Graphene-supported Pd/Pt nano-catalysts for enhanced colorimetric detection of dopamine and NADH using paper-based microfluidic devices: Original scientific article

Ruri Wahyuono; Jovin Jovin; Ignacius Gilbert Chano; Arda Fridua Putra; Annisa Septyana Ningrum; Muhammad Yusuf Hakim  Widianto; Irkham Irkham; Yeni Wahyuni  Hartati; Wulan Tri Wahyuni; Isnaini Rahmawati; Chi-Hsien Huang; Yi-Ting Lai

doi:10.5599/admet.3247

Authors

Ruri Wahyuono Department of Engineering Physics, Institut Teknologi Sepuluh Nopember, Surabaya 60111, Indonesia and School of Interdisciplinary Management and Technology, Institut Teknologi Sepuluh Nopember, Surabaya 60264, Indonesia https://orcid.org/0000-0002-6937-9907
Jovin Jovin Department of Engineering Physics, Institut Teknologi Sepuluh Nopember, Surabaya 60111, Indonesia https://orcid.org/0009-0005-3431-8409
Ignacius Gilbert Chano Department of Engineering Physics, Institut Teknologi Sepuluh Nopember, Surabaya 60111, Indonesia https://orcid.org/0009-0005-1290-1556
Arda Fridua Putra Department of Engineering Physics, Institut Teknologi Sepuluh Nopember, Surabaya 60111, Indonesia https://orcid.org/0009-0009-3816-459X
Annisa Septyana Ningrum Department of Engineering Physics, Institut Teknologi Sepuluh Nopember, Surabaya 60111, Indonesia https://orcid.org/0009-0009-9833-8328
Muhammad Yusuf Hakim Widianto Department of Mathematics, Institut Teknologi Sepuluh Nopember, Surabaya 60111, Indonesia https://orcid.org/0000-0002-1720-9754
Irkham Irkham Department of Chemistry, University of Padjadjaran, Sumedang 45363, Indonesia https://orcid.org/0000-0001-9938-2931
Yeni Wahyuni Hartati Department of Chemistry, University of Padjadjaran, Sumedang 45363, Indonesia https://orcid.org/0000-0003-1463-6352
Wulan Tri Wahyuni Department of Chemistry, Institut Pertanian Bogor (IPB) University, Bogor 16680, Indonesia https://orcid.org/0000-0002-3071-4974
Isnaini Rahmawati Department of Chemistry, University of Indonesia, Depok 16424, Indonesia https://orcid.org/0000-0003-1327-592X
Chi-Hsien Huang Department of Engineering Physics, Institut Teknologi Sepuluh Nopember, Surabaya 60111, Indonesia and Department of Materials Engineering, Ming Chi University of Technology, New Taipei City 243303, Taiwan- https://orcid.org/0000-0003-0369-3124
Yi-Ting Lai Department of Materials Engineering, Ming Chi University of Technology, New Taipei City 243303, Taiwan- https://orcid.org/0000-0002-5662-2090

DOI:

https://doi.org/10.5599/admet.3247

Keywords:

Biomarker, colorimetry, nanocomposites, microfluidic paper-based analytical devices, sensor

Abstract

Background and purpose: Dopamine and nicotinamide adenine dinucleotide (NADH) are key biomarkers associated with neurological and metabolic disorders. Developing rapid, low-cost, and portable detection platforms of these biomarkers is essential for a point-of-care diagnostic kit. In this work, we report a colorimetric sensing approach using paper-based microfluidic devices (µPADs) modified with graphene-supported palladium (G/Pd) and platinum (G/Pt) nanocatalysts to enhance detection performance. Experimental approach: Monolayer G/Pd and G/Pt nanocomposites were synthesized via a hydrothermal method with precursor concentrations ranging from 0.1 to 10 mM. The catalytic behaviour and metal-graphene interactions were further investigated using spin-polarized density functional theory (DFT) calculation (PHASE/0). Microfluidic paper-based analytical devices (µPADs) were laser-printed on commercial filter paper and folded into 3D origami structures. Colorimetric responses were quantified using red, green, blue (RGB) and hue, saturation, value (HSV) analysis, where time-dependent Euclidean distance in RGB colour space was used to assess the reaction kinetics. Key results: DFT results indicate that Pd and Pt clusters preferentially adopt a top-site configuration on graphene, facilitating interfacial charge redistribution and enhancing catalytic activity experimentally. Catalyst-modified µPADs significantly improve reaction kinetics, reducing detection time by up to 3.7× for dopamine and 2.5× for NADH compared to unmodified devices. G/Pt (10 mM) exhibits the best overall performance, achieving limits of detection of 0.16 µM for dopamine and 0.195 µM for NADH with good linearity (R² = 0.91). G/Pd displays competitive sensitivity, particularly at lower precursor concentration. Conclusion: The findings highlight that optimizing catalyst morphology and interfacial electronic structure is more critical than minimizing activation energy for achieving high-performance colorimetric sensing. The resulting platform shows potential as a cost-effective and portable tool for the detection of clinically relevant biomarkers in point-of-care settings.

