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Text from PDF Page: 001The role of the electrolysis and enzymatic hydrolysis in the enhancement of the electrochemical properties of 3D-printed carbon black/poly(lactic acid) structures Adrian Koterwa1,#, Iwona Kaczmarzyk2,#, Szymon Mania3, Mateusz Cieślik3,4, Robert Tylingo3, Tadeusz Ossowski1, Robert Bogdanowicz2, Paweł Niedziałkowski1, Jacek Ryl4,* 1 Department of Analytical Chemistry, University of Gdansk, Wita Stwosza 63, 80-308 Gdansk, Poland 2 Department of Metrology and Optoelectronics and Advanced Materials Center, Gdansk University of Technology, Narutowicza 11/12, 80-233 Gdansk, Poland 3 Faculty of Chemistry, Gdansk University of Technology, Narutowicza 11/12, 80-233 Gdansk, Poland 4 Institute of Nanotechnology and Materials Engineering and Advanced Materials Center, Gdansk University of Technology, Narutowicza 11/12, 80-233 Gdansk, Poland * Correspondence: Jacek Ryl – firstname.lastname@example.org # these authors contributed equally to the manuscript Abstract: Additive manufacturing, called 3D printing, starts to play an unprecedented role in developing many applications in industrial or personalized products. The conductive composite structures require additional treatment to achieve an electroactive surface useful for electrochemical devices. In this paper, the surfaces of carbon black/poly(lactic acid) CB-PLA printouts were activated by electrolysis or enzymatic digestion with proteinase K, or a simultaneous combination of both. Proposed modification protocols allowed for tailoring electrochemically active surface area and electron transfer kinetics determined by electrochemical techniques (CV, EIS) with [Fe(CN)6]4-/3- redox probe. The X-ray photon spectroscopy and SEM imaging were applied to determine the delivered surface chemistry. The CB-PLA hydrolysis in alkaline conditions and under anodic polarization greatly impacts the charge transfer kinetics. The enzymatic hydrolysis of PLA with proteinase K has led to highly efficient results yet requiring an unsatisfactory prolonged activation duration of 72 h, efficiently reduced by the electrolysis carried out in the presence of the enzyme. Our studies hint that the activation protocol originates from surface electropolymerization rather than synergistic interaction between electrolysis and enzymatic hydrolysis. The detailed mechanism of CB-PLA hydrolysis supported by electrolysis has been elaborated since it pawed a new route towards a time-efficient and environmentally-friendly activation procedure.
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