Yuan Qinlin, Wang Mingyu, Ma Mingyue, Sun Pingping, Zeng Chaoyuan, Chi Weijie
School of Chemistry and Chemical Engineering, Hainan University, Haikou, 570228, China.
J Mol Model. 2024 Oct 29;30(11):385. doi: 10.1007/s00894-024-06179-6.
The dyes in the second near-infrared (NIR-II) region play a crucial role in advancing imaging technology. However, developing small-molecule dyes in NIR-II poses a significant bottleneck to meet the substantial demands in biological fields, which may be attributed to the lack of a rational design strategy. Herein, we designed a series of rhodamine analogs with more red-shifted emission by replacing the oxygen-bridge atom in xanthene-based dyes with -C(CH), -Si(CH), -SO, and -P(O)Ph. We investigated the frontier molecular orbital, electrostatic potential surfaces, the interaction region indicator, electron-hole distribution, and absorption and emission spectrum of xanthene-based dyes using (time-dependent) density functional theory. Our results demonstrated that these designed small molecular dyes exhibit long emission wavelengths covering 1377-1809 nm. We expected these findings to enable the targeted design of long-wavelength rhodamines.
Geometry optimization of dyes in the ground and excited states was carried out at ω-B97XD/Def2SVP level using Gaussian 16 A03. The absorption and emission wavelengths were evaluated using 13 functional, including TPSSH, O3LYP, B3LYP*, B3LYP, PBE0, MPW1B95, PBE-1/3, PBE38, MPWB1K, MN15, BHandHLYP, ω-B97XD, and CAM-B3LYP.
第二近红外（NIR-II）区域的染料在推进成像技术方面发挥着关键作用。然而，开发用于 NIR-II 的小分子染料是满足生物领域大量需求的一个重大瓶颈，这可能归因于缺乏合理的设计策略。在此，我们通过用 -C(CH)、-Si(CH)、-SO 和 -P(O)Ph 取代基于呫吨的染料中的氧桥原子，设计了一系列发射波长更红移的罗丹明类似物。我们使用（含时）密度泛函理论研究了基于呫吨的染料的前沿分子轨道、静电势表面、相互作用区域指标、电子 - 空穴分布以及吸收和发射光谱。我们的结果表明，这些设计的小分子染料表现出覆盖 1377 - 1809 nm 的长发射波长。我们期望这些发现能够实现长波长罗丹明的靶向设计。
使用 Gaussian 16 A03 在 ω-B97XD/Def2SVP 水平上对染料的基态和激发态进行几何优化。使用包括 TPSSH、O3LYP、B3LYP*、B3LYP、PBE0、MPW1B95、PBE-1/3、PBE38、MPWB1K、MN15、BHandHLYP、ω-B97XD 和 CAM-B3LYP 在内的 13 种泛函评估吸收和发射波长。
