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TPE
RSC Advances · 2019 ·Vol. 9 ·期 32 ·18098-18105 · IF 3.049

Synthesis of π-conjugated network polymers based on triphenylamine (TPA) and tetraphenylethylene (TPE) as building blocks via direct Pd-catalyzed reactions and their application in CO2 capture and explosive detection

Lamaocao Ma,Hengchang Ma

In this study, we report the synthesis of π-conjugated network polymers via palladium-catalyzed direct arylation polycondensation of triphenylamine (TPA) and tetraphenylethylene (TPE) with different active substrates. Moreover, six conjugated porous polymers were obtained (named as TPA-TPA-MA, TPA-PB-MA, TPA-TFB-MA, TPA-TPE-MA, TPE-PB-MA, and TPE-TFB-MA). Then, the fluorescence properties in the solid and dispersed states, the corresponding microporous structures, and the Brunauer–Emmett–Teller (BET) surface areas of all polymers were well studied. Among the obtained materials, TPA-PB-MA possessed not only largest BET surface area (686 m2 g−1) and largest pore volume (0.716 cm3 g−1), but also the smallest pore size of 0.823 nm. These properties are very beneficial for the application of TPA-PB-MA in CO2 storage and PA sensing. At 1 bar, TPA-PB-MA demonstrated the significant CO2 uptake of 2.70 and 1.35 mmol g−1 at 273 and 298 K, respectively. Furthermore, TPA-PB-MA was most sensitive and selective towards PA recognition. The KSV constant was measured as 4.0 × 104 M−1.

研究领域: 材料科学 · 化学工程 · 环境科学
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ANALYTICAL AND BIOANALYTICAL CHEMISTRY · 2024 · IF 3.8

Reversible addition-fragmentation chain transfer enhanced aggregation signal-on fluorescence detection of alkaline phosphatase

Yu Shuaibing,Li Lianzhi,Kong Qiyun,Zhang Wenqi,Chen Huan,Zhang Xueji,Kong Jinming

The instability of the signal intensity of fluorescent biosensors and the false signals have been significant factors affecting the performance of biosensors. Herein, a novel signaling system is devised through the application of reversible addition-fragmentation chain transfer (RAFT) polymerization with monomers containing the tetraphenylethylene (TPE) groups. TPE exhibits an aggregation-induced emission (AIE) phenomenon in certain solvents, mainly due to the blockage of the rotation of its four benzene rings, which also exist in the aggregated state. With this property, a series of molecules are modified based on click chemistry for RAFT polymerization using Fe 3 O 4 magnetic beads as the carriers, and stable aggregated luminescent TPE polymers are formed on the surface of magnetic beads to realize the transformation of fluorescence signal from “0” to “1”. In addition, the fluorescence signal demonstrates a positive correlation with alkaline phosphatase (ALP) activity, which can be quantified by measuring the fluorescence intensity. The biosensor exhibits high sensitivity and good linearity in the range of 0.1–5 U/L, with a LOD of 0.079 U/L. Furthermore, the designed strategy demonstrated satisfactory performance in the quantitative determination of ALP activity in serum samples, indicating that the signaling system developed by combining RAFT polymerization and AIE molecules has an important application in the field of fluorescent biosensors. Graphical Abstract

研究领域: 分析化学 · 生物技术 · 生物化学
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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH · 2021 · IF 3.764

PhotoATRP Approach to Poly(methyl methacrylate) with Aggregation-Induced Emission

