Waterproof Cellulose-Based Substrates for In-Drop Plasmonic Colorimetric Sensing of Volatiles: Application to Acid-Labile Sulfide Determination in Waters

The present work reports on the assessment of widely available waterproof cellulose-based substrates for the development of sensitive in-drop plasmonic sensing approaches. The applicability of three inexpensive substrates, namely, Whatman 1PS, polyethylene-coated filter paper, and tracing paper, as holders for microvolumes of colloidal solutions was evaluated. Waterproof cellulose-based substrates demonstrated to be highly convenient platforms for analytical purposes, as they enabled <i>in situ</i> generation of volatiles and syringeless drop exposure unlike conventional single-drop microextraction approaches and can behave as sample compartments for smartphone-based colorimetric sensing in an integrated way. Remarkably, large drop volumes (≥20 μL) of colloidal solutions can be employed for enrichment processes when using Whatman 1PS as holder. In addition, the stability and potential applicability of spherical, rod-shaped, and core-shell metallic NPs onto waterproof cellulose-based substrates was evaluated. In particular, Au@AgNPs showed potential for the colorimetric detection of <i>in situ</i> generated H₂S, I₂, and Br₂, whereas AuNRs hold promise for I₂, Br₂, and Hg⁰ colorimetric sensing. As a proof of concept, a smartphone-based colorimetric assay for determination of acid-labile sulfide in environmental water samples was developed with the proposed approach taking advantage of the ability of Au@AgNPs for H₂S sensing. The assay showed a limit of detection of 0.46 μM and a repeatability of 4.4% (<i>N</i> = 8), yielding satisfactory recoveries (91-107%) when applied to the analysis of environmental waters.