The effective functionalization and self-assembly of MXene are of crucial importance for a broad range of nanomaterial applications. In this work, we investigated the aggregates of sulfanilic acid-modified MXene (abbreviated as MXene-SO3H) with three model dyes at the air–water interface and demonstrated the morphological and aggregation changes of composite films, using Langmuir-Blodgett (LB) technology, as well as excellent uniformity and reproducibility by using surface-enhanced Raman scattering (SERS) spectra. This research has found that cationic dye molecules were adsorbed onto negatively charged MXene-SO3H particles mainly through electrostatic interaction and the particles induced dyes to form highly ordered nanostructures including H- and/or J-aggregates corresponding to monomers in bulk solution. The surface pressure-area isotherms from different dye sub phases confirmed that the stable composite films have been successfully formed. And the spectral results reveal that different dyes have different types of aggregations. In addition, the SERS spectra indicated that the optimal layers of MXene-SO3H/methylene blue (MB) films was 50 layers using rhodamine 6G (R6G) as probe molecule. And the formed 50 layers of MXene-SO3H/MB films (MXene-SO3H/MB-50) as SERS substrate were proved to possess excellent uniformity and repeatability.

A flexible and stable biomimetic SERS substrate was successfully fabricated by depositing gold (Au) nanoislands on the dragonfly wings (DW) via a simple DC magnetron sputtering system. Characterizations of the Au/DW nanostructure indicated that the optimum Au/DW-45 (sputtering time was 45 min) substrate owns high sensitivity, good stability and outstanding reproducibility. The limit of detection (LOD) for Rhodamine 6 G (R6G) was as low as 10⁻⁷ M and enhancement factor (EF) was calculated to be 2.8 × 10⁶. 70-day-duration stability tests showed that Raman intensity of R6G reduced only by 12.9% after aging for 70 days. The maximum relative standard deviations (RSD) of SERS intensities from 100 positions of Au/DW-45 substrate were less than 8.3%, revealing outstanding uniformity and reproducibility. Moreover, the flexible Au/DW-45 bioscaffold arrays were employed to solve the vital problem of pesticide residues. By directly sampling from tomato peels via a “press and peel off” approach, cypermethrin has been rapidly and reliably determined with a LOD centered at 10⁻³ ng/cm² and a correlation coefficient (R²) of 0.987. The positive results demonstrated that the Au-based DW biomimetic arrays may offer an efficient SERS platform for the identification of various pesticide residues on real samples.

Considering the complexity and high-consumption of the existing approaches to fabricate three-dimensional (3D) regular substrate templates, the scales of the moth wings with evenly-distributed nanoarrays were discovered to provide an ideal bioscaffold for metal silver (Ag) to decorate on to fabricate a flexible, highly-ordered, low-cost and large-scale Ag nanoislands/moth wing (Ag/MW) SERS-active substrate. The grating-like substrate with the optimal morphology of rough and hierarchical Ag nanoislands exhibited high enhancement factor (EF, ~4.16 × 10⁵), low detection limit (10⁻¹⁰ M) to 4-aminothiophenol (4-ATP), outstanding signal uniformity (the relative standard deviations were less than 15%) and superior identification performance in the quantitative detection of pesticide cypermethrin. The three-dimensional finite-difference time-domain (3D-FDTD) method simulated the spatial distribution of the electric field intensity in the substrates with different morphologies, showing a potential strong enhancement of Raman signals in sub-10 nm gaps between two adjacent Ag nanoislands of different layers. These prominent SERS properties of novel Ag/MW SERS-active substrates suggest their potential value in rapid on-side biological and chemical sensing. Meanwhile, the highly-ordered nanoarrays of moth wings provide a new idea for the preparation of regular biomimetic nanomaterials.