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摘要
不同手性的生物分子具有不同甚至相反的生物和药理活性。由于很多生物大分子的振动和转动能级分布在太赫兹波段，使得太赫兹波谱技术成为生物大分子识别的有效手段，但是太赫兹时域光谱系统都采用线偏振光源，无法对手性分子进行有效识别。我们在理论上利用线偏振的琼斯矩阵模型合成圆偏振下的琼斯矩阵，根据圆偏光的透射率差异性进一步计算样品的透射圆二色光谱，为表征不同手性分子提供了一种有效方法。基于透射式太赫兹时域光谱系统，对(R)-(-)-Ibuprofen和(S)-(+)-Ibuprofen的光谱进行测试，计算了(R)-(-)-Ibuprofen和(S)-(+)-Ibuprofen的线偏透过率和圆偏透过率；并计算出透射性圆二色光谱，两种手性物质的圆二色性值达到0.015，有效地实现了对(R)-(-)-Ibuprofen和(S)-(+)-Ibuprofen的识别效果。这一方法为利用太赫兹光谱技术检测和识别手性分子提供了参考。
Abstract
Biomolecules with different chirality have different or even opposite biological and pharmacological activities. Since vibration and rotation energy levels of many biomolecules lie within the terahertz range, terahertz spectroscopy has emerged as a useful tool for biomolecular identification. Nevertheless, linearly polarized light sources are used in terahertz time-domain spectroscopy, which is ineffective for identifying chiral compounds. We theoretically constructed a circularly polarized Jones matrix using a linearly polarized Jones matrix model. We also calculated the transmission circular dichroism spectrum of the sample based on the difference in transmittance of circularly polarized light, offering a useful technique for describing various chiral compounds. The spectra of (R)-(-)-Ibuprofen and (S)-(+)-Ibuprofen were investigated using a transmission terahertz time-domain spectroscopy system, and the linear polarization biased transmittance and circular polarization transmittance of (R)-(-)-Ibuprofen and (S)-(+)-Ibuprofen were computed. Additionally, the transmittance circular dichroic spectra were calculated, and the two chiral compounds' circular dichroic values reached 0.015, successfully achieving the (R)-(-)-Ibuprofen and (S)-(+)-Ibuprofen recognition effect. This technique serves as a guide for chiral molecule identification and detection using terahertz spectroscopy technology.
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Key words:
- Jones matrix /
- circular dichroism /
- terahertz /
- chiral recognition
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Overview
Overview: Chiral molecules are defined as materials that have chiral centers, also referred to as asymmetric centers in chemical structure. Biomolecules with different chirality exhibit distinct or even opposing biological and pharmacological effects, even when their structural groups are the same. Chirality detection and recognition have long been a significant issue in the realm of life sciences. Circular dichroism, a method of identifying chiral substances, is produced when left- and right-handed circularly polarized light are absorbed differently by different chiral molecules. This results in different amplitudes of circularly polarized light passing through different rotations. Currently, available techniques for detecting chiral drugs include high performance liquid chromatography, chiral Raman spectroscopy, nuclear magnetic resonance spectroscopy, and polarimeter detection; nevertheless, there are drawbacks, such as costly and difficult-to-use procedures. The terahertz spectroscopy technique becomes an excellent way to identify biological macromolecules since many of them have vibrational and rotational energy levels that fall in the terahertz range. Currently, linearly polarized light sources are used in the terahertz time-domain spectroscopy system, which is unable to detect chiral compounds. Theoretically, we can synthesize the Jones matrix under circular polarization using the Jones matrix model of linear polarization. We can then determine the circular dichroism spectrum of the sample based on the transmission difference of circular polarization light. This approach offers a useful way to characterize various chiral molecules. By rotating the crystal and the experimental sample through four measurements, the time-domain spectra under various polarization states are obtained based on the transmitted-terahertz time-domain spectroscopy system. The Jones matrix of the sample online polarization space is obtained, which is then converted into the circular polarization space. The circular polarization space's Jones matrix component is utilized to compute the sample's circular dichroism (CD) spectrum. This study presents the measurement of the spectra of (R)-(-)-Ibuprofen and (S)-(+)-Ibuprofen, together with the calculation of their linear and circular bias transmittances. The circular dichroism spectra of the two chiral substances are calculated, and the circular dichroism values of the two chiral substances reach 0.015, which effectively realizes the recognition effect of (R)-(-)-Ibuprofen and (S)-(+)-Ibuprofen. This work provides a reference for the following chiral recognition in the terahertz band by using the superstructure surface and improving the local intensity of the light field through high-quality resonance to improve the accuracy and sensitivity of chiral recognition.
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图 1 (a) 透射式太赫兹时域光谱系统示意图。其中HWP表示半波片，PBS表示偏振分光棱镜，L表示透镜，PM表示抛面镜，QWP表示四分之一玻片，P表示偏振片。(b) 实验压片样品及其分子式
Figure 1. (a) Schematic diagram of transmissive terahertz time-domain spectroscopy. HWP: half-wave plate, PBS: polarization splitting prism, L: lens, PM: parabolic mirror, QWP: quarter wave plate, and P: polarizer; (b) Experimental tablet sample and corresponding molecular formula
图 2 太赫兹时域光谱系统的(a)时域信号和(b)频域谱
Figure 2. (a) Time domain signal and (b) frequency domain spectrum of the THz-TDS
图 3 (R)-(-)-Ibuprofen和(S)-(+)-Ibuprofen的线偏振透过率。(a) (R)-(-)-Ibuprofen的同线偏透过率；(b) (R)-(-)-Ibuprofen的交叉线偏透过率；(c) (S)-(+)-Ibuprofen的同线偏透过率；(d) (S)-(+)-Ibuprofen的交叉线偏透过率
Figure 3. Transmittances of (R)-(-)-ibuprofen and (S)-(+) -ibuprofen for linear polarized terahertz wave. (a) Transmittances of (R)-(-)-Ibuprofen for same linear polarization; (b) Transmittances of (R)-(-)-Ibuprofen for cross linear polarization; (c) Transmittances of (S)-(+)-Ibuprofen for same linear polarization; (d) Transmittance of (S)-(+)-Ibuprofen for cross linear polarization
图 4 (R)-(-)-Ibuprofen和(S)-(+)-Ibuprofen的圆偏振透过率。(a) (R)-(-)-Ibuprofen的同圆偏透过率；(b) (R)-(-)-Ibuprofen的交叉圆偏透过率；(c) (S)-(+)-Ibuprofen的同圆偏透过率；(d) (S)-(+)-Ibuprofen的交叉圆偏透过率
Figure 4. Transmittances of (R)-(-)-Ibuprofen and (S)-(+) -ibuprofen for circular polarized wave. (a) Transmittances of (R)-(-)-Ibuprofen for same circular polarization; (b) Transmittance of (R)-(-)-Ibuprofen for cross circular polarization; (c) Transmittance of (S)-(+)-Ibuprofen for same circular polarization; (d) Transmittance of (S)-(+)-Ibuprofen for cross circular polarization
图 5 (R)-(-)-Ibuprofen和(S)-(+)-Ibuprofen的太赫兹圆二色性光谱
Figure 5. Terahertz CD spectra of (R)-(-)-Ibuprofen and (S)-(+)-ibuprofen
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