Cooperative Action of Laser-Induced Thermal Effects and Ionic Coordination on the Order of TPPA0 Porphyrin Derivatives Self-Assembled Interface Probed via Real-Time Second Harmonic Generation
Cooperative Action of Laser-Induced Thermal Effects and Ionic Coordination on the Order of TPPA0 Porphyrin Derivatives Self-Assembled Interface Probed via Real-Time Second Harmonic Generation
复制标题
激光诱导热效应和离子配位对 TPPA0 卟啉衍生物自组装界面有序性的协同作用通过实时二次谐波产生探测
DOI：
10.1021/acs.jpcc.9b03165
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发表时间：
2019
影响因子：
3.7
通讯作者：
Guo Yuan
中科院分区：
文献类型：
--
作者：
Dong Bin;Bai Ruipeng;Zheng Wuming;Xue Man;Liu Caihe;Liu Minghua;Zhang Zhen;Guo Yuan
利用实时二次谐波发生技术研究了激光诱导热效应和离子配位对TPPA 0（5，10，15，20-四（乙氧羰基甲氧基）苯基）卟啉单分子膜在三种水溶液界面上有序/无序的协同作用.在p-in/p-out、s-in/p-out和45°-in/s-out极化组合下，测量了TPPA 0单分子膜在纯水、ZnCl 2水溶液和CuCl 2水溶液界面上的SH信号随时间的变化曲线。所有的SH信号都在开始时随时间变化，然后达到平衡状态。对于纯水和ZnCl 2水溶液界面，在p-in/p-out极化下，SH信号随时间衰减;而在CuCl 2水溶液界面，SH信号随时间增加。为了解释SH信号随时间的变化，我们还测量了p-in/p-out、s-in/p-out和45°-in/s-out偏振下的SH信号随时间的变化曲线，这些曲线都可以用来确定取向角和相应的取向分布宽度。结果表明，取向角δ分布不能解释SH信号变化的比例，因此，取向分布宽度的高斯分布代替δ分布，意味着TPPA 0单分子膜经历了取向有序度的变化过程，直至达到平衡。此外，使用旋转槽，在p-in/p-out极化下的三个界面上的TPPA 0单层的SH信号在测量期间几乎不变。这些结果表明，所有的SH信号随时间的变化是由本地积累的热量与重复的激光激发在82 MHz。最后，我们提出了一种分子机制来解释TPPA 0单分子膜上SH信号的变化。激光诱导热效应与离子配位的协同作用导致信号随时间变化，说明卟啉衍生物自组装界面的有序性受到离子与热的结合作用的影响。这一发现对生物科学和功能分子器件的研究具有重要意义。
We performed real-time second harmonic generation (SHG) to study the cooperative action of laser-induced thermal effects and ionic coordination on the order/disorder of TPPA0 (5,10,15,20-(tetrakis((ethoxycarbonyl)methoxy)phenyl)porphyrin) monolayers on the interface of three aqueous solutions. Time dependence curves of SH signals of TPPA0 monolayers on pure water and ZnCl2aqueous and CuCl2aqueous interfaces were detected under the polarization combinations of p-in/p-out, s-in/p-out and 45°-in/s-out. All the SH signals changed with time at the beginning and then reached the equilibrium state. For the pure water and ZnCl2aqueous interfaces, SH signals under the polarization of p-in/p-out declined with time; while on the CuCl2aqueous interfaces, the SH signals raised with time. To explain the various change of the SH signals with time, we also measured these time dependence curves under the polarizations of the p-in/p-out, s-in/p-out, and 45°-in/s-out, all of which can be used to determine the orientation angle and corresponding orientation distribution width. It is found that the orientation angle with δ distribution cannot explain the ratios of the SH signal change; thus, the gauss orientational distribution width has to be considered instead of δ distribution, which means the TPPA0 monolayers undergone the change process of the orientational order until reaching equilibrium. Furthermore, using a rotating trough, the SH signals of TPPA0 monolayer on the three interfaces under the p-in/p-out polarization are nearly unchanged during the measurement. These results indicated that all of the SH signal changes with time are induced by local accumulated heat with repetitive laser excitation at 82 MHz. At last, we propose a molecular mechanism to explain the changes of the SH signal on TPPA0 monolayers. The cooperative action of laser-induced thermal effects and the ionic coordination cause the signal change with time, which means the order of the porphyrin derivatives self-assembled interface is affected by the combination of ions and heat. The finding in this work is important to the bioscience, as well as the functional molecular devices.