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References

[1] F.G. Valikchali, M. Rahimnejad, A. Ramiar, M. Ezoji. Diagnostics devices for improving the world: μPADs integrated with smartphone for colorimetric detection of dopamine. International Journal of Engineering 35 (2022) 1723-1727. https://dx.doi.org/10.5829/ije.2022.35.09C.07 DOI: https://doi.org/10.5829/IJE.2022.35.09C.07

[2] R.M. Wise, A. Wagener, U.M. Fietzek, T. Klopstock, E.V. Mosharov, F.A. Zucca, D. Sulzer, L. Zecca, L.F. Burbulla. Interactions of dopamine, iron, and alpha-synuclein linked to dopaminergic neuron vulnerability in Parkinson’s disease and neurodegeneration with brain iron accumulation disorders. Neurobiology of Disease 175 (2022) 105920. https://dx.doi.org/10.1016/j.nbd.2022.105920 DOI: https://doi.org/10.1016/j.nbd.2022.105920

[3] E. Bezard, C.E. Gross, J.M. Brotchie. Presymptomatic compensation in Parkinson’s disease is not dopamine-mediated. Trends in Neurosciences 26 (2003) 215-221. https://dx.doi.org/10.1016/S0166-2236(03)00038-9 DOI: https://doi.org/10.1016/S0166-2236(03)00038-9

[4] R. Sangubotla, J. Kim. Recent trends in analytical approaches for detecting neurotransmitters in Alzheimer’s disease. TrAC - Trends in Analytical Chemistry 105 (2018) 240-250. https://dx.doi.org/10.1016/j.trac.2018.05.014 DOI: https://doi.org/10.1016/j.trac.2018.05.014

[5] S.D. Niyonambaza, P. Kumar, P. Xing, J. Mathault, P. De Koninck, E. Boisselier, M. Boukadoum, A. Miled. A review of neurotransmitters sensing methods for neuro-engineering research. Applied Sciences 9 (2019) 4719. https://dx.doi.org/10.3390/app9214719 DOI: https://doi.org/10.3390/app9214719

[6] I. Rahmawati, A. Fiorani, I. Irkham, W.T. Wahyuni, R.A. Wahyuono, Y. Einaga, T.A. Ivandini. Comparison between electrochemiluminescence of luminol and electrocatalysis by Prussian blue for the detection of hydrogen peroxide. Analytical Methods 17 (2025) 1790-1796. https://dx.doi.org/10.1039/D4AY02175D DOI: https://doi.org/10.1039/D4AY02175D

[7] W.T. Wahyuni, S.A.H. Ta'alia, A.Y. Akbar, B.R. Elvira, I. Rahmawati, R.A. Wahyuono, B.R. Putra. Electrochemical sensors based on the composite of reduced graphene oxide and multiwalled carbon nanotube-modified glassy carbon electrode for simultaneous detection of hydroquinone, dopamine, and uric acid. RSC Advances 14 (2024) 27999-28016. https://dx.doi.org/10.1039/D4RA05537C DOI: https://doi.org/10.1039/D4RA05537C

[8] T. Akyazi, L. Basabe-Desmonts, F. Benito-Lopez. Review on microfluidic paper-based analytical devices towards commercialisation. Analytica Chimica Acta 1001 (2018) 1-17. https://dx.doi.org/10.1016/j.aca.2017.11.010 DOI: https://doi.org/10.1016/j.aca.2017.11.010

[9] A.W. Martinez, S.T. Phillips, G.M. Whitesides, E. Carrilho. Diagnostics for the developing world: Microfluidic paper-based analytical devices. Analytical Chemistry 82 (2010) 3-10. https://dx.doi.org/10.1021/ac9013989 DOI: https://doi.org/10.1021/ac9013989

