State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, China.
Anal Chem. 2013 Feb 19;85(4):2436-42. doi: 10.1021/ac303487b. Epub 2013 Feb 4.
In this work, a universal chemiluminescence (CL) flow-through device suitable for various CL resonance energy transfer (CRET) systems has been successfully fabricated. Highly efficient CRET in solid-state photoactive organic molecules can be achieved by assembling them on the surface of layered double hydroxides (LDHs). We attribute these observations to the suppression of the intermolecular π-π stacking interactions among aromatic rings and the improvement of molecular orientation and planarity in the LDH matrix, enabling a remarkable increase in fluorescence lifetime and quantum yield of organic molecules. Under optimal conditions, using peroxynitrous acid-fluorescein dianion (FLUD) as a model CRET system, trace FLUD (10 μM) was assembled on the surface of LDHs. Peroxynitrous acid/nitrite could be assayed in the range of 1.0-500 μM, and the detection limit for peroxynitrous acid/nitrite (S/N = 3) was 0.6 μM. This CL flow-through device exhibited operational stability, high reproducibility, and long lifetime. While LDHs were immobilized in a flow-through device in the absence of FLUD, the detection limit for peroxynitrous acid/nitrite was 100 μM. On the other hand, FLUD at the same concentration can not enhance the CL intensity of peroxynitrous acid system. This fabricated CL flow-through column has been successfully applied to determine nitrite in sausage samples with recoveries of 98-102%. These satisfactory results demonstrated that our studies pave a novel way toward flow-through column-based CRET using solid-state organic molecules as acceptors for signal amplification.
在这项工作中，成功制备了一种适用于各种化学发光（CL）共振能量转移（CRET）体系的通用 CL 流通式装置。通过将固态光活性有机分子组装在层状双氢氧化物（LDH）的表面上，可以实现高效的CRET。我们将这些观察结果归因于抑制芳香环之间的分子间π-π堆积相互作用，以及改善 LDH 基质中分子的取向和平整度，从而使有机分子的荧光寿命和量子产率显著提高。在最佳条件下，使用过氧亚硝酸-荧光素二阴离子（FLUD）作为模型 CRET 体系，将痕量 FLUD（10 μM）组装在 LDH 的表面上。过氧亚硝酸/亚硝酸盐可以在 1.0-500 μM 的范围内进行测定，过氧亚硝酸/亚硝酸盐的检测限（S/N = 3）为 0.6 μM。该 CL 流通式装置表现出操作稳定性、高重现性和长寿命。当 LDH 固定在没有 FLUD 的流通式装置中时，过氧亚硝酸/亚硝酸盐的检测限为 100 μM。另一方面，相同浓度的 FLUD 不能增强过氧亚硝酸体系的 CL 强度。该制备的 CL 流通式柱已成功应用于香肠样品中亚硝酸盐的测定，回收率为 98-102%。这些令人满意的结果表明，我们的研究为使用固态有机分子作为信号放大的接受体的基于流通式柱的 CRET 开辟了一条新途径。
