tetraphenylethylene

四苯基乙烯
  • 文章类型: Journal Article
    发光木质材料是一类新兴的生物质混合基质材料,由于其分层的多孔结构和功能化的多功能性。荧光特性在很大程度上取决于外源荧光团,它们是,然而,经常被臭名昭著的聚集效应所困扰。在这项工作中,通过在脱木质素回填透明过程中掺入四苯基乙烯衍生的聚集诱导发射(AIE)活性荧光团,开发了制备发光透明木材材料的有效策略。这些木材杂种显示出意想不到的发光增强,显着增加荧光团的荧光量子产率高达99%,远高于其他状态的荧光团,例如结晶固体或掺杂在聚合物基材中。机理研究表明,在脱木质素的微孔木框架中预聚合甲基丙烯酸甲酯的原位聚合会产生高分子量的有序PMMA聚合物,导致刚性的分子环境,提高了TPE基荧光团在PMMA聚合物和细胞壁界面处的发光效率。通过共聚焦激光扫描显微镜(CLSM),这种优异的荧光染色能力还被用来可视化木材的内在多孔网络在三维大体积与亚微米分辨率。从而为研究此类木杂种的结构-功能关系提供了一种替代方法。
    Luminescent wood materials are an emerging class of biomass hybrid host materials owing to the hierarchical porous structure and functionalization versatility. The fluorescence properties are largely dependent on exogenous fluorophores, which are, however, often plagued by notorious aggregation effects. In this work, an efficient strategy for the preparation of luminescent transparent wood materials is developed by incorporating tetraphenylethylene-derived aggregation-induced emission (AIE)-active fluorophores during a delignification-backfill transparency process. These wood hybrids showed unexpected luminescence enhancement that significantly increased the fluorescence quantum yield of the fluorophores up to 99%, much higher than that of the fluorophores in other states such as crystalline solids or doped in a polymer substrate. Mechanistic investigations reveal that in situ polymerization of prepolymerized methyl methacrylate in delignified microporous wood frames produces high molecular weight ordered PMMA polymers, resulting in a rigid molecular environment that improves the luminescence efficiency of TPE-based fluorophores at the interfaces of PMMA polymer and cell walls. By confocal laser scanning microscopy (CLSM), this excellent fluorescence staining capability was furthermore utilized to visualize the intrinsic porous network of wood in three dimensions over a large volume with submicrometer resolution, thus providing an alternative approach to the study of structure-function relationships in such wood hybrids.
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  • 文章类型: Journal Article
    在这项研究中,一种新型的多刺激响应RGB荧光有机分子,RTPE-NH2,是基于聚集诱导发射四苯基乙烯(TPE)发光体和酸响应荧光分子开关罗丹明B的组合设计和合成的。RTPE-NH2表现出聚集诱导发射行为,以及紫外线辐射刺激和酸刺激响应的荧光特性。它可以发出橙红色(R),绿色(G),和在365nm激发下的溶液和PMMA膜中的蓝(B)光。提出了暗通过键能量转移(DTBET)机制,并得到了控制实验和TD-DFT计算的支持。RTPE-NH2的合成和应用可以促进高灵敏度和优异光学性能的有机智能材料的发展。
    In this study, a novel multi-stimulus responsive RGB fluorescent organic molecule, RTPE-NH2, was designed and synthesized based on the combination of aggregation-induced emission tetraphenylethylene (TPE) luminophore and acid-responsive fluorescent molecular switch Rhodamine B. RTPE-NH2 exhibits aggregation-induced emission behavior, as well as UV irradiation-stimulus and acid-stimulus responsive fluorescence properties. It could emit orange-red (R), green(G), and blue(B) light in both solution and PMMA film under 365 nm excitation. The dark through-bond energy transfer (DTBET) mechanism was proposed and supported by control experiments and TD-DFT calculations. The synthesis and application of RTPE-NH2 could accelerate the development of organic smart materials with high sensitivity and excellent optical properties.
