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瞬态布鲁斯特角反射法研究螺吡喃单层膜。

Transient Brewster angle reflectometry of spiropyran monolayers.

机构信息

Institute of Materials Research and Engineering, A*STAR (Agency for Science, Technology and Research), 3 Research Link, Singapore117602.

出版信息

Photochem Photobiol Sci. 2010 Feb;9(2):141-51. doi: 10.1039/b9pp00105k. Epub 2009 Dec 15.

Abstract

Brewster angle reflectometry has been developed as a tool for determining the absorbance and refractive index changes in molecular monolayers containing spiropyran. The method is sensitive to changes in both the real and imaginary parts of the refractive index in the monolayers. It was used to monitor the conversion of spiropyran to merocyanine and the reversal of this reaction when the molecules were immobilised on quartz using silane coupling. An analytical solution of Fresnel formula allowed the transient reflectometry data to be converted into transient absorption information. Absorbances of transients as low as approximately 10(-6) were possible using the current apparatus with a single laser pulse transient measurement. It was found that spiropyran photoconverted to merocyanine with an efficiency of approximately 0.1. The photochemical reversion of converted merocyanine to spiropyran occurred with efficiencies of 0.03-0.2 and this was probably site dependent. It was found that the thermal conversion from merocyanine to spiropyran was slow and even after 10 min there was no significant thermal reversion. This measurement was possible because the real part of the refractive index of the monolayer could be monitored with time using an off-resonance probe at a wavelength where the merocyanine did not absorb light meaning that the probe did not photobleach the sample. Thus our method also provides a non-intrusive method for probing changes in molecules in thin films.

摘要

布鲁斯特角反射率法已被开发为一种用于确定含有螺吡喃的分子单层中吸收和折射率变化的工具。该方法对单层中折射率的实部和虚部的变化都很敏感。它被用于监测螺吡喃向变色烯的转化,以及当分子通过硅烷偶联固定在石英上时,这种反应的逆转。菲涅耳公式的解析解允许将瞬态反射率数据转换为瞬态吸收信息。使用当前的仪器,通过单次激光脉冲瞬态测量,吸收的瞬态值低至约 10(-6)是可能的。结果发现,螺吡喃的光致变色效率约为 0.1。转化的变色烯的光化学回复到螺吡喃的效率为 0.03-0.2,这可能与位置有关。结果发现,从变色烯到螺吡喃的热转化很慢,即使 10 分钟后也没有明显的热回复。这种测量是可能的,因为可以使用非共振探针监测单层中折射率的实部随时间的变化,探针的波长选择在变色烯不吸收光的位置,这意味着探针不会使样品光漂白。因此,我们的方法还提供了一种非侵入性的方法来探测薄膜中分子的变化。

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