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On-capillary Surface Enhanced Raman Spectroscopy: Determination of Glutathione in Whole Blood Microsamples Ángel Sánchez-Illana, Fritz Mayr, Daniel Cuesta-García, José David Piñeiro-Ramos, Andres Cantarero, Miguel De La Guardia, Maximo Vento, Bernhard Lendl, Guillermo Quintas, and Julia Kuligowski Anal. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.analchem.8b01492 • Publication Date (Web): 25 Jun 2018 Downloaded from http://pubs.acs.org on June 25, 2018
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Analytical Chemistry
On-capillary Surface Enhanced Raman Spectroscopy: Determination of Glutathione in Whole Blood Microsamples Ángel Sánchez-Illanaa‡, Fritz Mayra‡, Daniel Cuesta-Garcíaa,b, José David Piñeiro-Ramosa, Andrés Cantarerob, Miguel de la Guardiac, Máximo Ventoa,d, Bernhard Lendle, Guillermo Quintásf,g*, Julia Kuligowskia* a
Neonatal Research Unit, Health Research Institute La Fe, Avda Fernando Abril Martorell 106, 46026 Valencia, Spain b Molecular Science Institute, University of Valencia , PO Box 22085, 46071 Valencia, Spain c Department of Analytical Chemistry, University of Valencia, 50 Dr. Moliner Street, 46100 Burjassot, Valencia, Spain b Division of Neonatology, University & Polytechnic Hospital La Fe, Avda Fernando Abril Martorell 106, 46026 Valencia, Spain e Institute of Chemical Technologies and Analytics, Vienna University of Technology, Getreidemarkt 9/151, A-1060 Vienna, Austria f Health and Biomedicine, Leitat Technological Center, Avda Fernando Abril Martorell 106, 46026 Valencia, Spain g Analytical Unit, Health Research Institute Hospital La Fe, Avda Fernando Abril Martorell 106, 46026 Valencia, Spain ‡ both authors contributed equally * e-mail:
[email protected];
[email protected] ABSTRACT Oxidative stress monitoring in the neonatal period supports early outcome prediction and treatment. Glutathione (GSH) is the most abundant antioxidant in most cells and tissues, including whole blood, and its usefulness as a biomarker has been known for decades. To date, the available methods for GSH determination require laborious sample processing and the use of sophisticated laboratory equipment. To the best of our knowledge, no tools suitable for point-of-care (PoC) sensing have been reported. Surface Enhanced Raman Spectroscopy (SERS), performed in a micro-volume capillary measurement cell, is proposed in this study as a robust approach for the quantification of GSH in human whole blood samples. The use of a silver colloid allowed a highly selective signal enhancement for GSH providing Analytical Enhancement Factors of three to four orders of magnitude. A highly accurate determination of GSH in whole blood samples with recoveries ranging from 99 to 107% and relative standard deviations ≤18% were achieved by signal normalization with the intensity of an isotopically labelled internal standard. GSH concentrations were retrieved within 4 min using small volume blood samples (2 µL). The developed procedure was applied to the analysis of blood of 20 healthy adults and 36 newborns, obtaining comparable results between literature and those found by SERS and a reference method. The characteristics of this novel tool are suitable for its implementation in a portable optical sensor device enabling PoC testing of oxidative stress levels in newborns. 1 ACS Paragon Plus Environment
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Keywords: Surface Enhanced Raman Scattering (SERS), isotopically labelled internal standard (IS), glutathione (GSH), oxidative stress, whole blood, silver colloid
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Analytical Chemistry
Under normal conditions, arterial oxygen saturation in the fetal-to-neonatal transition rises from 55% in the fetus up to >95% in the newly born infant within approximately 10 min, generating physiologic oxidative stress1,2. However, in very preterm infants (i.e.
