Synthesis of 5-Cyano-Tryptophan as a Two-Dimensional Infrared Spectroscopic Reporter of Structure.
Synthesis of 5-Cyano-Tryptophan as a Two-Dimensional Infrared Spectroscopic Reporter of Structure.
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DOI：
10.1002/anie.201803849
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发表时间：
2018-06-18
期刊：
影响因子：
--
通讯作者：
Tucker MJ
中科院分区：
文献类型：
--
作者：
Chalyavi F;Gilmartin PH;Schmitz AJ;Fennie MW;Tucker MJ
保护的5-氰基-L-色氨酸（Trp 5CN）的简明合成已被开发用于肽或蛋白质的二维红外光谱研究。为了评估不同取代的氰基-Dahans的潜力，使用IR光谱表征了几种模型氰基吲哚系统。在评估它们的光谱特性后，将Trp 5CN整合到模型肽序列Trp 5CN-Gly-Phe 4CN中以阐明其结构。该肽证明了该探针Trp 5CN和Phe 4CN通过2D IR光谱捕获结构信息的能力。模拟肽在水中的2D IR光谱，以揭示由偶极偶联的存在产生的独特光谱特征。通过匹配模拟光谱和实验光谱之间的最大等高线的斜率沿着，确定氰基标记物之间的耦合强度为1.4 cm-1。使用跃迁偶极耦合，计算出两个探针之间的距离为13 μ m。以Trp 5CN-Gly-Phe 4CN为模型肽，研究了5-氰基-L-色氨酸的二维红外光谱（2D IR）。在该短肽中，捕获了氰基标记的探针对之间的振动耦合。通过匹配模拟光谱和实验光谱之间的最大等高线的斜率沿着，确定氰基标记物之间的耦合强度为1.4 cm-1。使用跃迁偶极耦合，计算出两个探针之间的距离为13 μ m。
A concise synthesis of protected 5-cyano-L-tryptophan (Trp5CN) has been developed for 2D IR spectroscopic investigations within peptides or proteins. To assess the potential of differently substituted cyano-tryptophans, several model cyanoindole systems were characterized using IR spectroscopy. Upon assessment of their spectroscopic properties, Trp5CN was integrated into a model peptide sequence, Trp5CN–Gly–Phe4CN, to elucidate its structure. This peptide demonstrates the capability of this probe, Trp5CN and Phe4CN, to capture structural information via 2D IR spectroscopy. The 2D IR spectrum of the peptide in water was simulated to reveal a unique spectral signature resulting from the presence of dipolar coupling. The coupling strength between cyano-labels was determined to be 1.4 cm−1 by matching the slopes along the max contour between the simulated and experimental spectrum. Using transition dipole coupling, a distance between the two probes of 13 Å was calculated. A reliable synthesis of protected 5-cyano-L-tryptophan has been developed for two-dimensional infrared (2D IR) spectroscopic investigations within a model peptide, Trp5CN–Gly–Phe4CN. In this short peptide, vibrational coupling between a cyano-labeled probe pair was captured. The coupling strength between cyano-labels was determined to be 1.4 cm−1 by matching the slopes along the max contour between the simulated and experimental spectrum. Using transition dipole coupling, a distance between the two probes of 13 Å was calculated.
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DOI：
10.1126/science.1202997
发表时间：
2011-06-03
期刊：
Science (New York, N.Y.)
影响因子：
--
作者：
Remorino A;Korendovych IV;Wu Y;DeGrado WF;Hochstrasser RM
通讯作者：
Hochstrasser RM
DOI：
10.1039/c6cp03426h
发表时间：
2016-10-19
期刊：
Physical chemistry chemical physics : PCCP
影响因子：
--
作者：
Markiewicz BN;Lemmin T;Zhang W;Ahmed IA;Jo H;Fiorin G;Troxler T;DeGrado WF;Gai F
通讯作者：
Gai F
DOI：
10.1021/jz2006447
发表时间：
2011-06-27
期刊：
The journal of physical chemistry letters
影响因子：
--
作者：
Lipkin JS;Song R;Fenlon EE;Brewer SH
通讯作者：
Brewer SH
影响因子：
3.6
作者：
Hernández, JN;Ramírez, MA;Martín, VS
通讯作者：
Martín, VS
影响因子：
2.9
作者：
Aprilakis, Konstantinos N.;Taskent, Humeyra;Raleighj, Daniel P.
通讯作者：
Raleighj, Daniel P.