Detection of arsenic is a long-standing challenge in environmental analytical chemistry. In recent years, using biomolecules and nanomaterials for sensing arsenic has been growingly reported. In this article, this field is critically reviewed based on some recent fundamental understandings including interactions between arsenic and gold, thiol, and DNA aptamers. First, taking advantage of the adsorption of As(III) on noble metal surfaces such as silver and gold, sensors were developed based on surface enhanced Raman spectroscopy, electrochemistry and colorimetry. In addition, by functionalizing metal nanoparticles with thiol containing molecules, As(III) induced aggregation of the particles based on As(III)/thiol interactions. As(V) interacts with metal oxides strongly and competitive sensors were developed by displacing pre-adsorbed DNA oligonucleotides. A DNA aptamer was selected for As(III) and many sensors were reported based on this aptamer, although careful binding measurements indicated that the sequence has no affinity towards As(III). Overall, bio/nano systems are promising for the detection of arsenic. Future work on fundamental studies, searching for more specific arsenic binding materials and aptamers, incorporation of sensors into portable devices, and more systematic test of sensors in real samples could be interesting and useful research topics.

An arsenic-binding aptamer named Ars-3 was reported in 2009, and it has been used for detection of As(III) in more than two dozen papers. In this work, we performed extensive binding assays using isothermal titration calorimetry, various DNA-staining dyes, and gold nanoparticles. By carefully comparing Ars-3 and a few random control DNA sequences, no specific binding of As(III) was observed in each case. Therefore, we conclude that Ars-3 cannot bind As(III). Possible reasons for some of the previously reported binding and detection were speculated to be related to the adsorption of As(III) onto gold surfaces, which were used in many related sensor designs, and As(III)/Au interactions were not considered before. The selection data in the original paper were then analyzed in terms of sequence alignment, secondary structure prediction, and dissociation constant measurement. These steps need rigorous testing before confirming specific binding of newly selected aptamers. This study calls for attention to the gap between aptamer selection and biosensor design, and the gap needs to be filled by careful binding assays to further the growth of the aptamer field.