Gu Zhenyan, Lei Wu, Shi Wenyan, Hao Qingli, Si Weimeng, Xia Xifeng, Wang Fengxiang
School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, China.
School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, China.
Spectrochim Acta A Mol Biomol Spectrosc. 2014 Nov 11;132:361-8. doi: 10.1016/j.saa.2014.05.025. Epub 2014 May 21.
The interaction between 9-fluorenylmethyl chloroformate (FMOC-Cl) and Fe3+ and Cu2+ ions was investigated using fluorescence, UV/Vis absorption spectroscopies and theoretical calculation. The optical property of FMOC-Cl was studied in detail in absence and presence of various transition metal ions with particular affinity to Fe3+ and Cu2+ ions. With the fluorescence characteristic band centered at 307 and 315 nm for FMOC-Cl, the introduction of Fe3+ or Cu2+ ions leads to the fluorescence quenching of FMOC-Cl with different shift and intensities of two fluorescent bands. It allows us to differentiate between FMOC-Cl and Fe3+ and Cu2+ ions interaction behavior. The study on fluorescent kinetics confirms that the fluorescence quenching of FMOC-Cl with Fe3+ and Cu2+ ions is based on the formation of non-fluorescent material, that is, static quenching. Further analyses of bond lengths, Mulliken atomic charges and the frontier orbital compositions for FMOC-Cl and its complexes with Fe3+ and Cu2+ ions were carried out. The theoretical calculations prove the fluorescence quenching originates from the formation of coordination bonds between the oxygen atom of the carbonyl group of FMOC-Cl and Fe3+ and Cu2+ ions. The commercially available FMOC-Cl can be used as excellent fluorescent probe toward Fe3+ and Cu2+ ions with high sensitivity.
采用荧光光谱、紫外可见吸收光谱以及理论计算方法,研究了9-芴甲氧羰基氯(FMOC-Cl)与Fe3+和Cu2+离子之间的相互作用。详细研究了在不存在和存在对Fe3+和Cu2+离子具有特殊亲和力的各种过渡金属离子的情况下FMOC-Cl的光学性质。FMOC-Cl的荧光特征带中心位于307和315 nm处,引入Fe3+或Cu2+离子会导致FMOC-Cl的荧光猝灭,且两个荧光带的位移和强度不同。这使我们能够区分FMOC-Cl与Fe3+和Cu2+离子的相互作用行为。荧光动力学研究证实,FMOC-Cl与Fe3+和Cu2+离子的荧光猝灭是基于非荧光物质的形成,即静态猝灭。进一步分析了FMOC-Cl及其与Fe3+和Cu2+离子形成的配合物的键长、 Mulliken原子电荷和前线轨道组成。理论计算证明,荧光猝灭源于FMOC-Cl羰基氧原子与Fe3+和Cu2+离子之间配位键的形成。市售的FMOC-Cl可作为对Fe3+和Cu2+离子具有高灵敏度的优良荧光探针。