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基于量子级联激光的振动圆二色性增强的平衡检测方案。

Quantum Cascade Laser-Based Vibrational Circular Dichroism Augmented by a Balanced Detection Scheme.

机构信息

Institute of Chemical Technologies and Analytics, TU Wien, Getreidemarkt 9/164-UPA, 1060 Vienna, Austria.

Photonics Institute, TU Wien, Gußhausstrasse 27-29, 1040 Vienna, Austria.

出版信息

Anal Chem. 2022 Jul 26;94(29):10384-10390. doi: 10.1021/acs.analchem.2c01269. Epub 2022 Jul 14.

Abstract

Vibrational circular dichroism (VCD) constitutes a powerful technique, enabling the determination of the absolute configuration of molecules without the need for specialized reagents. While delivering critical information, VCD signals commonly are several orders of magnitude weaker than classical absorbance signals, which so far necessitated long measurement times to achieve acceptable signal-to-noise ratios (SNRs) in VCD experiments. We present here an improved setup for the measurement of VCD in the range between 5.6 and 6.5 μm. Employing an external cavity quantum cascade laser (EC-QCL) as a high-power light source, we collected spectra with competitive noise levels in less than 5 min. The basis for this improvement was a balanced detection module combined with an optical path catered to VCD measurements. With the stabilization provided by the two-detector setup, noise originating from the laser source could be suppressed effectively. Noise level improvement up to a factor of 4 compared to the classical single detector EC-QCL-VCD could be reported. Compared to commercial Fourier transform infrared (FT-IR) instruments, the presented setup offers measurement time reductions of a factor of at least 6, with comparable noise levels. The applicability of the setup for qualitative and quantitative VCDs was proven. With the comparatively high temporal resolution provided, the monitoring of optically active processes will be possible in future applications.

摘要

振动圆二色性(VCD)是一种强大的技术,可在无需特殊试剂的情况下确定分子的绝对构型。虽然 VCD 信号提供了关键信息,但通常比经典吸收信号弱几个数量级,这使得 VCD 实验需要很长的测量时间才能达到可接受的信噪比(SNR)。我们在此介绍了一种用于测量 5.6 至 6.5μm 范围内 VCD 的改进装置。我们使用外部腔量子级联激光器(EC-QCL)作为高功率光源,在不到 5 分钟的时间内收集具有竞争噪声水平的光谱。这种改进的基础是平衡检测模块与专为 VCD 测量设计的光路相结合。通过双通道探测器的设置稳定,可有效抑制来自激光源的噪声。与传统的单探测器 EC-QCL-VCD 相比,我们可以报告噪声水平提高了 4 倍。与商用傅里叶变换红外(FT-IR)仪器相比,该装置的测量时间减少了至少 6 倍,且噪声水平相当。该装置已被证明可用于定性和定量 VCD。由于其提供了相对较高的时间分辨率,未来的应用中有望实现对光活性过程的监测。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/47fa/9330291/7454d57f3044/ac2c01269_0002.jpg

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