[10] L.C. Muhimmah, Roekmono, H. Hadi, R.A. Yuwono, R.A. Wahyuono. Blood plasma separation in ZnO nanoflowers-supported paper-based microfluidic for glucose sensing. AIP Conference Proceedings 1945 (2018) 020006. https://dx.doi.org/10.1063/1.5030228 DOI: https://doi.org/10.1063/1.5030228

[11] B. Kuswandi, M.A. Hidayat, E. Noviana. Paper-based sensors for rapid important biomarkers detection. Biosensors and Bioelectronics: X 12 (2022) 100246. https://dx.doi.org/10.1016/j.biosx.2022.100246 DOI: https://doi.org/10.1016/j.biosx.2022.100246

[12] A. Espinosa, J. Diaz, E. Vazquez, L. Acosta, A. Santiago, L. Cunci. Fabrication of paper-based microfluidic devices using a 3D printer and a commercially available wax filament. Talanta Open 6 (2022) 100142. https://dx.doi.org/10.1016/j.talo.2022.100142 DOI: https://doi.org/10.1016/j.talo.2022.100142

[13] J. Zheng, M. Zhu, J. Kong, Z. Li, J. Jiang, Y. Xi, F. Li. Microfluidic paper-based analytical device by using Pt nanoparticles as highly active peroxidase mimic for simultaneous detection of glucose and uric acid with use a smartphone. Talanta 237 (2022) 122954. https://dx.doi.org/10.1016/j.talanta.2021.122954 DOI: https://doi.org/10.1016/j.talanta.2021.122954

[14] V.S.A. Piriya, P. Joseph, S.C.G.K. Daniel, S. Lakshmanan, T. Kinoshita, S. Muthusamy. Colorimetric sensors for rapid detection of various analytes. Materials Science and Engineering C 78 (2017) 1231-1245. https://dx.doi.org/10.1016/j.msec.2017.05.018 DOI: https://doi.org/10.1016/j.msec.2017.05.018

[15] C. Wang, M. Liu, Z. Wang, S. Li, Y. Deng, N. He. Point-of-care diagnostics for infectious diseases: From methods to devices. Nano Today 37 (2021) 101092. https://dx.doi.org/10.1016/j.nantod.2021.101092 DOI: https://doi.org/10.1016/j.nantod.2021.101092

[16] J.I. Ayogu, N. Elahi, C.D. Zeinalipour-Yazdi. Emerging trends in palladium nanoparticles: Sustainable approaches for enhanced cross-coupling catalysis. Catalysts 15 (2025) 181. https://dx.doi.org/10.3390/catal15020181 DOI: https://doi.org/10.3390/catal15020181

[17] S. Singh, P. Tripathi, N. Kumar, S. Nara. Colorimetric sensing of malathion using palladium-gold bimetallic nanozyme. Biosensors and Bioelectronics 92 (2017) 280-286. https://dx.doi.org/10.1016/j.bios.2016.11.011 DOI: https://doi.org/10.1016/j.bios.2016.11.011

[18] K.V. Ragavan, P. Egan, S. Neethirajan. Multi-mimetic graphene-palladium nanocomposite based colorimetric paper sensor for detection of neurotransmitters. Sensors and Actuators B: Chemical 273 (2018) 1789-1798. https://dx.doi.org/10.1016/j.snb.2018.07.048 DOI: https://doi.org/10.1016/j.snb.2018.07.048

[19] Y. Si, E.T. Samulski. Exfoliated graphene separated by platinum nanoparticles. Chemistry of Materials 20 (2008) 6792-6797. https://dx.doi.org/10.1021/cm801356a DOI: https://doi.org/10.1021/cm801356a

[20] Y. Jia, H. Sun, X. Li, D. Sun, T. Hu, N. Xiang, Z. Ni. Paper-based graphene oxide biosensor coupled with smartphone for quantification of glucose in oral fluid. Biomedical Microdevices 20 (2018) 87. https://dx.doi.org/10.1007/s10544-018-0332-2 DOI: https://doi.org/10.1007/s10544-018-0332-2

[21] P. Szczyglewska, A. Feliczak-Guzik, I. Nowak. Nanotechnology—general aspects: A chemical reduction approach to the synthesis of nanoparticles. Molecules 28 (2023) 4932. https://dx.doi.org/10.3390/molecules28134932 DOI: https://doi.org/10.3390/molecules28134932

