Triplet–triplet annihilation upconversion

  • 文章类型: Journal Article
    三重态-三重态湮没上转换(TTA-UC)的当前研究面临诸如有机溶剂的过度使用和分子氧对激发的三重态敏化剂的猝灭等困难。在这里,为了克服这些问题,我们提出了一种高效,简便的TTA-UC微乳制备策略。设备简单,制备过程短,在由TritonX114,四氢呋喃和上转换发色团(铂八乙基卟啉和9,10-二苯基蒽)共组装的微乳液中,实现了空气稳定的TTA-UC,上转换效率高达16.52%。这与TTA-UC微乳液体系有史以来报道的最高UC效率相当。TX114-THF的优异UC性能可归因于两个方面。首先,小尺寸胶束容纳发色团在有机相中达到高浓度,这促进了有效的分子碰撞。此外,532nm处的高吸收率确保了激发光的充分利用,获得更多的长波长光子参与TTA-UC过程。此外,空气稳定的TTA-UC在具有各种表面活性剂的微乳液中也表现良好,包括非离子表面活性剂(吐温20,吐温80,TritonX-110,TritonX-114),离子表面活性剂(十二烷基硫酸钠,十六烷基三甲基溴化铵)和嵌段共聚物(pluronicF127,pluronicP123),根据表面活性剂分子的结构特征,通过三个猜想组装模型(浓缩,未压实和分散)。这些发现可为TTA-UC相关领域表面活性剂的选择提供参考。
    Current research of triplet-triplet annihilation upconversion (TTA-UC) faces difficulty such as overuse of organic solvents and quenching of excited triplet sensitizers by molecular oxygen. Herein, we propose an efficient and facile preparation strategy of TTA-UC microemulsion to overcome these issues. With simple device and short preparation process, air-stable TTA-UC with a high upconversion efficiency of 16.52% was achieved in microemulsion coassembled from TritonX114, tetrahydrofuran and upconverting chromophores (platinum octaethyl-porphyrin and 9,10-diphenylanthracene). This is comparable to the highest UC efficiency ever reported for TTA-UC microemulsion systems. The excellent UC performance of TX114-THF could be attributed to two perspectives. Firstly, small-size micelle accommodated chromophores up to high concentrations in organic phase, which promoted efficient molecular collision. Additionally, high absorbance at 532 nm ensured full use of excitation light, getting more long wavelength photons involved in the TTA-UC process. Moreover, air-stable TTA-UC also performed well in microemulsion with various surfactants, including nonionic surfactants (Tween 20, Tween 80, Triton X-110, Triton X-114), ionic surfactants (sodium dodecyl sulfate, cetyltrimethyl ammonium bromide) and block copolymers (pluronic F127, pluronic P123), through three conjectural assembly models according to the structural characteristics of surfactant molecules (concentrated, uncompacted and scattered). These discoveries could provide estimable reference for selection of surfactants in relevant fields of TTA-UC.
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  • 文章类型: Journal Article
    具有高编码容量的光学信息加密可以在保证广泛的普通和奢侈品的真实性的情况下显著提高防伪的安全级别。在这项工作中,一种具有高度复杂性的新型伪造材料是通过微囊化胆甾型液晶和三重态-三重态湮没上转换荧光团以将结构着色与荧光和上转换光致发光相结合来制造的。此外,多模安全油墨通过各种印刷技术在柔性基材上呈现可调整的光学行为和可编程能力,它在不同的光学模式下提供不同的信息加密。先进的策略为高安全级别的多模光学墨水提供了一个实用的通用平台,具有大大增强的编码能力,可编程性,可印刷性,和成本效益,这显示了信息加密和防伪技术的巨大潜力。
    Optical information encryption with high encoding capacities can significantly boost the security level of anti-counterfeiting in the scenario of guaranteeing the authenticity of a wide scope of common and luxury goods. In this work, a novel counterfeiting material with high-degree complexity is fabricated by microencapsulating cholesteric liquid crystals and triplet-triplet annihilation upconversion fluorophores to integrate structural coloration with fluorescence and upconversion photoluminescence. Moreover, the multimode security ink presents tailorable optical behaviors and programmable abilities on flexible substrates by various printing techniques, which offers distinct information encryption under different optical modes. The advanced strategy provides a practical versatile platform for high-secure-level multimode optical inks with largely enhanced encoding capacities, programmability, printability, and cost-effectiveness, which manifests enormous potentials for information encryption and anti-counterfeiting technology.
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  • 文章类型: Journal Article
    三重态-三重态湮没上转换(TTA-UC)是一种非常有前途的技术,可用于将低能光子转换为高能光子,并已被证明在各个领域具有很大的价值。卟啉具有高摩尔吸光度的特点,可以与不同的金属离子和高比例的三重态以及可调结构形成络合物,因此它们是TTA-UC的重要敏化剂。卟啉基TTA-UC在TTA-UC体系中起着举足轻重的作用,在太阳能电池、传感和圆偏振发光。近年来,已经出现了基于卟啉的TTA-UC系统在光诱导反应中的应用,但很少有人注意。因此,这篇综述密切关注了基于卟啉的TTA-UC系统引发的光反应的最新进展。首先,卟啉基TTA-UC用于化学转化的光化学,如光异构化,光催化合成,光聚合,光降解和光化学/光电化学水分解,进行了详细的讨论,揭示了TTA-UC的不同机理以及进行合理的分子创新和纳米结构学以解决实际应用中存在的问题的方法。随后,证明了由基于卟啉的TTA-UC驱动的用于生物医学应用的光反应。最后,简要讨论了基于卟啉的光反应TTA-UC系统的未来发展。
    Triplet-triplet annihilation upconversion (TTA-UC) is a very promising technology that could be used to convert low-energy photons to high-energy ones and has been proven to be of great value in various areas. Porphyrins have the characteristics of high molar absorbance, can form a complex with different metal ions and a high proportion of triplet states as well as tunable structures, and thus they are important sensitizers for TTA-UC. Porphyrin-based TTA-UC plays a pivotal role in the TTA-UC systems and has been widely used in many fields such as solar cells, sensing and circularly polarized luminescence. In recent years, applications of porphyrin-based TTA-UC systems for photoinduced reactions have emerged, but have been paid little attention. As a consequence, this review paid close attention to the recent advances in the photoreactions triggered by porphyrin-based TTA-UC systems. First of all, the photochemistry of porphyrin-based TTA-UC for chemical transformations, such as photoisomerization, photocatalytic synthesis, photopolymerization, photodegradation and photochemical/photoelectrochemical water splitting, was discussed in detail, which revealed the different mechanisms of TTA-UC and methods with which to carry out reasonable molecular innovations and nanoarchitectonics to solve the existing problems in practical application. Subsequently, photoreactions driven by porphyrin-based TTA-UC for biomedical applications were demonstrated. Finally, the future developments of porphyrin-based TTA-UC systems for photoreactions were briefly discussed.
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  • 文章类型: Journal Article
    Metal⁻organic framework thin film-based dye sensitized solar cell is fabricated with highly oriented, crystalline, and porous Zn-perylene metal-organic framework (MOF) thin film (SURMOF) which is integrated with Bodipy embedded in poly(methyl methacrylate). It has been demonstrated that the photocurrent can be enhanced by a factor of 5 relative to Zn-perylene MOF thin film due to triplet⁻triplet annihilation up-conversion between the Bodipy/PMMA sensitizer and the Zn-perylene MOF thin film acceptor using Co(bpy)₃2+/3+ as redox mediator.
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