Wenli Liu,Qizhi Yang,Yili Yang,Feiyue Xing,Pu Xiao

In the past decades, polymeric fluorescent materials with aggregation-induced emission (AIE) properties play important roles in the fields of biomedical and analytical chemistry, and the synthesis of well-defined polymers under mild conditions is in demand. In this report, narrowly distributed poly(methyl methacrylate)s (PMMAs) with AIE properties were prepared in mild conditions using 4-(1,2,2-triphenylvinyl)benzyl 2-bromo-2-phenylacetate (TPE-BPA), a novel initiator with an AIE-based functional group. This approach resulted in PMMAs with a fluorescent tag at the chain end (TPE-PMMA). Specifically, a high efficiency of initiation was observed using a low amount of air-stable copper(II) bromide/tris(2-pyridylmethyl)amine (CuIIBr2/TPMA) as a photocatalyst under the irradiation of LED@405 nm. Moreover, the TPE presented in the system did not affect the polymerization kinetics of MMA and the temporal control. The dispersities of the obtained PMMAs were as low as 1.12. Interestingly, TPE-PMMA with narrow dispersity was also obtained (Mw/Mn < 1.25) in the presence of air. Regarding the fluorescent properties of TPE-PMMAs, it was observed that their AIE intensities increased with the molecular weights. Moreover, they could also be used to probe the increased viscosity of the solution, indicating their potential of synthesizing functional sensors. The approach proposed in this work is convenient to prepare poly(methacrylate)s with well-defined structures in the presence of AIE-based fluorescent tags, and it thus paves a new way for the rational design of AIE-functionalized polymeric materials.

CAS / MDL: 80-62-6
研究领域: 高分子化学 · 材料科学 · 分析化学 · 生物医学工程
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Journal of Materials Chemistry C · 2020 ·Vol. 8 ·期 45 ·16121-16128 · IF 7.059

Luminescent two-way reversible shape memory polymers prepared by hydroxyl–yne click polymerization

Kaojin Wang,Han Si,Qing Wan,Zhiming Wang,Anjun Qin,Ben Zhong Tang

Two-way reversible shape memory polymers (2W-SMPs), capable of changing their shape reversibly, are highly desirable for many potential applications. However, the polymerization reactions used for preparing 2W-SMPs always require harsh conditions, such as metal catalysts, light irradiation and elevated temperature. Furthermore, there are few reports on SMPs that integrated with other functions, such as luminescence. Herein, luminescent 2W-SMPs of semi-crystalline PCL-based networks bearing an aggregation-induced emission (AIE) moiety of tetraphenylethylene (TPE) are designed and prepared via an organobase-catalyzed hydroxyl–yne click polymerization under mild reaction conditions. For comparison, a TPE-free polymer network is also prepared through the same polymerization. The TPE-containing polymer network shows stronger emission than that of the TPE-containing monomer because of the restriction of intramolecular rotation. Both the polymer networks are able to perform excellent reversible shape motions, such as bending–unbending, coiling–uncoiling, and closing–blooming, when they are exposed to cold and warm water. By taking advantage of the shape memory and luminescence properties, the TPE-containing polymer network could be used to construct a luminescent robotic gripper, which can grab and release weights with payload-to-weight ratios much higher than that of many industrial robotic grippers. Moreover, it could also be used to realize a double anti-counterfeiting function. This work represents the first example of luminescent 2W-SMPs, which might be widely applied in diverse areas.

研究领域: 材料科学 · 高分子化学 · 机械工程 · 光电技术
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RSC Advances · 2018 ·Vol. 8 ·期 27 ·14995-15000 · IF 2.936

A sensitive fluorescent probe for alkaline phosphatase and an activity assay based on the aggregation-induced emission effect

Wenjuan Zhang,Hanxiao Yang,Nan Li,Na Zhao

In this work, we report a fluorescent probe (TPEQN-P) for detecting alkaline phosphatase (ALP) with high sensitivity and monitoring its activity based on the specific aggregation-induced emission (AIE) effect. TPEQN-P can be constructed by conjugating the phosphate moiety into an AIE molecule (TPE-QI) through a reactive p-hydroxybenzyl group, which exhibits very weak emission in aqueous media due to its good water solubility. In the presence of ALP, TPEQN-P undergoes dephosphorylation and releases the hydrolysis product TPE-QI, which is intensely fluorescent because of its poor water solubility. The detection limit for ALP using TPEQN-P can be as low as 0.0077 U L−1 with a linear range of 0–30 mU mL−1 in solution. TPEQN-P also shows excellent applicability in serum samples, demonstrating potential applications in clinical diagnosis and biomedical research. TPEQN-P also can be applied for the determination of ALP activity and in ALP inhibitor screening.

