tetraphenylethylene

四苯基乙烯
  • 文章类型: Journal Article
    两种发蓝光的材料,4-(12-([1,1\':3\',1″-三联苯]-5′-基)chrysen-6-基)-N,N-二苯基苯胺(TPA-C-TP)和6-([1,1\':3\',1″-三联苯]-5′-基)-12-(4-(1,2,2-三苯基乙烯基)苯基(TPE-C-TP),用菊心部分和三联苯(TP)的组成制备,三苯基胺(TPA),和四苯基乙烯(TPE)部分作为侧基。TPA-C-TP和TPE-C-TP的最大光致发光(PL)发射波长在溶液状态下为435和369nm,在膜状态下为444和471nm。TPA-C-TP通过引入TPA有效防止了分子间的堆积,庞大的芳香胺基,在薄膜状态下表现出86%的优异的光致发光量子产率(PLQY)。TPE-C-TP表现出聚集诱导的发射;从溶液状态到膜状态,PLQY从0.1%急剧增加到78%。两种合成材料均具有优异的热稳定性,具有超过460°C的高分解温度。这两种化合物用作非掺杂器件中的发光层。TPA-C-TP器件实现了优异的电致发光(EL)性能,国际委员会的计算坐标为(0.15,0.07),外部量子效率为4.13%,对应于439nm的EL峰值波长。
    Two blue-emitting materials, 4-(12-([1,1\':3\',1″-terphenyl]-5\'-yl)chrysen-6-yl)-N,N-diphenylaniline (TPA-C-TP) and 6-([1,1\':3\',1″-terphenyl]-5\'-yl)-12-(4-(1,2,2-triphenylvinyl)phenyl)chrysene (TPE-C-TP), were prepared with the composition of a chrysene core moiety and terphenyl (TP), triphenyl amine (TPA), and tetraphenylethylene (TPE) moieties as side groups. The maximum photoluminescence (PL) emission wavelengths of TPA-C-TP and TPE-C-TP were 435 and 369 nm in the solution state and 444 and 471 nm in the film state. TPA-C-TP effectively prevented intermolecular packing through the introduction of TPA, a bulky aromatic amine group, and it showed an excellent photoluminescence quantum yield (PLQY) of 86% in the film state. TPE-C-TP exhibited aggregation-induced emission; the PLQY increased dramatically from 0.1% to 78% from the solution state to the film state. The two synthesized materials had excellent thermal stability, with a high decomposition temperature exceeding 460 °C. The two compounds were used as emitting layers in a non-doped device. The TPA-C-TP device achieved excellent electroluminescence (EL) performance, with Commission Internationale de L\'Eclairage co-ordinates of (0.15, 0.07) and an external quantum efficiency of 4.13%, corresponding to an EL peak wavelength of 439 nm.
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  • 文章类型: Journal Article
    阿尔茨海默病(AD),淀粉样蛋白相关疾病,严重危害老年人的健康。根据目前的研究,其主要致病因子是淀粉样蛋白,它是一种由蛋白质非共价自组装形成的纤维状聚集体。基于聚集诱导发射(AIE)的特征,双乳糖基修饰的四苯基乙烯(TPE)分子TMNL(TPE+丙二腈+乳糖),带有两个丙二腈取代基,在这项工作中设计和合成。两亲性TMNL可以在生理PBS(磷酸盐缓冲盐水)中自组装成具有近红外(NIR)荧光发射的荧光有机纳米颗粒(FONs),在与Aβ1-42原纤维组合时实现优异的荧光增强(47倍)。TMNL已成功应用于AD转基因小鼠脑组织中Aβ1-42斑块的成像,由于TMNL的AIE特性,没有额外的冲洗过程是必要的。据信,这项工作中报道的探针对于与阿尔茨海默病相关的Aβ1-42聚集体的灵敏检测和准确定位作图应该是有用的。
    Alzheimer\'s disease (AD), an amyloid-related disease, seriously endangers the health of elderly individuals. According to current research, its main pathogenic factor is the amyloid protein, which is a kind of fibrillar aggregate formed by noncovalent self-assembly of proteins. Based on the characteristics of aggregation-induced emission (AIE), a bislactosyl-decorated tetraphenylethylene (TPE) molecule TMNL (TPE + malononitrile + lactose), bearing two malononitrile substituents, was designed and synthesized in this work. The amphiphilic TMNL could self-assemble into fluorescent organic nanoparticles (FONs) with near-infrared (NIR) fluorescence emission in physiological PBS (phosphate buffered saline), achieving excellent fluorescent enhancement (47-fold) upon its combination with Aβ1-42 fibrils. TMNL was successfully applied to image Aβ1-42 plaques in the brain tissue of AD transgenic mice, and due to the AIE properties of TMNL, no additional rinsing process was necessary. It is believed that the probe reported in this work should be useful for the sensitive detection and accurate localization mapping of Aβ1-42 aggregates related to Alzheimer\'s disease.