[22] K. Gotoh, K. Kawabata, E. Fujii, K. Morishige, T. Kinumoto, Y. Miyazaki, H. Ishida. The use of graphite oxide to produce mesoporous carbon supporting Pt, Ru, or Pd nanoparticles. Carbon 47 (2009) 2120-2124. https://dx.doi.org/10.1016/j.carbon.2009.03.052 DOI: https://doi.org/10.1016/j.carbon.2009.03.052

[23] I. Khalil, N.M. Julkapli, W.A. Yehye, W.J. Basirun, S.K. Bhargava. Graphene-gold nanoparticle hybrids-synthesis, functionalization, and application in electrochemical and surface-enhanced raman scattering biosensors. Materials 9 (2016) 406. https://dx.doi.org/10.3390/ma9060406 DOI: https://doi.org/10.3390/ma9060406

[24] F.N. Xiao, M. Wang, F.B. Wang, X.H. Xia. Graphene-ruthenium(II) complex composites for sensitive ECL immunosensors. Small 10 (2014) 706-716. https://dx.doi.org/10.1002/smll.201301566 DOI: https://doi.org/10.1002/smll.201301566

[25] S. Yang, J. Dong, Z. Yao, C. Shen, X. Shi, Y. Tian, S. Lin, X. Zhang. One-pot synthesis of graphene-supported monodisperse Pd nanoparticles as catalyst for formic acid electro-oxidation. Scientific Reports 4 (2014) 4501. https://dx.doi.org/10.1038/srep04501 DOI: https://doi.org/10.1038/srep04501

[26] F. Xu, Y. Sun, Y. Zhang, Y. Shi, Z. Wen, Z. Li. Graphene-Pt nanocomposite for nonenzymatic detection of hydrogen peroxide with enhanced sensitivity. Electrochemistry Communications 13 (2011) 1131-1134. https://dx.doi.org/10.1016/j.elecom.2011.07.017 DOI: https://doi.org/10.1016/j.elecom.2011.07.017

[27] T. Yamasaki, A. Kuroda, T. Kato, J. Nara, J. Koga, T. Uda, K. Minami, T. Ohno. Multi-axis decomposition of density functional program for strong scaling up to 82,944 nodes on the K computer: Compactly folded 3D-FFT communicators in the 6D torus network. Computer Physics Communications 244 (2019) 264-276. https://dx.doi.org/10.1016/j.cpc.2019.04.008 DOI: https://doi.org/10.1016/j.cpc.2019.04.008

[28] A.F. Putra, A.S. Ningrum, S. Suyanto, V.M. Pratiwi, M.Y.H. Widianto, I. Irkham, W.T. Wahyuni, I. Rahmawati, F.-M. Wang, C.-H. Huang, R.A. Wahyuono. Monolayer graphene/platinum-modified 3D origami microfluidic paper-based biosensor for smartphone-assisted biomarkers detection. ADMET and DMPK 13 (2025) 2833. https://dx.doi.org/10.5599/admet.2833 DOI: https://doi.org/10.5599/admet.2833

[29] A.B.D. Nandiyanto, R. Oktiani, R. Ragadhita. How to read and interpret FTIR spectroscopy of organic materials. Indonesian Journal of Science and Technology 4 (2019) 97-118. https://dx.doi.org/10.17509/ijost.v4i1.15806 DOI: https://doi.org/10.17509/ijost.v4i1.15806

[30] L. Morsch, S. Farmer, and K. Cunningham, “Infrared Spectra of Some Common Functional Groups,” in Organic Chemistry, LibreTexts, 2022, ch. 12-8, pp. 1-10. https://chem.libretexts.org/Bookshelves/Organic_Chemistry/Organic_Chemistry_(Morsch_et_al.) (accessed 15 January 2025).