CAS / MDL: 9048-46-8
研究领域: 分析化学 · 生物化学 · 分子生物学 · 临床化学
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DYES AND PIGMENTS · 2019 · IF 4.018

Precise control for the aggregation and deaggregation with the aid of a tetraphenylethylene derivative: Luminescence modulation and sensing performance

Xiangqian Li,Jiapei Gu,Zhan Zhou,Wanqiang Liu,Jinwei Gao,Qianming Wang

The versatility of the organic fluorophores enables us to track its emission curves and sharp luminescence changes under controllable conditions. A tetraphenylethylene-based fluorescent probe (1-methyl-4-(4-(1,2,2-triphenylvinyl)styryl)pyridin-1-ium iodide, abbreviated as TPE-py-I ) has been synthesized and yields efficient red emission in organic phase (DMSO). The incorporation of ClO − in its DMSO solution triggers efficient “on-off” quenching effect due to ions exchange from iodide to hypochlorite. The inactivation of the original red luminescence can be also realized by the addition of water and the typical aggregation-caused-quenching (ACQ) has been observed. Unexpectedly, such ACQ process will be suppressed and lead to an aggregation-induced-emission (AIE) effect, providing distinct fluorescent read-out from pale-red to bright yellow in the presence of hypochlorite. The limit of detection (LOD) has been calculated to be 0.25 μM via ratiometric operation with an excellent linear range from 1 μM to 50 μM. This non-invasive and in-situ detection of ClO − via AIE modes can be employed as an indicator for the evaluation of ions responses in real environments.

研究领域: 材料科学 · 分析化学 · 光学传感
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Polymer Chemistry · 2020 ·Vol. 11 ·期 35 ·5619-5629 · IF 5.342

Azoreductase-triggered fluorescent nanoprobe synthesized by RAFT-mediated polymerization-induced self-assembly for drug release

Yechun Zhou,Zhe Wang,Yuqing Wang,Lishan Li,Nianchen Zhou,Yuanli Cai,Zhengbiao Zhang,Xiulin Zhu

Azobenzene-based polymeric nanoparticles have emerged as promising candidate for biological detection and controlled drug release in an anaerobic environment for colon disease treatment. Herein, we report a novel and efficient polymerization-induced self-assembly (PISA) strategy for fabricating polymeric nanovehicles to load drugs for triggered release and fluorescence detection based on a TPE (tetraphenylethylene)-azobenzene fluorescence probe sensitive to hypoxic microenvironments. In this study, a series of PISA-nanoparticles, including micelles and vesicles, were synthesized by reversible addition–fragmentation transfer (RAFT) dispersion copolymerization of monomers butyl methacrylate (BMA) and reductive-responsive TPE-AZO-MA (TPE-azobenzene derived methacrylate) in a 1,4-dioxane/water mixture. Subsequently, polymeric micelles loaded with doxorubicin (DOX) in situ were successfully obtained by PISA. Furthermore, the release and fluorescence change of PISA-formed micelles loaded with DOX were studied in a simulated colon environment under the action of azoreductase. As expected, the drug-loaded micelles showed an effective DOX release during enzyme hydrolysis within 24 h owing to azo bond cleavage. Meanwhile, significant fluorescence enhancement was observed, accompanied by the release process. This was due to the aggregation-induced emission (AIE) performance of TPE being efficiently activated by elimination of the fluorescence resonance energy transfer (FRET) process, also owing to azo bond cleavage. Finally, the cytotoxicity and cellular uptake of the blank micelles and DOX-loaded micelles in vitro were evaluated.