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  • 文章类型: Journal Article
    我们合成了一种新的四苯基乙烯改性壳聚糖生物缀合物,CS-TPE,这表明了聚集诱导的发射效应。它可以在pH5.3的水溶液中单独或与水溶性碗状六倍羧化三苯并三并喹并苯衍生物TBTQ-C6通过主客体结合自组装成荧光聚合物纳米颗粒。由CS-TPE两亲物或TBTQ-C6/CS-TPE超两亲物形成的球形纳米颗粒在pH10.4的碱性刺激下崩解,并且在TBTQ-C6的存在下崩解后聚集体的分散性大大提高。此外,通过引入TBTQ-C6,CS-TPE的荧光显着增强,并且随着CS-TPE和TBTQ-C6/CS-TPE的pH变化保持相对稳定。这种基于CS-TPE或TBTQ-C6/CS-TPE的具有稳定荧光发射的pH响应型超分子球形纳米颗粒可在各个领域找到应用。包括视觉口服药物递送系统的开发。
    We synthesized a new tetraphenylethylene-modified chitosan bioconjugate, CS-TPE, that shows the aggregation-induced emission effect. It can self-assemble into fluorescent polymeric nanoparticles in an aqueous solution at pH 5.3 either alone or with the water-soluble bowl-shaped six-fold carboxylated tribenzotriquinacene derivative TBTQ-C6 via host-guest binding. The spherical nanoparticles formed by CS-TPE amphiphiles or TBTQ-C6/CS-TPE supra-amphiphiles disintegrated under alkaline stimulation at pH 10.4 and the dispersion of the aggregates after the collapse in the presence of TBTQ-C6 was greatly improved. In addition, the fluorescence of CS-TPE was significantly enhanced by introducing TBTQ-C6, and remained relatively stable with variations in pH for both CS-TPE and TBTQ-C6/CS-TPE. Such pH-responsive supramolecular spherical nanoparticles with stable fluorescence emission based on CS-TPE or TBTQ-C6/CS-TPE may find applications in various fields, including the development of visual oral drug delivery systems.
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  • 文章类型: Journal Article
    在这项工作中,通过氧化石墨烯(GO)的湿法化学还原制备了具有聚集诱导发射(AIE)特性的可分散石墨烯基材料。在GO还原过程中,由于π-π相互作用和包裹作用,使用含有四苯基乙烯(TPE)和芘的共轭分子TPEP作为稳定剂。所制备的rGO-TPEP不仅在溶液中具有良好的分散性,而且还具有处理AIE的特征。在相同条件下,其荧光强度是TPEP的2.23倍。独特的光学特性和AIE效应使rGO-TPEP能够作为化学传感器,用于聚集态和固态的高灵敏度爆炸物检测。在聚合状态下,痕量2,4-二硝基甲苯(DNT)可以通过rGO-TPEP检测到,即使浓度低至0.91ppm,淬火常数高达2.47×104M-1。
    In this work, a dispersible graphene-based material with a characteristic of aggregation-induced emission (AIE) was prepared by wet chemical reduction of graphene oxide (GO). During the GO reduction process, a conjugated molecule TPEP containing tetraphenylethylene (TPE) and pyrene was employed as a stabilizer because of the π-π interactions and the wrapping effect. The as-prepared rGO-TPEP not only has good dispersion in solution but also processes the AIE feature. Its fluorescence intensity is 2.23 times higher than that of TPEP at the same condition. The unique optical properties and AIE effect enable the rGO-TPEP as a chemical sensor for highly sensitive explosive detection in aggregated state and solid state. In the aggregated state, trace 2,4-dinitrotoluene (DNT) can be detected by the rGO-TPEP even when the concentration is as low as 0.91 ppm, and the quenching constant is as high as 2.47 × 104 M-1.
