Crosslinked zwitterionic polymeric ionic liquid-functionalized nitinol wires for fiber-in-tube solid-phase microextraction and UHPLC-MS/MS as an amyloid beta peptide binding protein assay in biological fluids

Author(s)

Souza, Israel D. ^[1] ; Anderson, Jared L. ^[2] ; Queiroz, Maria Eugenia C. ^[1]

Affiliation

^[1] Univ Sao Paulo, Fac Filosofia Ciencias & Letras Ribeirao Preto, Dept Quim, Ribeirao Preto, SP - Brazil

^[2] Iowa State Univ, Dept Chem, Ames, IA 50011 - USA

• Document type: Journal article
• Source: Analytica Chimica Acta; v. 1193, FEB 8 2022.
• Web of Science Citations: 0

Abstract

Alzheimer disease (AD) is a neurodegenerative disorder characterized by extracellular accumulation of amyloid-beta peptide (A beta) in the brain interstitium. Human serum albumin (HSA) highly binds to A beta in blood plasma and is thought to inhibit plaque formation in peripheral tissue. Thus, the evaluation of albumin binding to A beta is an important key to understand the dynamics of these molecules in the biological system of patients with AD. In this work, a fiber-in-tube solid-phase microextraction (fiber-in-tube SPME) and ultra-high-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) method was developed to estimate A beta fraction binding to HSA in cerebrospinal fluid (CSF) and plasma samples. Crosslinked zwitterionic polymeric ionic liquid (zwitterionic PIL)-coated nitinol wires were developed and packed into a polyether ether ketone (PEEK) capillary for a fiber-in-tube SPME and UHPLC-MS/MS method. Zwitterionic PIL sorbent was synthetized from 1-vinyl-3-(butanesulfonate)imidazolium ({[}VIm(+)C(4)SO(3)(-)]) and 1,12-di(3-vinylimidazolium)dodecane dibromide ({[}(VIm)(2)C-12](2){[}Br]) monomers by in-situ thermally-initiated polymerization. Morphological characterization by scanning electron microscopy (SEM) and atomic force microscopy (AFM) revealed a decrease in the surface roughness of the nitinol wires from similar to 17 nm to 1 nm after the in-situ polymerization. The zwitterionic PIL sorbent selectively preconcentrates A beta through a two-pronged interaction mechanism. The fiber-in-tube SPME and UHPLC-MS/MS method presented lower limits of quantification (LLOQ) of 0.4 ng mL(-1) for A beta 38 and 0.3 ng mL(-1) for A beta 40 and A beta 42, a linear range from LLOQ values to 15 ng mL(-1) with coefficients of determination higher than 0.99, precision with coefficient of variation (CV) values ranging from 2.1 to 7.3% and accuracy with relative standard deviation (RSD) values from -0.3 to 7.4. This method was successfully applied to evaluate the binding of HSA to A beta in cerebrospinal fluid (CSF) and plasma samples. (C) 2021 Elsevier B.V. All rights reserved. (AU)

• FAPESP's process: 17/02147-0 - Single drop chromatography and its coupling to mass spectrometry: instrumental strategies, development of materials, automation and analytical applications
• Grantee: Fernando Mauro Lanças
• Support Opportunities: Research Projects - Thematic Grants
• FAPESP's process: 19/19485-0 - Development of nitinol fiber chemically coated with zwitterionic polymeric ionic liquids for determination of beta-amyloids in plasma samples from patients with Alzheimer's disease by direct coupling fiber-in-tube SPME and MS/MS
• Grantee: Israel Donizeti de Souza
• Support Opportunities: Scholarships in Brazil - Post-Doctoral
• FAPESP's process: 20/00126-8 - Development of the methods of the microextraction hyphenated with LC-MS/MS or directly to MS/MS for the determination of biomarkers in biological samples of patient or rats with neurodegenerative diseases
• Grantee: Maria Eugênia Queiroz Nassur
• Support Opportunities: Regular Research Grants