Simple and Versatile Platform for Air-Tolerant Photon Upconverting Hydrogels by Biopolymer-Surfactant-Chromophore Co-assembly
Simple and Versatile Platform for Air-Tolerant Photon Upconverting Hydrogels by Biopolymer-Surfactant-Chromophore Co-assembly
复制标题
DOI：
10.1021/jacs.8b05821
复制
发表时间：
2018-08-29
影响因子：
15
通讯作者：
Kimizuka, Nobuo
中科院分区：
文献类型：
--
作者：
Bharmoria, Pankaj;Hisamitsu, Shota;Kimizuka, Nobuo
在水环境中探索基于三重态三重态湮灭的光子上转换（TTA-UC）面临着诸如生色团不溶性和溶解氧分子使激发三重态失活等困难。我们提出了一种生物聚合物表面活性剂发色团共组装的新策略来克服这些问题。由明胶、Triton X-100 和上转换发色团（三重态敏化剂和发射体）共组装的水凝胶实现了空气稳定的 TTA-UC，上转换效率高达 13.5%。这与迄今为止观察到的空气饱和水性UC 系统的最高UC 效率相当。此外，这是水凝胶形式的空气稳定TTA-UC的第一个例子，拓宽了TTA-UC在生物应用中的适用性。钥匙有两重。首先，明胶和表面活性剂在水中自组装，形成具有疏水域的发达分层结构，可容纳高浓度的发色团。其次，明胶骨架的厚氢键网络阻止 O-2 流入疏水内部，4.9 ms 的长受体三重态寿命证明了这一点。明胶与其他非离子表面活性剂（Tween 80 和 Pluronic f127）以及 Triton X-100 与其他胶凝生物聚合物（海藻酸钠和琼脂糖）的空气稳定 TTA-UC 也实现了，证明了当前策略的多功能性。
Exploration of triplet triplet annihilation based photon upconversion (TTA-UC) in aqueous environments faces difficulty such as chromophores insolubility and deactivation of excited triplets by dissolved oxygen molecules. We propose a new strategy of biopolymer surfactant chromophore coassembly to overcome these issues. Air-stable TTA-UC with a high upconversion efficiency of 13.5% was achieved in hydrogel coassembled from gelatin, Triton X-100 and upconverting chromophores (triplet sensitizer and emitter). This is comparable to the highest UC efficiency observed to date for air-saturated aqueous UC systems. Moreover, this is the first example of air stable TTA-UC in the form of hydrogels, widening the applicability of TTA-UC in biological applications. The keys are two-fold. First, gelatin and the surfactant self-assemble in water to give a developed hierarchical structure with hydrophobic domains which accommodate chromophores up to high concentrations. Second, thick hydrogen-bonding networks of gelatin backbone prevent O-2 inflow to the hydrophobic interior, as evidenced by long acceptor triplet lifetime of 4.9 ms. Air-stable TTA-UC was also achieved for gelatin with other nonionic surfactants (Tween 80 and Pluronic f127) and Triton X-100 with other gelling biopolymers (sodium alginate and agarose), demonstrating the versatility of current strategy.