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  • 文章类型: Journal Article
    间充质干细胞(MSCs),由于他们的肿瘤嗜性,被各种实体瘤强烈募集,并被肿瘤微环境中的炎症信号动员。然而,有效的细胞摄取对于基于MSC的药物递送是关键的。在这项研究中,我们合成了一种球形共聚物,聚乙烯亚胺-聚(ε-己内酯),与聚集诱导发射(AIE)材料和抗癌药物,紫杉醇,涂在它的内核上。随后添加转录反式激活因子(TAT)肽,一种细胞穿透肽,以修饰纳米粒子(NPs)。最后,MSCs用于将TAT修饰的AIE-NP药物携带至肿瘤部位,并协助同时进行癌症诊断和靶向肿瘤治疗.体外,TAT修饰的AIE-NP表现出良好的生物相容性,瞄准,以及在水溶液中的稳定性,除了高的载药量和包封效率。体外,AIE-NP在弱酸性环境下表现出可控的释放。体内和体外研究表明,AIE-NP药物具有较高的抗肿瘤功效和较低的细胞毒性,而生物分布证实了MSCs的肿瘤嗜性。总结一下,基于MSC的负载TAT的AIE-NP药物通过增强的NP-药物摄取具有良好的生物相容性和高抗肿瘤功效。此外,MSCs的肿瘤嗜性提供了肿瘤细胞的选择性药物摄取,从而减少了全身副作用。
    Mesenchymal stem cells (MSCs), due to their tumor tropism, are strongly recruited by various solid tumors and mobilized by inflammatory signals in the tumor microenvironment. However, effective cellular uptake is critical for MSC-based drug delivery. In this study, we synthesized a spherical copolymer, polyethylenimine-poly(ε-caprolactone), with aggregation-induced emission (AIE) material and the anticancer drug, paclitaxel, coloaded onto its inner core. This was followed by the addition of a transactivator of transcription (TAT) peptide, a type of cell-penetrating peptide, to modify the nanoparticles (NPs). Finally, the MSCs were employed to carry the TAT-modified AIE-NPs drug to the tumor sites and assist in simultaneous cancer diagnosis and targeted tumor therapy. In vitro, the TAT-modified AIE-NPs showed good biocompatibility, targeting, and stability in an aqueous solution besides high drug-loading and encapsulation efficiency. In vitro, the AIE-NPs exhibited a controllable release under a mildly acidic environment. The in vivo and in vitro studies showed high antitumor efficacy and low cytotoxicity of the AIE-NP drug, whereas biodistribution confirmed the tumor tropism of MSCs. To summarize, the MSC-based AIE-NP drugs loaded with TAT possessed good biocompatibility and high antitumor efficacy via the enhanced NP-drug uptake. In addition, the tumor tropism of MSCs provided selective drug uptake by the tumor cells and thus reduced the systemic side effects.
