Han Yangxia, Kou Manchang, Zhang Haixia, Shi Yan-Ping
CAS Key Laboratory of Chemistry of Northwestern Plant Resources and Key Laboratory for Natural Medicine of Gansu Province, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, China.
University of Chinese Academy of Sciences, Beijing 100049, China.
Anal Chem. 2024 Dec 10;96(49):19511-19518. doi: 10.1021/acs.analchem.4c04172. Epub 2024 Nov 26.
Long-wavelength emission fluorescent chiral silicon nanoparticles (c-SiNPs) hold significant potential for biological imaging and complex sample analysis due to their superior optical properties. However, the synthesis of these materials remains a considerable challenge. The activity of lysine is intrinsically linked to its configuration, making it crucial to develop a rapid, sensitive, and selective method for differentiating lysine enantiomers in biochemical and biomedical fields. In this study, -[3-(trimethoxysilyl)propyl]ethylenediamine and chlorogenic acid were innovatively employed as precursors, and the yellow-emitting c-SiNPs with an emission wavelength of 572 nm were synthesized at room temperature for the first time by adjusting experimental parameters. The obtained c-SiNPs exhibited excellent optical properties, stability, and cell compatibility. Furthermore, the c-SiNPs demonstrated outstanding fluorescence and colorimetric recognition capabilities for lysine enantiomers. Consequently, fluorescence/colorimetric dual-mode sensing methods with high selectivity and sensitivity for the recognition of lysine enantiomers were established, and the linear ranges of these methods for d-lysine were 0.050-20 and 0.10-30 mM, with detection limits of 7.5 and 17 μM, respectively. Additionally, the c-SiNPs demonstrated an ability to bioimaging d-lysine within HeLa cells. Using density functional theory to calculate the recognition mechanism and correlating this with fluorescence and ultraviolet-visible (UV-vis) absorption spectra data, it was confirmed that the recognition mechanism was associated with the Gibbs free energy, binding energy, and hydrogen bond number difference between the c-SiNPs and lysine enantiomers. The method developed in this study for preparing c-SiNPs provided a reference for synthesizing fluorescent c-SiNPs with longer emission wavelengths. Moreover, the established method for identifying lysine enantiomers holds significant guiding implications for the use of high-purity lysine.
长波长发射荧光手性硅纳米颗粒（c-SiNPs）因其优异的光学性能在生物成像和复杂样品分析方面具有巨大潜力。然而，这些材料的合成仍然是一个相当大的挑战。赖氨酸的活性与其构型内在相关，因此开发一种快速、灵敏且选择性的方法来区分生物化学和生物医学领域中的赖氨酸对映体至关重要。在本研究中，创新性地使用-[3-(三甲氧基甲硅烷基)丙基]乙二胺和绿原酸作为前体，通过调整实验参数首次在室温下合成了发射波长为572 nm的发黄光的c-SiNPs。所获得的c-SiNPs表现出优异的光学性能、稳定性和细胞相容性。此外，c-SiNPs对赖氨酸对映体表现出出色的荧光和比色识别能力。因此，建立了对赖氨酸对映体具有高选择性和灵敏度的荧光/比色双模式传感方法，这些方法对d-赖氨酸的线性范围分别为0.050 - 20 mM和0.10 - 30 mM，检测限分别为7.5和17 μM。此外，c-SiNPs证明了能够对HeLa细胞内的d-赖氨酸进行生物成像。利用密度泛函理论计算识别机制，并将其与荧光和紫外可见（UV-vis）吸收光谱数据相关联，证实识别机制与c-SiNPs和赖氨酸对映体之间的吉布斯自由能、结合能和氢键数差异有关。本研究中开发的制备c-SiNPs的方法为合成发射波长更长的荧光c-SiNPs提供了参考。此外，所建立的鉴定赖氨酸对映体的方法对高纯度赖氨酸的使用具有重要的指导意义。