[31] S.A. Putri, Y. Yamaguchi, T.A. Ariasoca, M.Y.H. Widianto, K. Tagami, M. Saito. Electronic band structures of group-IV two-dimensional materials: Spin-orbit coupling and group theoretical analysis. Surface Science 714 (2021) 121917. https://dx.doi.org/10.1016/j.susc.2021.121917 DOI: https://doi.org/10.1016/j.susc.2021.121917

[32] S. Minami, I. Sugita, R. Tomita, H. Oshima, M. Saito. Group-theoretical analysis of two-dimensional hexagonal materials. Japanese Journal of Applied Physics 56 (2017) 105102. https://dx.doi.org/10.7567/JJAP.56.105102 DOI: https://doi.org/10.7567/JJAP.56.105102

[33] U. Kreibig, M. Vollmer. Optical Properties of Metal Clusters. Springer, Berlin, Germany, 1995, p. 532. https://dx.doi.org/10.1007/978-3-662-09109-8 DOI: https://doi.org/10.1007/978-3-662-09109-8

[34] F.T. Johra, J.W. Lee, W.G. Jung. Facile and safe graphene preparation on solution-based platform. Journal of Industrial and Engineering Chemistry 20 (2014) 2883-2887. https://dx.doi.org/10.1016/j.jiec.2013.11.022 DOI: https://doi.org/10.1016/j.jiec.2013.11.022

[35] R.A. Wahyuono, D.D. Risanti, T. Shirosaki, S. Nagaoka, M. Takafuji, H. Ihara. Photoelectrochemical performance of DSSC with monodisperse and polydisperse ZnO spherical particles. AIP Conference Proceedings 1586 (2014) 78-81. https://dx.doi.org/10.1063/1.4866734 DOI: https://doi.org/10.1063/1.4866734

[36] R.A. Wahyuono, D.D. Risanti. Quasi-solid state DSSC performance enhancement by bilayer mesoporous TiO₂ structure modification. Advanced Materials Research 789 (2013) 93-96. https://dx.doi.org/10.4028/www.scientific.net/AMR.789.93 DOI: https://doi.org/10.4028/www.scientific.net/AMR.789.93

[37] G. Oskam, A. Nellore, R.L. Penn, P.C. Searson. The growth kinetics of TiO₂ nanoparticles from titanium(IV) alkoxide at high water/titanium ratio. Journal of Physical Chemistry B 107 (2003) 1734-1738. https://dx.doi.org/10.1021/jp021237f DOI: https://doi.org/10.1021/jp021237f

[38] M. Harada, H. Einaga. Formation mechanism of Pt particles by photoreduction of Pt ions in polymer solutions. Langmuir 22 (2006) 2371-2377. https://dx.doi.org/10.1021/la052378m DOI: https://doi.org/10.1021/la052378m

[39] T. Teranishi, M. Miyake. Size control of palladium nanoparticles and their crystal structures. Chemistry of Materials 10 (1998) 594-600. https://dx.doi.org/10.1021/cm9705808 DOI: https://doi.org/10.1021/cm9705808

[40] J. Tao, Y. Sun, G.G.Z. Zhang, L. Yu. Solubility of small-molecule crystals in polymers: D-mannitol in PVP, indomethacin in PVP/VA, and nifedipine in PVP/VA. Pharmaceutical Research 26 (2009) 855-864. https://dx.doi.org/10.1007/s11095-008-9784-z DOI: https://doi.org/10.1007/s11095-008-9784-z

[41] Y. Wang, J. Liu, L. Liu, D.D. Sun. High-quality reduced graphene oxide-nanocrystalline platinum hybrid materials prepared by simultaneous co-reduction of graphene oxide and chloroplatinic acid. Nanoscale Research Letters 6 (2011) 241. https://dx.doi.org/10.1186/1556-276X-6-241 DOI: https://doi.org/10.1186/1556-276X-6-241

[42] D. Chu, A. Nemoto, H. Ito. Effects of geometric parameters for superhydrophobicity of polymer surfaces fabricated by precision tooling machines. Microsystem Technologies 20 (2014) 223-235. https://dx.doi.org/10.1007/s00542-013-1758-3 DOI: https://doi.org/10.1007/s00542-013-1758-3

[43] C. Liu, F.A. Gomez, Y. Miao, P. Cui, W. Lee. A colorimetric assay system for dopamine using microfluidic paper-based analytical devices. Talanta 194 (2019) 171-176. https://dx.doi.org/10.1016/j.talanta.2018.10.039 DOI: https://doi.org/10.1016/j.talanta.2018.10.039

[44] D. Lavogina, H. Lust, M.J. Tahk, T. Laasfeld, H. Vellama, N. Nasirova, M. Vardja, K.L. Eskla, A. Salumets, A. Rinken, J. Jaal. Revisiting the resazurin-based sensing of cellular viability: Widening the Application Horizon. Biosensors 12 (2022) 196. https://dx.doi.org/10.3390/bios12040196 DOI: https://doi.org/10.3390/bios12040196