TADF-based NIR-II semiconducting polymer dots for <i>in vivo</i> 3D bone imaging

Hsu, Keng-Fang; Su, Shih-Po; Lu, Hsiu‐Feng; Liu, Ming-Ho; Chang, Yuan Jay; Lee, Yi Jang; Chiang, Huihua Kenny; Hsu, Chao‐Ping; Lu, Chin‐Wei; Chan, Yang-Hsiang

doi:10.1039/d2sc03271f

Cited by 13 publications

(11 citation statements)

References 85 publications

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“…Hsu et al used a similar method to produce Pdots from conjugated donor−acceptor fluorophores, integrated with geometrically twisted TADF emitters to modulate their structural packing. 25 This resulted in Pdots 23−29 nm in diameter with fluorescent emission at λ max = 1064−1100 nm. When injected into mice, these nanoparticles facilitated imaging of the skeletal system by accumulating in bone structures, possibly due to their small size 26 and PEGylated coronas which increase blood-circulation times.…”

Section: Polymer Dotsmentioning

confidence: 99%

“…The quantum yield was diminished from 72% in the free polymer to 26% in the Pdot but demonstrated good resistance to quenching by oxygen. Hsu et al used a similar method to produce Pdots from conjugated donor–acceptor fluorophores, integrated with geometrically twisted TADF emitters to modulate their structural packing . This resulted in Pdots 23–29 nm in diameter with fluorescent emission at λ max = 1064–1100 nm.…”

Section: Tadf Dyes Encapsulated Within Polymer Nanoparticlesmentioning

confidence: 99%

See 1 more Smart Citation

Unlocking New Applications for Thermally Activated Delayed Fluorescence Using Polymer Nanoparticles

Caine,

Hu,

Gogoulis

et al. 2023

Acc. Mater. Res.

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Metrics & MoreArticle Recommendations CONSPECTUS: Thermally activated delayed fluorescence (TADF) materials are widely used in organic light-emitting diodes, but their long emission lifetimes also make them ideal for use in bioimaging probes, fluorescent sensors, and phototheranostics. Unfortunately, their development toward these applications has been restricted by the poor compatibility of most TADF materials with aqueous conditions. This problem can be addressed by encapsulating TADF dyes into nanoparticles that form stable aqueous suspensions, while preserving�or even enhancing�the photophysical properties of the TADF emitters they contain. Free of heavy metals, these nanoparticles can exhibit reduced cytotoxicity, improved oxygen tolerance, and higher brightness compared to unencapsulated TADF emitters. This Account discusses recent advances in the development and application of TADF-active polymer nanoparticles for use as biocompatible imaging probes and stimuli-responsive materials. We demonstrate that the encapsulation of TADF emitters into semiconducting polymer dots (Pdots), aggregated organic dots (a-Odots) and glassy organic dots (g-Odots) results in nanoparticles with tunable sizes, surface chemistries, and optoelectronic properties. These nanomaterials are particularly well-suited for bioimaging applications, with customizable bioconjugate chemistry and emission profiles ranging from deep-blue to near-infrared. As TADF materials generate long-lived emission, time-resolved fluorescence imaging can be used to obtain images with high signal-to-noise ratios against background biological autofluorescence. Materials with multiphoton absorbance properties capable of near-infrared excitation are also presented. We further discuss strategies for chemically modifying the nanoparticles' coronas using biomolecules and cell-penetrating motifs to target biological structures both internal and external to the cell. With these strategies, high-contrast imaging of human breast, liver, and kidney cancer cells has been achieved. The ability to target TADF-active nanoparticles to specific tissues, such as cancer cells, has also spurred advances in phototheranostics, which harness the ability for TADF materials to produce cytotoxic singlet oxygen upon irradiation with light. Lastly, as TADF materials can exhibit changes in emission with response to oxygen, temperature, and solvent conditions, we discuss how polymer integration can be used to generate highly effective probes for environmental stimuli. These sensors have potential applications as both in vitro nanosensors and in vivo molecular reporters for disease detection. As an alternative type of sensor, TADF materials have also been employed as reporters in electrochemiluminescence assays for biomarker detection. To explore stimulus−polymer interactions on a fundamental level, the incorporation of TADF materials into bottlebrush polymers is also discussed. Overall, this Account demonstrates that polymer nanoparticles containing TADF emitters have great potential to ...