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  • 文章类型: Journal Article
    有机发光分子的常规合成方法通常涉及劳动密集型的溶液相有机合成,这违反了原子经济转型的原则。后合成改性(PSM)提供了一个有前途的替代方案,允许从一个荧光团直接转化为另一个。虽然PSM通常在扩展框架中实现,其在多孔分子晶体中的应用仍然具有挑战性。在这里,我们专注于利用多孔分子晶体,特别是四苯基乙烯核心骨架,作为串联PSM反应定制有机荧光团的多功能平台。定制的骨架设计确保了多孔结构的形成和串联固溶体反应的发生,同时在每个步骤中保持反应物和产物的固态。框架的固有非共价键合性质有利于加工和表征,为多孔网络提供无与伦比的优势。伴随的固态荧光从绿色到蓝色,然后到绿色(或黄色)的转变,可以实时监测串联反应,并提供直观的机械见解。这种现象被用于使用荧光快速响应代码的动态信息加密系统的简单构造。
    Conventional synthetic methods of organic luminescent molecules often involve labor-intensive solution-phase organic synthesis, which violate the principles of atom-economic transformation. Post-synthetic modification (PSM) offers a promising alternative, allowing direct transformation from one fluorophore to another. Although PSM is commonly implemented in extended frameworks, its application in porous molecular crystals remains challenging. Herein, we focus on utilizing porous molecular crystals, specifically tetraphenylethylene-cored frameworks, as versatile platforms for tandem PSM reactions to customize organic fluorophores. The tailored skeleton design ensures both the formation of porous structures and the occurrence of tandem solid-solution reactions while maintaining the solid state of reactants and products in each step. The inherent non-covalent bonding nature of the frameworks facilitates processing and characterization, offering unparalleled advantages for porous networks. The accompanying solid-state fluorescence transition from green to blue and then to green (or yellow) enables real-time monitoring of tandem reactions and provides intuitive mechanistic insights. This phenomenon is exploited for the facile construction of a dynamic information encryption system using fluorescent quick response codes.
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  • 文章类型: Journal Article
    使用离子自组装策略合成了四苯基乙烯衍生物(TPE-DHAB)的新型室温液晶。TPE-DHAB复合物表现出典型的聚集诱导发射性质和独特的螺旋超分子结构。此外,通过进一步的手性溶剂化可以实现圆偏振发光(CPL)的产生和手性反转,通过离子自组装和手性溶剂化过程的协同策略,为制备具有可控超分子结构和可调CPL性能的室温液晶材料提供了一种简便的方法。
    A novel room-temperature liquid crystal of tetraphenylethylene derivative (TPE-DHAB) was synthesized using an ionic self-assembly strategy. The TPE-DHAB complex exhibits typical aggregation-induced emission properties and a unique helical supramolecular structure. Moreover, the generation and handedness inversion of circularly polarized luminescence (CPL) can be achieved through further chiral solvation, providing a facile approach to fabricate room-temperature liquid crystalline materials with controllable supramolecular structures and tunable CPL properties through a synergistic strategy of ionic self-assembly and chiral solvation process.
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  • 文章类型: Journal Article
    硝基还原酶(NTR)是评估肿瘤缺氧水平的常用生物标志物。作为酶的主要来源之一,溶酶体的功能障碍通常会导致各种疾病。在这项研究中,NTR触发的溶酶体靶向探针,M-TPE-P,是基于四苯基乙烯核设计的。DFT计算表明,探针具有窄的单线态-三重态能隙(ΔEST),使它成为一种有效的光敏剂。M-TPE-P与NTR的对接亲和力揭示了它们之间的强结构匹配。光物理性质表明,该探针在kcat/Km为2.18×104M-1s-1的宽pH范围内检测NTR具有很高的选择性和灵敏度。检测极限在80%PBS/DMSO溶液中测定为53.6ng/mL。细胞成像研究表明,该探针可以用绿色荧光追踪细胞内NTR行为。共定位分析表明其优异的溶酶体靶向特异性。此外,该探针在NIR照射后表现出有效的ROS生成能力和显著的PDT效应,将其定位为癌症治疗的有前途的光敏剂。
    Nitroreductase (NTR) is a frequently used biomarker for the assessment of hypoxia level in tumors. As one of the main sources of enzymes, the dysfunction of lysosomes typically leads to various diseases. In this study, an NTR-triggered lysosome-targeting probe, M-TPE-P, was designed based on a tetraphenylethylene core. DFT calculation indicated that the probe possessed a narrow singlet-triplet energy gap (ΔEST), rendering it an efficient photosensitizer. The docking affinity of M-TPE-P to NTR revealed a strong structural match between them. Photophysical properties demonstrated that the probe exhibited high selectivity and sensitivity in a broad pH rang for detecting NTR with kcat/Km as 2.18 × 104 M-1 s-1. The detection limit was determined to be 53.6 ng/mL in 80 % PBS/DMSO solution. Cell imaging studies showed the probe could trace intracellular NTR behavior with green fluorescence. The colocalization analysis indicated its excellent lysosome-targeting specificity. In addition, the probe exhibited effective ROS generation ability and significant PDT effect after NIR irradiation, positioning it as a promising photosensitizer for cancer treatment.
