Stretching the Bisalkyne Raman Spectral Palette Reveals a New Electrophilic Covalent Motif.
Stretching the Bisalkyne Raman Spectral Palette Reveals a New Electrophilic Covalent Motif.
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拉伸双炔拉曼光谱调色板揭示了一种新的亲电共价基序。
DOI：
10.1002/chem.202300953
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发表时间：
2023
期刊：
影响因子：
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通讯作者：
Ravindra MP
中科院分区：
文献类型：
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作者：
Ravindra MP
设计了具有不同振动频率和生理学相关cLogP的小杂芳基-二炔（Het-DY）标签用于多路生物正交拉曼成像。Pd-Cu催化的偶联，结合使用Lei配体，被证明可以提高所需的heterocoupledHet-DY标签的总产率，最大限度地减少同偶联副产物的产生。光谱数据与DFT计算预测的趋势一致，富电子/贫电子环的系统引入扩展了芳基封端的二炔的频率极限（2209-2243 cm−1）。 这些Het-DY标签的LogP改善从它们在细胞摄取研究中的扩散分布中是明显的，并且具有细胞器标记的功能化标签允许获取位置特异性生物图像。基于LC-MS和NMR的分析表明，一些杂芳基封端的内部炔是具有结构依赖性反应性的潜在亲核试剂陷阱。这些具有共价反应性的生物相容性Het ‐ DY标签为拉曼生物正交成像开辟了新的途径。
Small heteroaryl‐diyne (Het‐DY) tags with distinct vibrational frequencies, and physiologically relevant cLogPwere designed for multiplexed bioorthogonal Raman imaging. Pd−Cu catalyzed coupling, combined with the use of Lei ligand, was shown to improve overall yields of the desired heterocoupledHet‐DYtags, minimizing the production of homocoupled side‐products. Spectral data were in agreement with the trends predicted by DFT calculations and systematic introduction of electron‐ rich/poor rings stretched the frequency limit of aryl‐capped diynes (2209–2243 cm−1). The improved LogPof theseHet‐DYtags was evident from their diffuse distribution in cellular uptake studies and functionalizing tags with organelle markers allowed the acquisition of location‐specific biological images. LC–MS‐ and NMR‐based assays showed that some heteroaryl‐capped internal alkynes are potential nucleophile traps with structure‐dependent reactivity. These biocompatibleHet‐DYtags, equipped with covalent reactivity, open up new avenues for Raman bioorthogonal imaging.