Tetrathienylethene based red aggregation-enhanced emission probes: super red-shifted mechanochromic behavior and highly photostable cell membrane imaging

Liu, Junjie; Yang, Jie; Wang, Jinliang; Chang, Zhengfeng; Li, Bo; Song, Wenting; Zhao, Zujin; Lou, Xiaoding; Dai, Jun; Xia, Fan

doi:10.1039/c8qm00008e

Cited by 41 publications

(18 citation statements)

References 67 publications

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“…Molecular construction of organic π‐conjugated materials owning long‐wavelength emissive properties has been of great demand and potential applications in the photoelectronic devices, such as organic light‐emitting diodes and luminescent solar concentrator . More importantly, long‐wavelength emissive fluorescent materials have many prominent merits in biological imaging, owing to their deep tissue penetration, less biological photodamage, and minimum interference from background autofluorescence of biomolecules in living systems . To date, this is still of great demand to develop new long‐wavelength emissive fluorophores.…”

Section: Methodsmentioning

confidence: 99%

Red/NIR‐Emissive Benzo[d]imidazole‐Cored AIEgens: Facile Molecular Design for Wavelength Extending and In Vivo Tumor Metabolic Imaging

et al. 2018

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biological imaging, [3] owing to their deep tissue penetration, less biological photodamage, and minimum interference from background autofluorescence of biomolecules in living systems. [4] To date, this is still of great demand to develop new long-wavelength emissive fluorophores. Lengthening the π-electron system has been recognized as one of the general design strategy to develop fluorescent materials with long wavelength absorbing or emitting, for example, oligo-olefins and polymethine dyes. [4a,5] However, these conventional fluorophores possess thermal and photochemical instability, small Stokes shift, high interference from the excitation light and/or self-absorption, and aggregation-caused quenching (ACQ) effect (strong emission in dilute solution but quenching upon the concentration increased due to their strong intermolecular π-π interactions). All these respective and collective drawbacks limit their biomedical applications. [6] The donor-acceptor (D-A) architecture has been a broadly adopted strategy for designing the long-wavelength emissive molecules, [7] whereby electron-donating and electron-withdrawing segments are incorporated into the molecular backbone. [8] After the molecular orbitals (MOs) of the conjugated Aggregation-induced emission (AIE) luminogens (AIEgens) with red/nearinfrared (NIR) emissions are appealing for applications in optoelectronics and biomedical engineering owing to their intrinsic advantages of efficient solidstate emission, low background, and deep tissue penetration. In this context, an AIEgen with long-wavelength emission is synthesized by introducing tetraphenylethene (TPE) to the periphery of electron-deficient spiro-benzo[d] imidazole-2,1′-cyclohexane (BI). The resulting AIEgen, abbreviated as 2TPE-BI, adopts a donor-acceptor structure and shows bathochromic absorption and emission with a larger Stokes shift of 157 nm in acetonitrile than that based on benzo[c][1,2,5]thiadiazole. It also exhibits a high solid-state fluorescence quantum yield of 56.6%. By further insertion of thiophene to its molecular structure generates 2TPE-2T-BI with higher conjugation and NIR emission. 2TPE-2T-BI can be fabricated into AIE dots for in vivo metabolic labeling through bio-orthogonal click chemistry. These results open a new approach for facile construction of long-wavelength emissive AIEgens based on the BI core.Molecular construction of organic π-conjugated materials owning long-wavelength emissive properties has been of great demand and potential applications in the photoelectronic devices, such as organic light-emitting diodes [1] and luminescent solar concentrator. [2] More importantly, long-wavelength emissive fluorescent materials have many prominent merits in Scheme 1. Design strategy of quinoidal AIEgens based on benzo[d]imidazole acceptor and antistacking spiro-cyclohexane substituent.

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Section: Methodsmentioning

confidence: 99%

Red/NIR‐Emissive Benzo[d]imidazole‐Cored AIEgens: Facile Molecular Design for Wavelength Extending and In Vivo Tumor Metabolic Imaging

et al. 2018

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“…The accumulation of AIE probes could cause bright fluorescence and large Stokes shifts, which is highly desirable for bioimaging . Although several AIE probes with PM specific have been reported, each of them has their own pros and cons. For instance, most of them require longer staining times and tedious post‐cleaning procedures, which could cause the loss of cell membranes, changes of the cellular microenvironment, and longer operational time thus limiting their further application.…”

