Oligo(maleic anhydride)s: a platform for unveiling the mechanism of clusteroluminescence of non-aromatic polymers

Zhou, Xingbang; Luo, Wenwen; Xu, Liguo; Hu, Rongrong; Zhao, Zujin; Qin, Anjun; Tang, Ben Zhong

doi:10.1039/c7tc00868f

Cited by 170 publications

(153 citation statements)

References 41 publications

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“…Nonconventional fluorescent biogenic and synthetic polymers without aromatic structures have recently attracted considerable attention, and their clusteroluminescence mechanism behind this abnormal phenomenon is increasingly deciphered . For instance, Tang and co‐workers found that the intra‐ and inter‐chain n →π* interaction of carbonyl groups plays a crucial role during the emission for oligo(maleic anhydride)s (OMAhs) in the aggregated state/condensed phase . Zhang and co‐workers also proposed clustering‐triggered emission mechanism, namely the clustering of nonconventional chromophores and subsequent electron cloud can overlap with the simultaneous rigidification of conformation in the process of poly(amino acids).…”

Section: Methodsmentioning

confidence: 99%

Self‐Assembly of a Monochromophore‐Based Polymer Enables Unprecedented Ratiometric Tracing of Hypoxia

Wang

Guo

et al. 2018

Advanced Materials

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Ratiometric optical imaging holds promise for noninvasive visualization of hypoxic microenvironment induced by cancer cells since it can provide real-time and accurate information on cancers from microscopic to macroscopic levels with built-in calibration. [1] To date, a host of works on ratiometric optical imaging of tumor hypoxia rely on bischromophorebased system, which inevitably compromises imaging accuracy and specificity because of the undesirable energy/charge transferring interactions between the internal reference moiety and sensing chromophore (Scheme 1a). [2] At present, the accurate diagnosis of cancer hypoxia via monochromophore-based sensor with ratiometric readout still remains challenging. [3] Nonconventional fluorescent biogenic and synthetic polymers without aromatic structures have recently attracted considerable attention, and their clusteroluminescence mechanism behind this abnormal phenomenon is increasingly deciphered. [4] For instance, Tang and co-workers found that the intra-and inter-chain n→π* interaction of carbonyl groups plays a crucial role during the emission for oligo(maleic anhydride)s (OMAhs) in the aggregated state/condensed phase. [5] Zhang and co-workers also proposed clustering-triggered emission mechanism, namely the clustering of nonconventional chromophores and subsequent electron cloud can overlap with the simultaneous rigidification of conformation in the process of poly(amino acids). [4c] Thus, we examine whether the nonaromatic clusteroluminescence can be utilized as additional internal reference signal to construct a monochromophore-based ratiometric hypoxia nanosensor.With this in mind, we borrowed the nonaromatic clusteroluminescence strategy and developed a monochromophore-based ratiometric hypoxia probe (Pt-TPP-PVP 430 , Scheme 1b,c), which consists of a hydrophobic oxygen-sensitive Pt(II) tetraphenylporphyrin (Pt-TPP) and a hydrophilic backbone poly(N-vinylpyrrolidone) (PVP). Due to its amphiphilic nature, Pt-TPP-PVP 430 can self-assemble into nanoclusters in an aqueous solution, highly preferential to accumulate at tumor site by passive enhanced permeation and retentionThe accuracy of traditional bischromophore-based ratiometric probes is always compromised by undesirable energy/charge transferring interactions between the internal reference moiety and the sensing chromophore. In this regard, ratiometric sensing with a monochromophore system is highly desirable. Herein, an unprecedented monochromophorebased ratiometric probe, which consists of a hydrophilic backbone poly(N-vinylpyrrolidone) (PVP) and single chromophore of platinum(II) tetraphenylporphyrin (Pt-TPP) is reported. Combination of the specific assembled clustering-triggered fluorescent emission (oxygen-insensitive) with the original Pt-TPP phosphorescence (oxygen-sensitive) enables successful construction of a monochromophore-based ratiometric nanosensor for directly tracing hypoxia in vivo, along with the preferable facilitation of enhanced permeation and retention effect and long excitation ...

