Critical Review: DNA Aptasensors, Are They Ready for Monitoring Organic Pollutants in Natural and Treated Water Sources?

There is a growing need to monitor anthropogenic organic contaminants detected in water sources. DNA aptamers are synthetic single-stranded oligonucleotides, selected to bind to target contaminants with favorable selectivity and sensitivity. These aptamers can be functionalized and are used with a variety of sensing platforms to develop sensors, or aptasensors. In this critical review, we (1) identify the state-of-the-art in DNA aptamer selection, (2) evaluate target and aptamer properties that make for sensitive and selective binding and sensing, (3) determine strengths and weaknesses of alternative sensing platforms, and (4) assess the potential for aptasensors to quantify environmentally relevant concentrations of organic contaminants in water. Among a suite of target and aptamer properties, binding affinity is either directly (e.g., organic carbon partition coefficient) or inversely (e.g., polar surface area) correlated to properties that indicate greater target hydrophobicity results in the strongest binding aptamers, and binding affinity is correlated to aptasensor limits of detection. Electrochemical-based aptasensors show the greatest sensitivity, which is similar to ELISA-based methods. Only a handful of aptasensors can detect organic pollutants at environmentally relevant concentrations, and interference from structurally similar analogs commonly present in natural waters is a yet-to-be overcome challenge. These findings lead to recommendations to improve aptasensor performance.

Selective Aptamers for Detection of Estradiol and Ethynylestradiol in Natural Waters.

We used in vitro selection to identify new DNA aptamers for two endocrine-disrupting compounds often found in treated and natural waters, 17ß-estradiol (E2) and 17α-ethynylestradiol (EE). We used equilibrium filtration to determine aptamer sensitivity/selectivity and dimethyl sulfate (DMS) probing to explore aptamer binding sites. The new E2 aptamers are at least 74-fold more sensitive for E2 than is a previously reported DNA aptamer, with dissociation constants (Kd values) of 0.6 µM. Similarly, the EE aptamers are highly sensitive for EE, with Kd of 0.5-1.0 µM. Selectivity values indicate that the E2 aptamers bind E2 and a structural analogue, estrone (E1), equally well and are up to 74-fold selective over EE. One EE aptamer is 53-fold more selective for EE over E2 or E1, but the other binds EE, E2, and E1 with similar affinity. The new aptamers do not lose sensitivity or selectivity in natural water from a local lake, despite the presence of natural organic matter (∼4 mg/L TOC). DMS probing suggests that E2 binding occurs in relatively flexible single-stranded DNA regions, an important finding for rational redesign of aptamers and their incorporation into sensing platforms. This is the first report of aptamers with strong selectivity for E2 and E1 over EE, or with strong selectivity for EE over E2 and E1. Such selectivity is important for achieving the goal of creating practically useful DNA-based sensors that can distinguish structurally similar estrogenic compounds in natural waters.

Investigation of dye functional group on the photocatalytic degradation of dyes by nano-TiO2.

The photocatalytic degradation of five anionic, eight cationic and three solvent dyes using combustion-synthesized nano-TiO(2) (CS TiO(2)) and commercial Degussa P-25 TiO(2) (DP-25) were evaluated to determine the effect of the functional group in the dye. The degradation of the dyes was quantified using the initial rate of decolorization and mineralization. The decolorization of the anionic dyes with CS TiO(2) followed the order: indigo carmine > eosin Y > amido black 10B > alizarin cyanine green > orange G. The decolorization of the cationic dyes with DP-25 followed the order: malachite green > pyronin Y > rhodamine 6G > azure B > nile blue sulfate > auramine O approximately = acriflavine approximately = safranin O. CS TiO(2) showed higher rates of decolorization and mineralization for all the anionic dyes compared to DP-25, while DP-25 was better in terms of decolorization for most of the cationic dyes. The solvent dyes exhibited adsorption dependent decolorization. The order of decolorization and mineralization of the anionic and cationic dyes (a) with CS TiO(2) and DP-25 was different and correlated with the surface properties of these catalysts (b) were rationalized with the molecular structure of the dye and the degradation pathway of the dye.