研究领域: 药学 · 材料科学 · 纳米技术 · 生物医学工程
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Nature Protocols · 2024 · IF 13.1

Preparation of AIEgen-based near-infrared afterglow luminescence nanoprobes for tumor imaging and image-guided tumor resection

Chen Chao,Zhang Xiaoyan,Gao Zhiyuan,Feng Guangxue,Ding Dan

Fluorescence imaging represents a vital tool in modern biology, oncology and biomedical applications. Afterglow luminescence (AGL), which circumvents the light scattering and tissue autofluorescence interference associated with real-time excitation source, shows remarkably increased imaging sensitivity and depth. Here we present a protocol for the design and synthesis of AGL nanoprobes with an aggregation-induced emission (AIE) effect to simultaneously red shift and amplify the afterglow signal for tumor imaging and image-guided tumor resection. The nanoprobe (AGL AIE dot) is composed of an enol ether format of Schaap’s agent and a near-infrared AIE fluorogen (AIEgen) (tetraphenylethylene-phenyl-dicyanomethylene-4H-chromene, TPE-Ph-DCM) to suppress the nonradiative dissipation pathway. Pre-irradiating AGL AIE dots with white light could generate singlet oxygen to convert Schaap’s agent to its 1,2-dioxetane format, thus initializing the AGL process. With the aid of AIEgen, the AGL shows simultaneously red shifted emission maximum (from ~540 nm to ~625 nm) and enhanced intensity (by 3.2-fold), facilitating better signal-to-background ratio, imaging sensitivity and depth. Intriguingly, the activated AGL can last for over 10 days. Compared with conventional approaches, our method provides a new solution to concurrently red shift and amplify afterglow signals for better in vivo imaging outcomes. The preparation of AGL AIE dots takes ~2 days, the in vitro characterization takes ~10 days (less than 1 day if not involving afterglow kinetic profile study) and the tumor imaging and image-guided tumor resection takes ~7 days. These procedures can be easily reproduced and amended after standard laboratory training in chemical synthesis and animal handling.

CAS / MDL: 7722-84-1
研究领域: 生物医学工程 · 肿瘤学 · 生物成像 · 纳米技术 · 化学
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Aggregate · 2024 · IF 13.9

Low-temperature-curable and photo-patternable benzocyclobutene-derived aggregation-induced emission-active polymer dielectrics

Ziwei Yuan,Meng Xie,Jianlei Qian,Wenjie Fan,Menglu Li,Liao Guo,Yan Sun,Wenxin Fu

The high curing temperatures required for traditional benzocyclobutene (BCB) materials have posed limitations on their applicability in high-temperature-sensitive fields. To address this challenge, our work focuses on the synthesis of a novel tetraphenylethylene (TPE)-functionalized BCB monomer, TPE–BCB, achieved through the introduction of an ether bond onto the BCB's four-membered ring via Williamson reaction. TPE–BCB demonstrates remarkable low-temperature curing properties, characterized by a ring-opening peak temperature of 190°C, representing a reduction of 60°C compared to conventional BCBs. Fully cured TPE–BCB resins exhibit exceptional dielectric and mechanical properties, coupled with minimal water absorption. Additionally, the incorporation of TPE with aggregation-induced emission characteristics enhances the resins’ luminescence and photolithographic capabilities. Notably, our TPE–BCB resins achieve impressive photolithography performance with a resolution ratio of up to 10 μm. In contrast to conventional BCB-functionalized resins, TPE–BCB offers the dual advantage of low-temperature curing and luminescence. This development marks a significant step in the advancement of low-temperature curing BCB materials and serves as a pioneering example in the realm of multilayer wafer bonding materials.

CAS / MDL: 1137-42-4 7550-45-0
研究领域: 材料科学 · 聚合物化学 · 电气工程 · 光子学
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SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY · 2022 · IF 4.831

Preparation of temperature-responsive nanomicelles with AIE property as fluorescence probe for detection of Fe3+ and Fe2+

