外消旋氨基酸薄膜在圆偏振莱曼-α光照射下出现的光学活性和表面形态变化

IF 2.8 4区 化学 Q2 CHEMISTRY, ANALYTICAL Chirality Pub Date : 2024-11-11 DOI:10.1002/chir.70004
Masahiro Kobayashi, Jun-ichi Takahashi, Hiroshi Ota, Koichi Matsuo, Mohamed I. A. Ibrahim, Taketoshi Minato, Gen Fujimori, Masahiro Katoh, Kensei Kobayashi, Yoko Kebukawa, Hiroaki Nakamura
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摘要

生命的同源性仍然是生命起源研究中最神秘的问题之一。一种拟议的对称性破缺机制涉及圆偏振光(CPL)的照射。为了研究氨基酸在圆偏振光辐照下的光反应,同步辐射光源 UVSOR-III 开发了一套真空紫外(VUV)圆偏振光辐照系统。氢 Lyman-α CPL(121.6 nm)被认为是潜在的空间不对称源。因此,我们用莱曼-α CPL 照射外消旋丙氨酸薄膜样品,以探索生物大分子的光反应。圆二色性(CD)光谱测量结果表明,在 180-240 纳米波长范围内,右旋(左旋)CPL 的辐照诱导了正(负)各向异性因子 g。不过,其光谱与对映体纯丙氨酸的光谱不同,波长范围较宽,且没有符号变化。液相色谱-质谱(LC-MS)测量结果表明,经过莱曼-α CPL 辐照后,会形成较大的分子,如低聚物丙氨酸加合物或改性低聚物。此外,氯化石蜡辐照大大改变了丙氨酸薄膜表面的微观结构,形成了 100 纳米尺度的环状网络聚集体。丙氨酸薄膜的形态变化和/或大分子的形成可能是导致各向异性因子光谱与对映纯丙氨酸光谱相比发生变化的原因。这些发现凸显了进一步研究固态生物大分子在紫外CPL辐照下的光反应的必要性,尤其是在光离子化能量范围内,以验证宇宙中的同手性假设。
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Emergence of Optical Activity and Surface Morphology Changes in Racemic Amino Acid Films Under Circularly Polarized Lyman-α Light Irradiation

The homochirality of life remains one of the most enigmatic issues in the study of the origin of life. A proposed mechanism for symmetry breaking involves irradiation by circularly polarized light (CPL). To investigate the photoreaction of amino acids under CPL irradiation, a vacuum ultraviolet (VUV) CPL irradiation system was developed at the synchrotron light source UVSOR-III. Hydrogen Lyman-α CPL (121.6 nm) is considered a potential asymmetric source in space. Therefore, racemic alanine film samples were irradiated with Lyman-α CPL to explore the photoreaction of biomolecules. Circular dichroism (CD) spectra measurements revealed that irradiation with right- (left-) handed CPL induced a positive (negative) anisotropy factor g in the wavelength range of 180–240 nm. However, the spectra differed from those of enantiopure alanine, exhibiting broad wavelength ranges and no sign change. Liquid chromatography-mass spectrometry (LC–MS) measurements indicate formation of larger molecules, such as oligomeric alanine adducts or modified oligomers after the Lyman-α CPL irradiation. Additionally, CPL irradiation considerably changes the microstructure of the alanine film surface, leading to the formation of circular network aggregates on the scale of 100 nm. The morphology changes in the alanine film and/or the formation of the larger molecules could be possible causes of the modified anisotropy factor spectra compared to those of enantiopure alanine. These findings highlight the need for further research on the photoreaction of biomolecules in solid states under VUV CPL irradiation, particularly in the photoionization energy range, to validate the cosmic scenario of homochirality.

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来源期刊
Chirality
Chirality 医学-分析化学
CiteScore
4.40
自引率
5.00%
发文量
124
审稿时长
1 months
期刊介绍: The main aim of the journal is to publish original contributions of scientific work on the role of chirality in chemistry and biochemistry in respect to biological, chemical, materials, pharmacological, spectroscopic and physical properties. Papers on the chemistry (physiochemical, preparative synthetic, and analytical), physics, pharmacology, clinical pharmacology, toxicology, and other biological aspects of chiral molecules will be published.
期刊最新文献
Multiwavelength Optical Rotation Detection: An Effective Approach for the Recognition of Analytical and Semi-Preparative HPLC Enantioseparation of the Chiral Pheromone Olean and Its Stereochemical Characterization Emergence of Optical Activity and Surface Morphology Changes in Racemic Amino Acid Films Under Circularly Polarized Lyman-α Light Irradiation Proceedings From 33rd Symposium on Chirality 2023, Rome, Italy Resolution and Absolute Configuration of Fargesin Enantiomers Chiroptical Sensing of Amines With Isatins
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