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Section: Polymer Dotsmentioning

confidence: 99%

Section: Tadf Dyes Encapsulated Within Polymer Nanoparticlesmentioning

confidence: 99%

Unlocking New Applications for Thermally Activated Delayed Fluorescence Using Polymer Nanoparticles

Caine,

Hu,

Gogoulis

et al. 2023

Acc. Mater. Res.

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“…Despite emerging progress of design strategies that have been successful in the fabrication of phosphorescent Pt(II) complexes with a maximum peak at approximately 965 nm, a high quantum yield of 22.8% was achieved at the cost of significantly short-lived signals of 52 ns . Given that J-aggregates of fluorescent materials had been successfully developed for NIR-II bioimaging, − the synthesis strategy via J-aggregates to modify Pt(II) complexes still is not competent enough to balance the phosphorescent lifetime and quantum yield . Suffering from serious photophysical barriers, the discovered NIR-II phosphorescence only has optically critical significance to constitute new types of luminophores, instead of enabling high-resolution in vivo bioimaging.…”

Section: Synthesis Strategies Of Room-temperature Phosphorescence In ...mentioning

confidence: 99%

Molecularly Engineered Room-Temperature Phosphorescence for Biomedical Application: From the Visible toward Second Near-Infrared Window

Chang,

Chen,

Bao

et al. 2023

Chem. Rev.

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“…The accumulation of Pdots in the bone was attributed to the small population of Pdots with sizes of 30−50 nm. 71,72 After removal of skin and internal organs in mice, the whole skeletal system became clearer under excitation (Figure 4G,H). Finally, the mice were anatomized and Pdot distribution in major organs was analyzed (Figure 4I).…”

Section: ■ Introductionmentioning

confidence: 99%

Rational Design of Asymmetric Polymethines to Attain NIR(II) Bioimaging at >1100 nm

Pan

Lin

et al. 2022

J. Am. Chem. Soc.

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Organic molecules having emission in the NIR(II) region are emergent and receiving enormous attention. Unfortunately, attaining accountable organic emission intensity around the NIR(II) region is hampered by the dominant internal conversion operated by the energy gap law, where the emission energy gap and the associated internal reorganization energy λ int play key roles. Up to the current stage, the majority of the reported organic NIR(II) emitters belong to those polymethines terminated by two symmetric chromophores. Such a design has proved to have a small λ int that greatly suppresses the internal conversion. However, the imposition of symmetric chromophores is stringent, limiting further development of organic NIR(II) dyes in diversity and versatility. Here, we propose a new concept where as far as the emissive state of the any asymmetric polymethines contains more or less equally transition density between two terminated chromophores, λ int can be as small as that of the symmetric polymethines. To prove the concept, we synthesize a series of new polymethines terminated by xanthen-9-yl-benzoic acid and 2,4-diphenylthiopyrylium derivatives, yielding AJBF1112 and AEBF1119 that reveal emission peak wavelength at 1112 and 1119 nm, respectively. The quantum yield is higher than all synthesized symmetric polymethines of 2,4-diphenylthiopyrylium derivatives (SC1162, 1182(SC1162, , 1185(SC1162, , and 1230) in this study. λ int were calculated to be as small as 6.2 and 7.3 kcal/mol for AJBF1112 and AEBF1119, respectively, proving the concept. AEBF1119 was further prepared as a polymer dot to demonstrate its in vitro specific cellular imaging and in vivo tumor/bone targeting in the NIR(II) region.

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TADF-based NIR-II semiconducting polymer dots for in vivo 3D bone imaging

Abstract: A series of NIR-II fluorescent TADF-incorporated polymer dots were successfully synthesized. The function of the TADF moiety was fully studied and the bio-applications of these polymer dots including bone imaging were also demonstrated.

Cited by 13 publications

References 85 publications

Unlocking New Applications for Thermally Activated Delayed Fluorescence Using Polymer Nanoparticles

Unlocking New Applications for Thermally Activated Delayed Fluorescence Using Polymer Nanoparticles

Molecularly Engineered Room-Temperature Phosphorescence for Biomedical Application: From the Visible toward Second Near-Infrared Window

Rational Design of Asymmetric Polymethines to Attain NIR(II) Bioimaging at >1100 nm

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