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  • 文章类型: Journal Article
    已开发出一种基于比色和荧光双重模式的柔性化学传感器,使用四苯基乙烯中心的四苯胺(TPE4A)快速,灵敏地检测次氯酸盐阴离子。荧光探针TPE4A表现出独特的聚集诱导发射(AIE)特性,随着水当量的增加,荧光峰从544到474nm的蓝移证明了这一点。在溶液中加入次氯酸盐,探针的吸光度发生变化,可以观察到响应的荧光颜色从浅绿色变为紫色。溶液中次氯酸盐的检出限为1.80×10-4M,对于柔性纸基化学传感器,肉眼的视觉检测极限为1.27µg/cm2。所提出的柔性化学传感器显示出良好的选择性和灵敏度,具有在不使用任何光谱仪器的情况下有效检测次氯酸盐阴离子的巨大潜力。
    A flexible chemosensor has been developed based on colorimetric and fluorescent dual modes using tetraphenylethylene-centered tetraaniline (TPE4A) for rapid and sensitive detection of hypochlorite anion. The fluorescent probe TPE4A exhibits a unique aggregation-induced emission (AIE) character which is proved by a blue shift of the fluorescent peak from 544 to 474 nm with the water equivalents increasing. With the addition of hypochlorite in solution, the absorbance of the probe changes and the responding fluorescence color can be observed to change from light green to purple. The detection limit of hypochlorite is 1.80 × 10-4 M in solution, and the visual detection limit is 1.27 µg/cm2 with the naked eye for the flexible paper-based chemosensor. The proposed flexible chemosensors show a good selectivity and sensitivity which has great potential for effective detection of hypochlorite anions without any spectroscopic instrumentation.
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  • 文章类型: Journal Article
    四苯基乙烯(TPE)及其衍生物表现出优异的聚集诱导发射(AIE)性能。TPE单元很容易接近,和许多官能团可以以容易的方式引入,以产生溶液和固态的有效发光材料。正因为如此,几种基于TPE的化合物已经被开发并应用于许多领域,如OLED和化学传感器。硼二吡咯亚甲基(BODIPY)是一类非常感兴趣的吡咯荧光团,在材料科学和生物医学应用中具有多种应用。通过将Pd催化的交叉偶联反应与传统的二吡咯亚甲基化学相结合,我们介绍了新型的四-BODIPY附加TPE衍生物的合成,TPE和BODIPY核心之间的距离不同。TPE-BODIPY阵列6和9在THF/H2O系统中显示出非常不同的AIE性质,有9个展示双AIE,以及两种缀合物被发现产生单线态氧(1O2)。我们假定合成的附加BODIPY的TPE支架可用于发光系统和治疗学领域的潜在应用。
    Tetraphenylethylene (TPE) and its derivatives exhibit excellent aggregation-induced emission (AIE) properties. The TPE unit is easily accessible, and many functional groups can be introduced in a facile manner to yield effective luminescent materials in both solution and the solid-state. It is because of this, several TPE-based compounds have been developed and applied in many areas, such as OLEDs and chemical sensors. Boron dipyrromethenes (BODIPYs) are a class of pyrrolic fluorophore of great interest with myriad application in both material science and biomedical applications. Through the combination of Pd-catalyzed cross-coupling reactions and traditional dipyrromethene chemistry, we present the syntheses of novel tetra-BODIPY-appended TPE derivatives with different distances between the TPE and BODIPY cores. The TPE-BODIPY arrays 6 and 9 show vastly differing AIE properties in THF/H2O systems, with 9 exhibiting dual-AIE, along with both conjugates being found to produce singlet oxygen (1O2). We presume the synthesized BODIPY-appended TPE scaffolds to be utilized for potential applications in the fields of light-emitting systems and theranostics.
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  • 文章类型: Journal Article
    Tetraphenylethylene (TPE), a typical luminogen with aggregation-induced emission (AIE) features, has been widely used to prepare AIE fluorescent materials. In this study, TPE-functionalized polydimethylsiloxane (n-TPE-AP-PDMS) was successfully synthesized by attaching TPE to polydimethylsiloxane via aza-Michael addition. The introduction of polydimethylsiloxane to TPE had no obvious effect on photophysical properties. Intriguingly, n-TPE-AP-PDMS exhibited two opposite fluorescence emission behaviors in different systems: aggregation-induced quenching (ACQ) behavior in a tetrahydrofuran/water mixture and typical AIE phenomenon in a tetrahydrofuran/hexane mixture. This unexpected transition from ACQ to AIE can be attributed to a twisted intramolecular charge-transfer effect and flexible aminopropyl polydimethylsiloxane. n-TPE-AP-PDMS was further used as a fluorescent probe to detect nitrobenzene and it showed high quenching efficiency. Moreover, the n-TPE-AP-PDMS film showed high reversibility so that the quenching efficiency remained constant after five cycles. This work can provide a deeper understanding of AIE behavior and guidance to develop a new AIE polymer for chemosensors with high performance.
