Department of Chemistry, Humboldt-Universität zu Berlin, Brook-Taylor-Str. 2, 12489 Berlin, Germany.
Phys Rev Lett. 2010 Aug 13;105(7):073003. doi: 10.1103/PhysRevLett.105.073003. Epub 2010 Aug 12.
We present a general mechanism for successful discrimination of spectroscopically indistinguishable biochromophores by shaped light. For this purpose we use nonadiabatic dynamics in excited electronic states in the frame of the field-induced surface hopping method driven by the experimentally shaped laser fields. Our findings show that optimal laser fields drive low-frequency vibrational modes localized in the side chains of two biochromophores, thus selecting the parts of their potential energy surfaces characterized by different transition dipole moments leading to different ionization probabilities. The presented mechanism leads to selective fluorescence depletion which serves as a discrimination signal. Our findings offer a promising perspective for using optimally shaped laser pulses in bioanalytical applications by increasing the selectivity beyond the current capability.
我们提出了一种通过整形光成功区分光谱不可分辨生色团的通用机制。为此，我们在实验整形激光场驱动的场致表面跳跃方法的框架内，使用激发电子态中的非绝热动力学。我们的研究结果表明，最优激光场驱动位于两个生色团侧链中的低频振动模式，从而选择其势能面的不同部分，这些部分具有不同的跃迁偶极矩，导致不同的离化概率。所提出的机制导致选择性荧光耗尽，这可作为区分信号。我们的研究结果为在生物分析应用中使用最佳整形激光脉冲提供了有希望的前景，使选择性超过当前能力。