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  • 文章类型: Journal Article
    基于四苯基乙烯的N的新家族,开发了具有聚集诱导发射(AIE)特征的O-螯合硼烷络合物(TPE-BA)。X射线晶体学分析表明,苯胺部分上的末端取代基显着影响分子间堆叠模式,从而影响光物理性质。这些化合物的稳定性与苯胺部分上的取代基密切相关。电子给体取代的TPE-BA-OMe表现出最佳的稳定性,而电子受体取代的化合物表现出较差的稳定性。受益于其AIE特性和合适的亲脂性,TPE-BA-OMe是一种出色的荧光探针,可用于活细胞中脂质滴的特异性生物成像。
    A new family of tetraphenylethylene-based N,O-chelated boranil complexes (TPE-BAs) with aggregation-induced emission (AIE) characteristics were developed. X-ray crystallographic analysis indicated that the terminal substituents on the aniline moiety significantly affected the intermolecular stacking mode, thereby influencing the photophysical properties. The stabilities of these compounds are closely related to the substituents on the aniline moiety. Electron-donor-substituted TPE-BA-OMe exhibited the best stability, whereas the electron-acceptor-substituted compounds exhibited poor stability. Benefitting from its AIE properties and suitable lipophilicity, TPE-BA-OMe served as an excellent fluorescent probe for the specific bioimaging of lipid droplets in living cells.
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  • 文章类型: Journal Article
    通过协同采用四个关键策略:(I)引入四苯基乙烯基团作为具有聚集诱导发射(AIE)特性的中心核心单元,(II)通过扩展积木分支来优化π共轭长度,(三)加入含有烯键的柔性基团,(四)应用晶体工程实现密集堆积模式和高度扭曲构象,我们成功地合成了一系列表现出单/双光子激发荧光的氢键有机骨架(HOFs)。值得注意的是,当使用荧光优越的构建块L2时,HOF-LIFM-7和HOF-LIFM-8表现出82.1%和77.1%的高量子产率(QY),并实现了148959.5GM和123901.1GM的超高双光子吸收(TPA)截面。这些材料已成功用于单光子和双光子激发的溶酶体靶向细胞成像。相信这一战略,积木优化与水晶工程相结合,具有指导杰出的荧光HOF材料发展的巨大潜力。
    By synergistically employing four key strategies: (I) introducing tetraphenylethylene groups as the central core unit with aggregation-induced emission (AIE) properties, (II) optimizing the π-conjugated length by extending the building block branches, (III) incorporating flexible groups containing ethylenic bonds, and (IV) applying crystal engineering to attain dense stacking mode and highly twisty conformation, we successfully synthesized a series of hydrogen-bonded organic frameworks (HOFs) exhibiting exceptional one/two-photon excited fluorescence. Notably, when utilizing the fluorescently superior building block L2, HOF-LIFM-7 and HOF-LIFM-8 exhibiting high quantum yields (QY) of 82.1 % and 77.1 %, and ultrahigh two-photon absorption (TPA) cross-sections of 148959.5 GM and 123901.1 GM were achieved. These materials were successfully employed in one and two-photon excited lysosome-targeting cellular imaging. It is believed that this strategy, combining building block optimization and crystal engineering, holds significant potential for guiding the development of outstanding fluorescent HOF materials.
