A sensitive quantum dots-based "OFF-ON" fluorescent sensor for ruthenium anticancer drugs and ctDNA

In this contribution, a simple and sensitive fluorescent sensor for the determination of both the three ruthenium anticancer drugs (1 to 3) and calf thymus DNA (ctDNA) was established based on the CdTe quantum dots (QDs) fluorescence "OFF-ON" mode. Under the experimental conditions, the fluorescence of CdTe QDs can be effectively quenched by ruthenium anticancer drugs because of the surface binding of these drugs on CdTe QDs and the subsequent photoinduced electron transfer (PET) process from CdTe QDs to ruthenium anticancer drugs, which render the system into fluorescence "OFF" status. The system can then be "ON" after the addition of ctDNA which brought the restoration of CdTe QDs fluorescence intensity, since ruthenium anticancer drugs broke away from the surface of CdTe QDs and inserted into double helix structure of ctDNA. The fluorescence quenching effect of the CdTe QDs-ruthenium anticancer drugs systems was mainly concentration dependent, which could be used to detect three ruthenium anticancer drugs. The limits of detection were 5.5 Chi 10(-8) M for ruthenium anticancer drug 1, 7.0 Chi 10(-8) M for ruthenium anticancer drug 2, and 7.9 Chi 10(-8) M for ruthenium anticancer drug 3, respectively. The relative restored fluorescence intensity was directly proportional to the concentration of ctDNA in the range of 1.0 Chi 10(-8) M similar to 3.0 Chi 10(-7) M, with a correlation coefficient (R) of 0.9983 and a limit of detection of 1.1 Chi 10(-9) M. The relative standard deviation (RSD) for 1.5 Chi 10(-7) M ctDNA was 1.5% (n = 5). There was almost no interference to some common chemical compounds, nucleotides, amino acids, and proteins. The proposed method was applied to the determination of ctDNA in three synthetic samples with satisfactory results. The possible reaction mechanism of CdTe QDs fluorescence "OFF-ON" was further investigated. This simple and sensitive approach possessed some potential applications in the investigation of interaction between drug molecules and DNA. (C) 2014 Elsevier B.V. All rights reserved.