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Influence of the tyrosine environment on the second harmonic generation of iturinic antimicrobial lipopeptides at the air-water interface

机译:酪氨酸环境对在空气-水界面的ituriic抗菌脂肽二次谐波产生的影响

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摘要

The second harmonic generation (SHG) response at the air-water interface from the tyrosine-containing natural iturinic cyclo-lipopeptides mycosubtilin, iturin A and bacillomycin D is reported. It is shown that this response is dominated by the single tyrosine residue present in these molecules owing to the large first hyperpolarizability arising from the non-centrosymmetric aromatic ring structure of this amino acid. The SHG response of these iturinic antibiotics is also compared to the response of surfactin, a cyclo-lipopeptide with a similar L,D-amino acid sequence but lacking a tyrosine residue, and PalmATA, a synthetic linear lipopeptide possessing a single tyrosine residue but lacking the amino acid sequence structuring the cycle of the iturinic antibiotics. From the light polarization analysis of the SHG response, it is shown that the tyrosine local environment is critical in defining the SHG response of these peptides at the air-water interface. Our results demonstrate that tyrosine, similar to tryptophan, can be used as an endogenous molecular probe of peptides and proteins for SHG at the air-water interface, paving the way for SHG studies of other tyrosine-containing bioactive molecules.
机译:据报道,在空气-水界面处,由含酪氨酸的天然ituriic环脂肽霉菌枯草杆菌素,iturin A和bacillomycin D产生了二次谐波(SHG)响应。结果表明,由于该氨基酸的非中心对称的芳香环结构而产生的第一超极化率很高,因此该反应以这些分子中存在的单个酪氨酸残基为主。还将这些促尿尿素抗生素的SHG反应与表面活性素(一种具有相似的L,D-氨基酸序列但缺少酪氨酸残基的环脂肽)和PalmATA(一种具有单个酪氨酸残基但缺乏蛋白的合成线性脂肽)的反应相比较。构成尿酸抗生素循环的氨基酸序列。从SHG响应的光偏振分析可以看出,酪氨酸的局部环境对于定义这些肽在气水界面的SHG响应至关重要。我们的结果表明,酪氨酸与色氨酸相似,可以用作空气-水界面上SHG的肽和蛋白质的内源性分子探针,为其他含酪氨酸的生物活性分子的SHG研究铺平了道路。

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