknown

Published: April 15, 2025

Language: Английский

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Coarctate reaction for synthesis of fluorescent N-heterocycles, late-stage functionalization, and photo-triggered drug delivery

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: April 22, 2025

Coarctate reactions, involving the simultaneous formation and cleavage of two bonds at single or multiple atoms, have remained largely unexplored for biomolecular applications. These reactions are characterized by complex helical orbitals in their transition state produce unique chemical entities unattainable other methods. This makes coarctate particularly useful expanding diversity properties biomolecules. In this study, we apply an azo-ene-yne reaction to synthesize isoindazole-based N-heterocycles explore The method demonstrates high chemoselectivity, thus enabling synthesis unnatural amino acids drug conjugates, late-stage peptide functionalization. exhibit inherent fluorescence, which can be enhanced red-shifted through electronic tuning. Additionally, discover a photo-triggered isoindazole moiety from 2-amine-isoindazole, light-triggered selective delivery secondary amine hydroxyl-containing drugs, represent over 70% current pharmaceuticals. We also employ deprotection amines functionalization peptides with isoindazole, access previously space.

Language: Английский

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Trifluoroacetyl‐Substituted D–π–A Fluorophores: Design Strategies for Strong Solvatochromism and Giga Stokes Shifts

Chemistry - An Asian Journal, Journal Year: 2025, Volume and Issue: unknown

Published: April 30, 2025

Solvatochromic fluorophores, widely employed in various analytical applications such as environmentally responsive dyes, typically feature a donor-π-acceptor (D-π-A) structure. Most recently, Klymchenko and we independently designed D-π-A fluorophores with strong acceptor, trifluoroacetyl group, to achieve fluorescent solvatochromism reported its application membrane analysis (Klymchenko et al. Anal. Chem. 2024, 96, 13242) molecular thermometer (Konishi J. Am. Soc. 2025, 147, 9953), respectively. However, these reports have only considered few π-electron donors including dialkylamines. There is not enough scope for solvatochromic that take advantage of the properties group. In this study, systematically investigated π-conjugated aromatic skeleton groups. The relationship between dye structure absorption, fluorescence, quantum yield were clarified, design strategy exhibit desired was established. Moreover, fluorescence quenching can occur depending on solvent selection or study provides insightful trifluoroacetyl-based strategy, emphasizing their prospective but underused acceptor units next fluorophore development.

Language: Английский

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A furo-fused coumarin dye with large Stokes shift and intensive emission intensity: its design, synthesis, characterizaiton, optical properties and solvatochromic applications

Journal of Molecular Structure, Journal Year: 2025, Volume and Issue: unknown, P. 142319 - 142319

Published: April 1, 2025

Language: Английский

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A Molecular Hybrid of the GFP Chromophore and 2,2′-Bipyridine: An Accessible Sensor for Zn2+ Detection with Fluorescence Microscopy

International Journal of Molecular Sciences, Journal Year: 2024, Volume and Issue: 25(6), P. 3504 - 3504

Published: March 20, 2024

The few commercially available chemosensors and published probes for in vitro Zn2+ detection two-photon microscopy are compromised by their flawed spectroscopic properties, causing issues selectivity or challenging multistep syntheses. Herein, we present the development of an effective small molecular GFP chromophore-based fluorescent chemosensor with a 2,2′-bipyridine chelator moiety (GFZnP BIPY) that has straightforward synthesis uncompromised properties. Detailed experimental characterizations free zinc-bound compounds within physiologically relevant pH range presented. Excellent photophysical characteristics reported, including 53-fold fluorescence enhancement excitation emission maxima at 422 nm 492 nm, respectively. A high cross section 3.0 GM 840 as well excellent metal ion reported. In experiments on HEK 293 cell culture were carried out using to demonstrate applicability novel sensor zinc bioimaging.

Language: Английский

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An Asymmetric NIR-II Organic Fluorophore with an Ultra-Large Stokes Shift for Imaging-Guided and Targeted Phototherapy

ACS Biomaterials Science & Engineering, Journal Year: 2024, Volume and Issue: 10(7), P. 4541 - 4551

Published: June 10, 2024

NIR-II imaging-guided phototherapy is an attractive, yet challenging, tumor treatment strategy. By monitoring the accumulation of reagents at site through imaging and determining appropriate therapy window, therapeutic effect could be significantly improved. Probes with (1000–1700 nm) fluorescence emission a large Stokes shift hold great promise for deep penetration, minimized self-quenching, high spatiotemporal resolution. However, due to lack suitable molecular framework, design simple small-molecule dye has rarely been reported. Herein, we prepare asymmetric D−π–A type probe (TBy). The incapsulated in amphiphilic polymer modified fibronectin targeting peptide CREKA, which recognize fibrin–fibronectin complex overexpressed multiple malignant tumors. nanoparticles thus constructed (TByC-NPs) have maximum 1037 nm 426 nm, largest among organic fluorescent dyes reported literature. TByC-NPs exhibit good performance, active targeting, photothermal photodynamic capabilities. In vitro vivo studies verify that TByC nanoplatform shows outstanding biocompatibility provides excellent antitumor effect.

Language: Английский

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BOPHY Derivatives as Phototherapeutic Agents for the Photodynamic Inactivation of Microorganisms

ChemPhotoChem, Journal Year: 2024, Volume and Issue: unknown

Published: July 3, 2024

Abstract The improvement of photodynamic inactivation (PDI) significantly depends on the development new families photosensitizers (PSs). In this sense, three BOPHY derivatives ( BP , BP‐Br and BP‐I ) were synthetized, studied, compared to assess their antimicrobial properties. is an interesting fluorescent probe for cell imaging, while halogenated analogs are excellent oxygen photosensitizing agents. compound presented a fluorescence quantum yield close unity showed no reactive species (ROS) production. contrast, did not show emission properties but exhibited high production ROS through both mechanisms, generating singlet (type II) superoxide radical anion I) under aerobic light irradiation. adequate balance between photokilling action binding bacterial cells these macrocycles evaluated in vitro against methicillin‐resistant Staphylococcus aureus (MRSA) Escherichia coli bacteria. Our results demonstrated that effective PSs inactivating MRSA using shorter irradiation periods. addition, sensitized by BOPHYs was potentiated adding KI. combination KI led complete elimination Gram‐positive Gram‐negative Hence, prove be potent broad‐spectrum PSs. To best our knowledge, first time have been applied photokill pathogenic microorganisms.

Language: Английский

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Rational Synthesis of Highly Stable Dithienopyrrole-Embedded BODIPYs Exhibiting Large Stokes Shift

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

Published: Dec. 17, 2024

A series of dithienopyrrole (DTP) embedded BODIPYs were synthesized and structurally characterized. These have strong absorption in the green region broad emission red with a large Stokes shift ranging from 3100 to 4200 cm–1. Interestingly, all three show intramolecular charge transfer interaction (ICT). Intriguingly, both (bis- tris-BOD) also exhibit excited state symmetry breaking (ES-SB). Single-crystal X-ray analysis unambiguously confirmed exact structures distinct BODIPYs.

Language: Английский

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Benzo[f]indazoles: a new class of glow dyes for the generation of versatile fluorophores

Dyes and Pigments, Journal Year: 2024, Volume and Issue: unknown, P. 112624 - 112624

Published: Dec. 1, 2024

Language: Английский

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