Department of Chemistry, University of Toronto , 80 Saint George Street, Toronto, Ontario M5S 3H6, Canada.
FPInnovations , 570 St. Jean Boulevard, Pointe-Claire, QC H9R 3J9, Canada.
ACS Nano. 2015 Oct 27;9(10):10377-85. doi: 10.1021/acsnano.5b04552. Epub 2015 Sep 9.
In the search for induced chiral plasmonic activity, cholesteric films formed by cellulose nanocrystals have attracted great interest as potential hosts for plasmonic nanoparticles. Circular dichroism (CD) spectra of the composite films exhibit two peaks, one of which is ascribed to the cholesteric host and the other one to plasmonic chiroptical activity of the plasmonic nanoparticles. Here we report the results of comprehensive studies of extinction and CD properties of composite films formed by different types of cellulose nanocrystals and different types of plasmonic nanoparticles. We show that the second peak in the CD spectra acquired using CD spectrometers appears as the result of the local reduction of the CD signal of the host material, due to excessive absorption by the nanoparticles, and thus it cannot be interpreted as induced plasmonic chiroptical activity. Instead, we propose an alternative way to measure CD spectra of plasmonic cholesteric films by using Mueller matrix transmission ellipsometry. The results of this study are important for ongoing research in the field of chiral plasmonics and for the optical characterization of a broad range of chiral nematic nanostructured materials.
在寻找诱导手性等离子体活性的过程中,由纤维素纳米晶体形成的胆甾相薄膜作为等离子体纳米粒子的潜在宿主引起了极大的兴趣。复合薄膜的圆二色(CD)光谱显示出两个峰,其中一个归因于胆甾相主体,另一个归因于等离子体纳米粒子的手性等离子体活性。在这里,我们报告了由不同类型的纤维素纳米晶体和不同类型的等离子体纳米粒子形成的复合薄膜的消光和 CD 性质的综合研究结果。我们表明,使用 CD 光谱仪获得的 CD 光谱中的第二个峰是由于纳米粒子的过度吸收导致主体材料的 CD 信号局部降低的结果,因此不能将其解释为诱导的等离子体手性活性。相反,我们提出了一种通过穆勒矩阵透射椭圆偏振术测量等离子体胆甾相薄膜 CD 光谱的替代方法。这项研究的结果对于手性等离子体领域的持续研究以及对广泛的手性向列型纳米结构化材料的光学特性具有重要意义。