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  • 文章类型: Journal Article
    In this work, we first designed and synthesized tetraphenylene-fused aryl-imidazole derivatives TM-1-4 via regulation of molecular structure, which were consisted of 1H-imidazo[4,5-f][1,10]phenanthroline, 1H-phenanthro[9,10-d]imidazole, 4,5-diphenyl-1H-imidazole, 3,3\'-(1H-imidazole-4,5-diyl)dipyridine moieties and AIE-active tetraphenylethene units, respectively. The results illustrated that TM-1-4 exhibited clear AIE characteristics. Meanwhile, TM-2 and TM-3 show excellent solid emission properties (ΦTM-2 =13.73 % and ΦTM-3 =36.21 %), whereas TM-1 and TM-4 exhibit the opposite properties (ΦTM-1 =1.48 % and ΦTM-4 =4.83 %). The multiple rotors (pyridine and benzene ring) causes twisted conformations of the molecule that prevents π-π stacking and enhances solid emission(ΦTM-2<ΦTM-3, ΦTM-1<ΦTM-4). Significantly, TM-2 and TM-3 also exhibited reversible mechanochromic behavior (Emission red shifts: ΔλTM-2 =43 nm and ΔλTM-3 =41 nm) with color changes between blue and green emissions. The powder X-ray diffraction (PXRD) suggested the disordered state of ground sample could be readily returned to an ordered crystalline. Therefore, the mechanochromisms of TM-2 and TM-3 are ascribable to the phase transformation between crystal and amorphous structure. The single crystal X-ray analysis of TM-2 reveals a twisted conformation for TPE moiety and the absence of π-π intermolecular stacking. These excellent optical properties of TM-2 and TM-3 make them potentially applications in mechanochromic materials and imaging agents.
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  • 文章类型: Journal Article
    两种小分子单体,ph-TPE和ph-TPE-CN,和它们的均聚物聚(ph-TPE)和聚(ph-TPE-CN)含有四苯基乙烯和硫酸盐结构,通过硫(VI)氟交换点击反应(SuFEx)和自由基聚合合成。所有单体和聚合物在固态和聚集状态下都表现出典型的聚集诱导发射(AIE)效应。此外,基于四苯基乙烯发色团和对硝基苯酚之间的分子间电荷转移(ICT)效应,两种聚合物均可用于对硝基苯酚的选择性检测。Poly(ph-TPE)的检出限和反应系数分别为0.081μM和5.15×104M-1,分别,而Poly(Ph-TPE-CN)的检出限和反应性系数分别为0.077μM和1.81×104M-1,分别。这可以归因于聚(ph-TPE-CN)比聚(ph-TPE)对对硝基苯酚更高的灵敏度。这项工作为侧链型AIE活性多硫酸盐荧光探针的制备和拓宽应用提供了一种新的方法。
    Two small molecular monomers, ph-TPE and ph-TPE-CN, and their homopolymers Poly (ph-TPE) and Poly (ph-TPE-CN) containing tetra phenylethylene and sulfate structures, were synthesized by a sulfur (VI) fluorine exchange click reaction (SuFEx) and radical polymerization. All the monomers and polymers exhibit a typical aggregation-induced emission (AIE) effect both in the solid state and aggregated state. Moreover, based on the intermolecular charge transfer (ICT) effect between the tetra phenylethylene chromophore and p-nitrophenol, both polymers could be used for the selective detection of p-nitrophenol. The detection limit and reactivity coefficient of Poly (ph-TPE) are 0.081 μM and 5.15×104  M-1 , respectively, whereas the detection limit and reactivity coefficient of Poly (ph-TPE-CN) are 0.077 μM and 1.81×104  M-1 , respectively. This can be attributed to the greater sensitivity of Poly (ph-TPE-CN) to p-nitrophenol than that of Poly (ph-TPE). This work provides a new methodology for the preparation and broadening application of side-chain type AIE-active polysulfate fluorescent probes.
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