Abstract
Arginine has an important role in the metabolomics of gastric cancer. Two 3D enantioselective needle stochastic sensors based on the physical immobilization of 2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphine manganese(III) chloride (solution, 10−3 mol L−1) in graphene paste matrices decorated with N and S atoms were designed, characterized and validated for the enantioanalysis of arginine in whole blood and tissue samples. The signature values obtained for the enantiomers of arginine confirmed that the stochastic sensors are enantioselective. The lowest limit of quantification obtained for both enantiomers of arginine was 1 fmol L−1, while sensitivity of up to 1011 s−1 mol−1 L was recorded for the stochastic sensors. High recoveries were obtained for the determination of one enantiomer in the presence of the other one; moreover, very good correlation was found between the results obtained with the two 3D enantioselective needle stochastic sensors.
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Jing F, Hu X, Cao Y, Xu M, Wang Y, Jing Y, Hu X, Gao Y, Zhu Z. Discriminating gastric cancer and gastric ulcer using human plasma amino acid metabolic profile. IUBMB Life. 2018;70:553–62.
Lind DS. Arginine and cancer. J Nutr. 2004;134:2837S–41.
Liu J, Lin S, Li Z, Zhou L, Yan X, Xue Y, Meng L, Lu J, Suo B, Jian W. Free amino acid profiling of gastric juice as a method for discovering potential biomarkers of early gastric cancer. Int J Clin Exp Pathol. 2018;11:2323–36.
Kögl F, Erxleben H. Zur ätiologie der malignen tumoren. Zeitschrift fűr Physiologische Chemie. 1939;258:57–95.
Bastings JJAJ, van Eijk HM, Damink SWO, Rensen SS. d-amino Acids in Health and Disease: A Focus on Cancer. Nutrients. 2019;11:2205.
Ilie-Mihai RM, Stefan-van Staden RI, Magerusan L, Coros M, Pruneanu S. Enantioanalysis of tryptophan in whole blood samples using stochastic sensors—A screening test for gastric cancer. Chirality. 2020;32:215–22.
Bogea IM, Stefan-van Staden RI, Gheorghe DC, Ilie-Mihai RM. Enantioanalysis of Aspartic Acid Using 3D Stochastic Sensors. Anal Lett. 2022;55:8592.
Stefan-van Staden RI, Ilie-Mihai RM, Magerusan L, Coros M, Pruneanu S. Enantioanalysis of glutamine—a key factor in establishing the metabolomics process in gastric cancer. Anal Bioanal Chem. 2020;412:3199–207.
Wei Z, Liu X, Cheng C, Yu W, Yi P. Metabolism of Amino Acids in Cancer. Frontiers Cell. Dev Biol. 2021;8:603837. https://doi.org/10.3389/fcell.2020.603837.
Glass RE, Goode AW, Houghton BJ, Rowell LW. Plasma arginine in cancer of the gastrointestinal tract: effect of surgical treatment. Gut. 1986;27:8448.
Al-Koussa H, El Mais N, Maalouf H, Abi-Habib R, El-Sibai. Arginine deprivation: a potential therapeutic for cancer cell metastasis? A review. M. Cancer Cell Int. 2020;20:150.
Rodriguez PC, Quiceno DG, Ochoa AC. L-arginine availability regulates T-lymphocyte cell-cycle progression. Blood. 2007;109:1568–73.
Scolaro LM, Castriciano M, Romeo A, Patané A, Cefali E, Allegrini M. Aggregation behaviour of Protoporphyrin IX in aqueous solutions: clear evidence of vesicle formation. J Phys Chem B. 2002;106:2453–9.
Coros M, Pruneanu S, Stefan-van Staden RI. Review—Recent Progress in the Graphene-Based Electrochemical Sensors and Biosensors. J Electrochem Soc. 2020;167:037528.
Pogacean F, Socaci C, Pruneanu SM, Biris AR, Coros M, Magerusan L, Katona G, Turcu R, Borodi G. Graphene based nanomaterials as chemical sensors for hydrogen peroxide—a comparison study of their intrinsic peroxidase catalytic behavior. Sensors Actuators B Chem. 2015;213:474–83.
Udayabhaskar R, Mangalaraja RV, Pandiyarajan T, Karthikeyan B, Mansilla HD, Contreras D. Spectroscopic investigation on graphene-copper nanocomposites with strong UV emission and high catalytic activity. Carbon. 2017;124:256–62.
Stasyuk N, Smutok O, Gayda G, Koval’chuk Y, Gonchar M. A new bi-enzyme potentiometric sensor for arginine analysis based on recombinant human arginase I and commercial urease. J Mater Sci Eng A. 2011;1:819–27.
Stasyuk N, Smutok O, Gayda G, Vus B, Gonchar M, Koval’chuk Y. Bi-enzyme l-arginine-selective amperometric biosensor based on ammonium-sensing polyaniline-modified electrode. Biosens Bioelectron. 2012;37:46–52.
Stasyuka NY, Gaydaa GZ, Gonchar MV. l-Arginine-selective microbial amperometric sensor based on recombinant yeast cells over-producing human liver arginase I. Sensors Actuators B. 2014;204:515–21.
Nikolelis DP, Hadjiioannou TP. Construction of an arginine enzyme electrode and determination of arginine in biological materials. Anal Chim Acta. 1983;147:33–9.
Acknowledgements
The authors are grateful to Alexandra Cioriţă for the SEM investigation of graphene samples and to Alexandru Turza for recording the XRD pattern of the samples.
Funding
This work was supported by a grant of the Ministry of Research, Innovation and Digitization, CNCS/CCCDI–UEFISCDI, project number PN-III-P4-ID-PCCF-2016-0006, within PNCDI III.
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Ethics committee approval no. 75/2015 obtained from the Hospital of Targu Mures
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Biological samples of whole blood and gastric tumor tissues were obtained from the Hospital of Targu Mures within the project PN-III-P4-ID-PCCF-2016-0006.
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Stefan-van Staden, RI., Bogea, M.I., Ilie-Mihai, RM. et al. N,S-Decorated graphenes modified with 2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphine manganese(III) chloride-based 3D needle stochastic sensors for enantioanalysis of arginine: a key factor in the metabolomics and early detection of gastric cancer. Anal Bioanal Chem 414, 6521–6530 (2022). https://doi.org/10.1007/s00216-022-04209-x
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DOI: https://doi.org/10.1007/s00216-022-04209-x