Section: Methodsmentioning

confidence: 99%

“…Nevertheless, because of poor PM specificity, imaging of PM in complex systems is still a great challenge. Herein, combined with the experience of preceding studies, we report a specific water‐soluble AIE probe Pent‐TMP and applied it to image the PM in different model systems, including 2D/3D cells, tissue model, and live zebrafish in vivo. To the best of our knowledge, this is the first time the erythrocyte membrane has been imaged in complex brain tissue.…”

Section: Methodsmentioning

confidence: 99%

An AIE‐Based Probe for Rapid and Ultrasensitive Imaging of Plasma Membranes in Biosystems

Shi

Liu

et al. 2019

Angewandte Chemie

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The abnormality of the plasma membrane (PM) is an important biomarker for cell status and many diseases. Hence, visualizing the PM, especially in complex systems, is an emerging field in the life sciences, especially in low‐resource settings. Herein, we developed a water‐soluble PM‐specific probe utilizing electrostatic and hydrophobic interaction strategies with aggregation‐induced emission as the signal output. The probe could image the PM with many advanced features (wash‐free, ultrafast staining process, excellent PM specificity, and good biocompatibility), which were demonstrated by the PM imaging of neurons. The probe allowed for the first time the imaging of erythrocytes in the complex brain environment through a fluorescence‐based method. Moreover, the PM of the epidermal and partial view of the eyeball structure of live zebrafish are also revealed.

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“…The intermediate TTE-4Br was synthesized from TTE according to the literature's methods. [18] The target isomers were obtained by Suzuki cross coupling reaction between TTE-4Br and ortho-/meta-/para-formyl phenylboronic acid with good yields of 66 %, 67 % and 80 % (For detail see SI). Molecular structures were characterized using 1 H NMR, 13 C NMR spectra, HR-ESI MS and single crystal Xray diffraction pattern ( Figure S1-S3).…”

Section: Synthesis and Characterizationmentioning

confidence: 99%

Tetrathienylethene‐based Positional Isomers with Aggregation‐induced Emission Enabling Super Red‐shifted Reversible Mechanochromism and Naked‐eye Sensing of Hydrazine Vapor

Song

Zhi

Wang

et al. 2019

Chemistry An Asian Journal

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AIE-active positional isomers, TTE-o-PhCHO, TTEm-PhCHO and TTE-p-PhCHO, tetrathienylethene (TTE) derivates with peripherally attached ortho-/meta-/para-formyl phenyl groups, were designed and synthesized. The formyl substitution position can effectively modulate their photophysical properties, mechanochromism and fluorescent response to hydrazine. TTE-o-PhCHO and TTE-m-PhCHO exhibit remarkable AIE characteristics, and TTE-p-PhCHO possesses aggregation-induced emission enhancement performance. They all exhibit high contrast mechanochromism, and TTE-m-PhCHO shows larger red-shift (164 nm) thanTTE-o-PhCHO (104 nm) and TTE-p-PhCHO (125 nm) due to the more twisted molecular conformation and much looser molecular packing. Moreover, TTE-o-PhCHO with a higher contrast color change can be used as ink-free rewritable paper. In addition, TTE-p-PhCHO, as a turn-on fluorescent probe, can selectively detect hydrazine with significant color changes that are visible by the naked eye . Therefore, the position dependence of groups would be an effective method to modulate the molecular arrangement, as well as develop AIE compounds for mechano-stimuli responsive materials, ink-free rewritable papers and chemosensors.[a] Dr.Supporting information and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

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Tetrathienylethene based red aggregation-enhanced emission probes: super red-shifted mechanochromic behavior and highly photostable cell membrane imaging

Abstract: A series of branched π-conjugated small molecular red aggregation-enhanced emission probes have been synthesized for mechanochromic applications and cell imaging.

Cited by 41 publications

References 67 publications

Red/NIR‐Emissive Benzo[d]imidazole‐Cored AIEgens: Facile Molecular Design for Wavelength Extending and In Vivo Tumor Metabolic Imaging

Red/NIR‐Emissive Benzo[d]imidazole‐Cored AIEgens: Facile Molecular Design for Wavelength Extending and In Vivo Tumor Metabolic Imaging

An AIE‐Based Probe for Rapid and Ultrasensitive Imaging of Plasma Membranes in Biosystems

Tetrathienylethene‐based Positional Isomers with Aggregation‐induced Emission Enabling Super Red‐shifted Reversible Mechanochromism and Naked‐eye Sensing of Hydrazine Vapor

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