Abstract
A new electrochemical device fabricated by the combination of 3D printing manufacturing and laser-generated graphene sensors is presented. Cell and electrodes were 3D printed by the fused deposition modeling (FDM) technique employing acrylonitrile butadiene styrene filament (insulating material that composes the cell) and conductive filament (lab-made filament based on graphite dispersed into polylactic acid matrix) to obtain reference and auxiliary electrodes. Infrared-laser engraved graphene, also reported as laser-induced graphene (LIG), was produced by laser conversion of a polyimide substrate, which was assembled in the 3D-printed electrochemical cell that enables the analysis of low volumes (50–2000 μL). XPS analysis revealed the formation of nitrogen-doped graphene multilayers that resulted in excellent electrochemical sensing properties toward the detection of atropine (ATR), a substance that was found in beverages to facilitate sexual assault and other criminal acts. Linear range between 5 and 35 μmol L−1, detection limit of 1 μmol L−1, and adequate precision (RSD = 4.7%, n = 10) were achieved using differential-pulse voltammetry. The method was successfully applied to beverage samples with recovery values ranging from 80 to 105%. Interference studies in the presence of species commonly found in beverages confirmed satisfactory selectivity for ATR sensing. The devices proposed are useful portable analytical tools for on-site applications in the forensic scenario.
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Acknowledgement
The authors are grateful for the financial support provided by Brazilian funding agencies: National Council for Scientific and Technological Development–CNPq (163330/2020-4, 315838/2021-3, 409680/2021-4, 304119/2019-9); and Coordination for the Improvement of Higher Education Personnel–CAPES (Project SCBA 88887.472618/2019-00 and Finance Code 001), MCTI/CNPQ/CAPES/FAPS N° 16/2014–PROGRAMA INCTBio (465389/2014-7), Research Support Foundation of the State of Minas Gerais–FAPEMIG (Grants APQ-02391-22, RED-00042–16 and APQ-03141–18), Carlos Chagas Filho Foundation for Research Support in the State of Rio de Janeiro–FAPERJ (26/205.806/2022), and São Paulo Research Foundation–FAPESP (2007/08244-5, 2007/54829-5, 2017/18574-4, 2021/08409-1). The authors express their gratitude to Prof. Dr. João Flávio da Silveira Petruci for providing the atropine reagent, to the Multiuser laboratory at the Institute of Physics for Raman experiments (equipment provided by CAPES supported by the “Pró-Equipamentos” grant), and to the Multiuser Laboratories of the Universidade Federal de Uberlândia (RELAM-UFU) for providing the equipment and technical support for experiments involving electron microscopy (FAPEMIG grant APQ-02391-22).
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Figure S1. Picture of the cell and its components. (A) the upper and (B) bottom parts. (C) Screws. (D) Pseudo-reference (with gray tip) and auxiliary (black) electrodes. (E) Steel plate for working electrode support and (F) LIG electrodes. (G) Cell set up for the experiments. Figure S2. (A) Schematic representation showing the distance between the electrodes (reference and counter) and (B) the working electrode and the distance between the reference and counter electrodes. Figure S3. (A) CVs recorded on the LIG electrode in the presence 1 mmol L-1 ATR using scan rate ranging from 40 to 200 mV s-1 using 0.12 mol L–1 BR buffer (pH=11.0) as supporting electrolyte; (B) Linear adjustment between Log I and Log v, and (C) I vs. v1/2. Figure S4. Linear relationship obtained between peak potential and log v. Figure S5. Successive baseline-corrected DPV recordings for 20 μmol L–1 ATR at LIG electrode using 0.12 mol L–1 BR buffer (pH=11.0) as supporting electrolyte. DPV conditions: a= 80 mV, tm= 80 ms and ΔEs= 8 mV. Figure S6. Calibration plots obtained by standard addition for the determination of ATR in spiked beverage samples: energetic drink (A), beer (B), white wine (C) and whisky (D). DPV conditions: a= 80 mV, tm= 80 ms and ΔEs= 8 mV. (DOCX 5982 kb)
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Matias, T.A., Ramos, D.L.O., Faria, L.V. et al. 3D-printed electrochemical cells with laser engraving: develo** portable electroanalytical devices for forensic applications. Microchim Acta 190, 297 (2023). https://doi.org/10.1007/s00604-023-05872-2
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DOI: https://doi.org/10.1007/s00604-023-05872-2