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  • 文章类型: Journal Article
    可编程发光材料的精确调制合成仍然是一个挑战。为了应对这一挑战,我们构建了四种基于四苯基乙烯的超分子结构(SA,SB,SC,和SD),揭示它们比四苯基乙烯单体表现出更高的电化学发光(ECL)强度和效率,并且可以归类为高效和精确调制的分子内聚集诱导的电化学发光(PI-AIECL)系统。性能最佳的系统(SD)显示出高的ECL阴极效率,比水溶液中的基准三(2,2'-联吡啶)氯化钌(II)高六倍。这些结构在有机溶剂中的电化学表征提供了更深入的机理见解,揭示SD具有最低的电化学带隙。密度泛函理论计算表明,SD结构中客体配体的带隙最小,与主体支架的带隙最接近。最后,SD系统用于在实际样品中实现基于ECL的半胱氨酸检测(检测限=14.4nM)。因此,这项研究不仅提供了一种精确调制的超分子策略,允许发色团在分子尺度上可控地调节,而且还激发了高性能聚集诱导电化学发光发射器的可编程合成。
    The precisely modulated synthesis of programmable light-emitting materials remains a challenge. To address this challenge, we construct four tetraphenylethylene-based supramolecular architectures (SA, SB, SC, and SD), revealing that they exhibit higher electrochemiluminescence (ECL) intensities and efficiencies than the tetraphenylethylene monomer and can be classified as highly efficient and precisely modulated intramolecular aggregation-induced electrochemiluminescence (PI-AIECL) systems. The best-performing system (SD) shows a high ECL cathodic efficiency exceeding that of the benchmark tris(2,2\'-bipyridyl)ruthenium(II) chloride in aqueous solution by nearly six-fold. The electrochemical characterization of these architectures in an organic solvent provides deeper mechanistic insights, revealing that SD features the lowest electrochemical band gap. Density functional theory calculations indicate that the band gap of the guest ligand in the SD structure is the smallest and most closely matched to that of the host scaffold. Finally, the SD system is used to realize ECL-based cysteine detection (detection limit=14.4 nM) in real samples. Thus, this study not only provides a precisely modulated supramolecular strategy allowing chromophores to be controllably regulated on a molecular scale, but also inspires the programmable synthesis of high-performance aggregation-induced electrochemiluminescence emitters.
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  • 文章类型: Journal Article
    我们通过将四苯基乙烯(TPE)和胆固醇成分掺入到亚苯基双酰亚胺(PBI)衍生物中来报告荧光染料TM。荧光发射光谱表明该染料具有稳定的红色发射和聚集诱导发射(AIE)特性。胆固醇组分的掺入触发TM通过超分子自组装显示诱导的手性。通过用两亲性聚合物基质包封荧光染料制备cRGD官能化纳米颗粒。功能化的荧光有机纳米粒子表现出优异的生物相容性,大斯托克斯位移和良好的光稳定性,这使它们成为具有高荧光对比度的靶向癌细胞的有效荧光探针。
    We report a fluorescent dye TM by incorporating the tetraphenylethylene (TPE) and cholesterol components into perylene bisimides (PBI) derivative. Fluorescence emission spectrum shows that the dye has stable red emission and aggregation-induced emission (AIE) characteristics. The incorporation of cholesterol components triggers TM to show induced chirality through supramolecular self-assembly. The cRGD-functionalized nanoparticles were prepared by encapsulating fluorescent dyes with amphiphilic polymer matrix. The functionalized fluorescent organic nanoparticles exhibit excellent biocompatibility, large Stokes\' shift and good photostability, which make them effective fluorescent probes for targeting cancer cells with high fluorescence contrast.
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  • 文章类型: Journal Article
    多组分金属可以集成其不同构建块的功能,以实现高级应用的协同效应。在这里,基于金属配位驱动的自组装,我们报告了一系列等网状四苯基乙烯基金属陶瓷的制备,多核核磁共振有很好的特征,ESI-TOF-MS和单晶X射线衍射技术。将光敏四苯基乙烯单元作为面和Re催化络合物作为支柱适当地整合到单个金属陶瓷中,可提供1707μmolg-1h-1的高光催化制氢速率,这是报道的金属陶瓷中的最高值之一。飞秒瞬态吸收和DFT计算表明,金属层可以作为两个构建块的精确和有组织排列的平台,使高效和定向电子转移高效的光催化性能。本研究提供了将多功能配体整合到一定的金属化合物中以提高光催化制氢效率的一般策略,这将指导未来的金属陶瓷设计走向光催化。
    Multicomponent metallacages can integrate the functions of their different building blocks to achieve synergetic effects for advanced applications. Herein, based on metal-coordination-driven self-assembly, we report the preparation of a series of isoreticular tetraphenylethylene-based metallacages, which are well characterized by multinuclear NMR, ESI-TOF-MS and single-crystal X-ray diffraction techniques. The suitable integration of photosensitizing tetraphenylethylene units as faces and Re catalytic complexes as the pillars into a single metallacage offers a high photocatalytic hydrogen production rate of 1707 μmol g-1  h-1 , which is one of the highest values among reported metallacages. Femtosecond transient absorption and DFT calculations reveal that the metallacage can serve as a platform for the precise and organized arrangement of the two building blocks, enabling efficient and directional electron transfer for highly efficient photocatalytic performance. This study provides a general strategy to integrate multifunctional ligands into a certain metallacage to improve the efficiency of photocatalytic hydrogen production, which will guide the future design of metallacages towards photocatalysis.
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