Facial Control Intramolecular Charge Transfer of Quinoid Conjugated Polymers for Efficient in Vivo NIR-II Imaging
Abstract
Low-band gap conjugated polymers with donor-acceptor (D-A) structures have emerged as second near-infrared (NIR-II) fluorescence probes for biological imaging. However, how to control the intramolecular charge transfer (ICT) to maintain the low band gap and improve the NIR-II fluorescence intensity is an urgent issue. Here, the quinoid polymers have been developed to effectively regulate the ICT for brighter NIR-II fluorescence signals. Thiophene repeat chain units of different lengths (T, 2T, and 3T) were utilized to link with electron-withdrawing ester-substituted thieno[3,4- b]thiophene (TT) to alter the density of the electron-withdrawing side groups for controlling the ICT. By increasing the thiophene chain length from TT-T to TT-3T, the density of the electron-withdrawing groups decreased and the ICT was weakened. In the case of NIR absorption and NIR-II emission, weakened ICT leads to brighter NIR-II fluorescence. After the preparation of the water-soluble quinoid polymer probes (CPs), TT-3T CPs with weak ICT exhibited the brightest NIR-II fluorescent signals among the three quinoid polymer probes. Several NIR-II biomedical imaging applications, including in vivo cell tracking, blood vascular system images, and lymphatic drainage mapping, show that the TT-3T CP-based nanoprobe had excellent characteristics of long-term stability and high NIR-II spatial resolutions in vivo.
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By increasing the length of the thiophene chain from TT-T to TT-3T, the density of the electron-withdrawing group decreased, leading to weaker ICT and thus brighter fluorescence.
“By increasing the length of the thiophene chain from TT-T to TT-3T, the density of the electron-withdrawing group decreased, leading to weaker ICT and thus brighter fluorescence.”
From The Pursuit of Shortwave Infrared-Emitting Nanoparticles with Bright Fluorescence through Molecular Design and Excited-State Engineering of Molecular Aggregates (2022) · cites this paper as [173]
Among the Pdots consisting of these CPs and an amphiphilic copolymer Pluronic F-127, TT-3T Pdots exhibited a largest Φfl (Φfl = 1.75% in water, 0.33% after correction, Φfl of R1061 = 0.32% in DCE) because of the weaker ICT compared with others.
“Among the Pdots consisting of these CPs and an amphiphilic copolymer Pluronic F-127, TT-3T Pdots exhibited a largest Φfl (Φfl = 1.75% in water, 0.33% after correction, Φfl of R1061 = 0.32% in DCE) because of the weaker ICT compared with others.”
From The Pursuit of Shortwave Infrared-Emitting Nanoparticles with Bright Fluorescence through Molecular Design and Excited-State Engineering of Molecular Aggregates (2022) · cites this paper as [173]
A series of quinoid polymers containing ester-substituted thieno [3,4-b] thiophene (TT) connected with a varied lengths of thiophene units (thiophene (T), bithiophene (2T), and terthiophene (3T)) were designed with the aim of controlling the fluorescence brightness in the SWIR range.
“A series of quinoid polymers containing ester-substituted thieno [3,4-b] thiophene (TT) connected with a varied lengths of thiophene units (thiophene (T), bithiophene (2T), and terthiophene (3T)) were designed with the aim of controlling the fluorescence brightness in the SWIR range (Figure 9a).173”
From The Pursuit of Shortwave Infrared-Emitting Nanoparticles with Bright Fluorescence through Molecular Design and Excited-State Engineering of Molecular Aggregates (2022) · cites this paper as [173]
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- Authors
- Zhang, W., Huang, T., Li, J., Sun, P., Wang, Y., Shi, W., Han, W., Wang, W., Fan, Q., & Huang, W.
- Affiliations
- Nanjing University of Posts and Telecommunications (CN)
- Nanjing Tech University (CN)
- Nanjing University (CN)
- Liaocheng University (CN)
- Northwestern Polytechnical University (CN)
- Corresponding author
- Sun, Pengfei
- Fan, Quli
- ORCID
- Venue
- ACS Applied Materials & Interfaces
- Publisher
- American Chemical Society (ACS)
- Published
- 2019-04-17
- Volume
- 11
- Issue
- 18
- Pages
- 16311-16319
- ISSN
- 1944-8244 (ISSN-L)
- 1944-8252
- OpenAlex
- W2940442761
- Cited by
- 80
- References
- 53
- Citations by year
- 2026: 6 · 2025: 5 · 2024: 11 · 2023: 6 · 2022: 16 · 2021: 14 · 2020: 18 · 2019: 4
- FWCI
- 4.69
- Type
- journal article
- Language
- en
- Open access
- closed
- Licence
- Locations
- ACS Applied Materials & Interfaces (publishedVersion)
- PubMed (publishedVersion)
- Funders
- National Natural Science Foundation of China (21604042, 21674048, 21574064)
- Nanjing University of Posts and Telecommunications (NY211003)
- Ministry of Science and Technology of the People's Republic of China (2015CB932200)
- Government of Jiangsu Province (BE2016770, BRA2016379)
- Topics
- Physical Sciences › Materials Science › Materials Chemistry › Luminescence and Fluorescent Materials
- Physical Sciences › Chemistry › Spectroscopy › Molecular Sensors and Ion Detection
- Physical Sciences › Chemistry › Physical and Theoretical Chemistry › Photochemistry and Electron Transfer Studies
- Keywords
- intramolecular charge transfer, NIR-II fluorescence, donor-acceptor polymers, electron-withdrawing substituents, water-soluble polymers, in vivo imaging, cell tracking, vascular imaging, lymphatic mapping, fluorescent nanoprobes
- MeSH terms
- Electrons, Fluorescent Dyes, Humans, Polymers, Spectrometry, Fluorescence, Thiophenes, Molecular Structure, Spectroscopy, Near-Infrared, Nanoparticles, Cell Tracking
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