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基于近红外区域泛频圆二色性测量的通用分光偏振计。

Universal spectropolarimeter based on overtone circular dichroism measurements in the near-infrared region.

作者信息

Tran C D, Grishko V I

机构信息

Department of Chemistry, Marquette University, Milwaukee, Wisconsin 53233.

出版信息

Anal Chem. 1994 Nov 1;66(21):3639-43. doi: 10.1021/ac00093a017.

Abstract

A novel and highly sensitive circular dichroism spectropolarimeter for the near-infrared region has been developed. In this instrument, a solid state titanium-sapphire laser that can be spectrally tuned from 670 to 1030 nm was used as the light source. The laser beam was converted into linearly polarized light by a polarizer and into left circularly polarized light and right circularly polarized light at 42 kHz by a photoelastic modulator (PEM). A limit of detection of 1.1 x 10(-6) AU was achieved by this instrument for (+)-Co(en)3(3+) at 765 nm. Further improvement including employing double modulation (at 42 kHz by the PEM and at 85 Hz by a chopper just before the laser beam was converted to CPL), demodulating and amplifying the signal with high-performance lock-in amplifiers, was made to enable the instrument to have the required sensitivity for the measurements of the circular dichroism of overtones and combination transitions of saturated chiral compounds, e.g., (R)- and (S)-camphor, (R)- and (S)-2-octanol, and (R)- and (S)-2-amino-1-octanol. Because the measured CD spectra originate from the overtones and combination transitions of the C-H and O-H groups, the spectropolarimeter can be used to detect virtually any compounds that have O-H and/or C-H groups.

摘要

一种新型的高灵敏度近红外圆二色光谱偏振仪已被研制出来。在该仪器中,一台可在670至1030纳米范围内进行光谱调谐的固态钛宝石激光器被用作光源。激光束通过一个偏振器被转换为线偏振光,并通过一个光弹调制器(PEM)在42千赫兹频率下被转换为左旋圆偏振光和右旋圆偏振光。该仪器在765纳米波长下对(+)-Co(en)3(3+)的检测限达到了1.1×10^(-6)AU。进一步的改进包括采用双调制(通过PEM在42千赫兹下调制,以及在激光束转换为圆偏振光之前通过一个斩波器在85赫兹下调制),并用高性能锁相放大器对信号进行解调与放大,以使该仪器能够具备测量饱和手性化合物(如(R)-和(S)-樟脑、(R)-和(S)-2-辛醇以及(R)-和(S)-2-氨基-1-辛醇)泛音和组合跃迁的圆二色性所需的灵敏度。由于所测量的圆二色光谱源自C-H和O-H基团的泛音和组合跃迁,该光谱偏振仪可用于检测几乎任何含有O-H和/或C-H基团的化合物。

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