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Section: Methodsmentioning

confidence: 99%

Self‐Assembly of a Monochromophore‐Based Polymer Enables Unprecedented Ratiometric Tracing of Hypoxia

Wang

Guo

et al. 2018

Advanced Materials

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“…The origin of fluorescence in those aliphatic polymers have been explained by clusteroluminescence, considering the roles of several structural aspects, such as location of tertiary aliphatic‐amines in branching units of hyperbranched polymers,2f oxygen‐amine like “contact” donor–acceptor complexes,2f hydrogen bond,2j coordination bond‐assisted aggregation, and interpenetration of lone pair ( n ) of one carbonyl group of amide in empty π* orbital of another adjacent carbonyl group of amide/ester,2i,k in decreasing the interior mobility of rigid structures. However, the precise detection of fluorophores and associated mechanisms of fluorescence based on simultaneous roles of hydrogen bonding, structural rigidity, and clusteroluminescence, have not been reported to date.…”

Section: Methodsmentioning

confidence: 99%

Fluorescent Terpolymers via In Situ Allocation of Aliphatic Fluorophore Monomers: Fe(III) Sensor, High‐Performance Removals, and Bioimaging

Mahapatra

Dutta

Roy

et al. 2019

Adv Healthcare Materials

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Herein, purely aliphatic intrinsically fluorescent terpolymers, i.e., 1 and 2, are synthesized through one-pot solution polymerization via N-H functionalized and multi C-C/C-N coupled in situ protrusion of fluorescent monomers using two nonemissive monomers. These scalable terpolymers are suitable for highly selective Fe(III) sensing, high-performance exclusion of Fe(III), logic function and the imaging of normal mammalian Madin-Darby canine kidney and human osteosarcoma cancer cell lines. The structures of terpolymers, in situ attachment of fluorescent monomers, clusteroluminescence, adsorption-mechanism, and cell-imaging abilities are understood via unadsorbed and/or adsorbed microstructural analyses using 1 H/ 13 C NMR, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, UV-vis spectroscopy, atomic absorption spectroscopy, thermogravimetric analysis, high-resolution transmission electron microscopy, dynamic light scattering, fluorescence imaging, and fluorescence lifetime. The geometries, electronic structures, location of fluorophores, and singlet-singlet absorption and emission of terpolymers are examined using density functional theory (DFT) and time-dependent DFT. For the precise identification of fluorophores, transition from occupied natural transition orbitals (NTOs) to unoccupied NTOs is computed. For 1/2, limit of detection (LOD) values and adsorption capacities are 6.0 × 10 −7 /8.0 × 10 −7 m and 147.82/120.56 mg g −1 at pH i = 7.0 and 303 K, respectively. The overall properties of 1 are more advantageous compared to 2 in sensing, cell imaging, and adsorptive exclusion of Fe(III).

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“…To achieve solid-state room-temperature phosphorescence,t he choice of functional groups,i ntermolecular interactions,and p-p interactions become very important. [21] In such cases,a saconsequence of the high band gap of the molecular entities,the effective band gap of the bulk materials often appears near the blue edge of the visible spectrum. Br) can increase the extent of intersystem crossing, weak interactions such as hydrogen bonding and halogen bonding can lock molecules in the condensed state,thereby enhancing the chances of observing phosphorescence.…”

Section: Luminogens In the Solid Statementioning

confidence: 99%

Renaissance of Organic Triboluminescent Materials

Mukherjee

Thilagar

2019

Angew Chem Int Ed

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Solid‐state luminescence of organic dyes is an elusive frontier, and understanding and designing solid‐state stimuli‐responsive materials is not trivial. “Mechanoluminescence” (ML) or “triboluminescence” (TL), which is associated with fracture or force‐initiated luminescence from a material, is currently attracting new interest. Fracturing the surfaces of organic crystals ordered in noncentrosymmetric space groups can electronically excite the surface and neighboring molecules through piezo‐ or pyroelectric effects, and this can result in luminescence when the molecules relax back to their ground states. The combined duration of these two consecutive phenomena leads to force‐generated luminescence or TL. Although TL has been known for a very long time, examples of TL‐active materials are scarce, but are increasing as synthetic and characterization procedures develop. The question is now whether the relatively rare phenomenon of TL needs to be reevaluated to obtain a broader understanding of the subject.

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Oligo(maleic anhydride)s: a platform for unveiling the mechanism of clusteroluminescence of non-aromatic polymers

Abstract: The mechanism of clusteroluminescence has been unveiled by investigating maleic anhydride-based polymers and copolymers.

Cited by 170 publications

References 41 publications

Self‐Assembly of a Monochromophore‐Based Polymer Enables Unprecedented Ratiometric Tracing of Hypoxia

Self‐Assembly of a Monochromophore‐Based Polymer Enables Unprecedented Ratiometric Tracing of Hypoxia

Fluorescent Terpolymers via In Situ Allocation of Aliphatic Fluorophore Monomers: Fe(III) Sensor, High‐Performance Removals, and Bioimaging

Renaissance of Organic Triboluminescent Materials

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