Xinhui Hou,Yifan Song,Yupeng Lv,Peiyao Wang,Kun Chen,Guiying Li,Lei Guo

Temperature-responsive nanomicelles with aggregation induced emission (AIE) property were prepared by the host–guest complexation of ferrocene functionalized tetraphenyl (TPE-Fc) and β-cyclodextrin-poly ( N -isopropylacrylamide) (β-CD-(PNIPAM) 7 ). The AIE chromophore TPE-Fc bound to the hydrophobic cavity of cyclodextrin serves as the core of micelles, and temperature sensitive PNIPAM serves as the shell to give the micelles good solubility. The size of the nanomicelles is about 100 nm. At the excitation wavelength of 340 nm, the strongest fluorescent emission peak was 421 nm. The introduction of cyclodextrin star polymer increased the fluorescence intensity of nanomicelles, thus improving the recognition of probe to Fe 3+ and Fe 2+ . The fluorescent probe can quickly detect Fe 3+ and Fe 2+ in water within 5 min even in the presence of various interfering ions. The detection limits of Fe 3+ and Fe 2+ were 1.04 μM and 0.78 μM, respectively in the range of 10–90 μM. The formation of complex between the probe and Fe 3+ /Fe 2+ was supported by Job’s plot. The probe was successfully applied to the detection of Fe 3+ and Fe 2+ in actual water sample with a good recovery. In addition, a possible sensing mechanism for the interaction of iron ions with amide bond groups of nanomicelles was proposed.

CAS / MDL: 77-86-1
研究领域: 材料科学 · 分析化学 · 纳米技术
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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2018 · IF 5.091

Facile fabrication of organic dyed polymer nanoparticles with aggregation-induced emission using an ultrasound-assisted multicomponent reaction and their biological imaging

Ruming Jiang,Meiying Liu,Hongye Huang,Liucheng Mao,Qiang Huang,Yuanqing Wen,Qian-yong Cao,Jianwen Tian,Xiaoyong Zhang,Yen Wei

Ultrasound as a powerful technique has increasingly been used in both industry and academia in recent years. Herein, an efficient approach to the ultrafast preparation of cross-linked fluorescent copolymers (PEGMA-AEMA-TPE) with aggregation-induced emission (AIE) via an ultrasound-assisted multicomponent reaction (MCR) is described. A number of characterization techniques were carried out to certify the successful preparation of these AIE-active copolymers. Due to the introduction of a hydrophilic PEG fragment and a hydrophobic AIE-active dye, the obtained fluorescent copolymers showed amphiphilic properties and could assemble into organic dyed polymer nanoparticles (ODPNs) with great water dispersibility. The final PEGMA-AEMA-TPE ODPNs demonstrated intense fluorescence, strong photostability, a low critical micelle concentration (CMC) of 0.007 mg mL −1 and high biocompatibility. More importantly, the PEGMA-AEMA-TPE ODPNs show obvious AIE characteristics, which could elegantly overcome the quenching effect caused by the aggregation of ODPNs based on conventional organic dyes. Considered the above results, we believe that these AIE-active ODPNs should be promising candidates for biological imaging and other biomedical applications.

研究领域: 材料科学 · 纳米技术 · 生物医学工程 · 化学
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Polymer Chemistry · 2020 ·Vol. 11 ·期 48 ·7704-7713 · IF 5.342

Enzyme-responsive polymeric micelles with fluorescence fabricated through aggregation-induced copolymer self-assembly for anticancer drug delivery

Ke Yan,Shujing Zhang,Kun Zhang,Yalei Miao,Yudian Qiu,Panke Zhang,Xu Jia,Xubo Zhao

Designing polymer-based nanostructures through self-assembly has great practical significance in biomedical applications, especially in drug delivery. In general, hydrophobic chains can induce the self-assembly of amphiphilic copolymer to form polymer-based nanostructures in an aqueous phase. However, the application of polymer-based nanostructures has been prevented due to the insufficient functionality of hydrophobic chains. To address these critical issues, the unique tetraphenylethene (TPE) moiety is employed with aggregation-induced emission (AIE) as functional hydrophobic chains to induce copolymer self-assembly and form polymeric micelles that can show strong fluorescence and a low critical micelle concentration (CMC) in aqueous solution. The novel polymeric micelles can efficiently encapsulate doxorubicin (DOX) molecules, and their favorable stability is demonstrated in a physiological medium. More importantly, the disassembly of polymeric micelles is triggered in the presence of esterase, then causing drug release and fluorescence quenching. It is demonstrated that DOX-loaded polymeric micelles have an obvious toxicity against cancer cells. This work confirms that the combination of AIE and self-assembly is an effective strategy for expanding the application of block copolymers and developing new enzyme-responsive polymeric micelles for cancer therapy.

研究领域: 生物医学工程 · 纳米技术 · 药学 · 材料科学
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