An integrated electrocatalytic nESI-MS platform for quantification of fatty acid isomers directly from untreated biofluids

Abstract

Positional isomers of alkenes are frequently transparent to the mass spectrometer and difficult to provide convincing data to support their presence. This work focuses on the development of a new...

Quantification and molecular imaging of fatty acid isomers from complex biological samples by mass spectrometry

“…The relative standard deviations (RSDs) (n ¼ 3) from all the examined samples were below 5.5%, 3.4%, and 8.9% for FA 16:1 (9Z), FA 18:1 (9Z), and FA 18:1 (11Z), respectively. These data show that the proposed method exhibits higher sensitivity for the detection of FA isomers than recently reported methods, 24,32,33 which attributes to the high labeling efficiency and high yield of diagnostic fragment ions.…”

“…18,23 Another emerging strategy to locate the C]C bond position is implementation of a C]C derivatization procedure prior to CID MS/MS interrogation. C]C bond chemical derivatization methods based on the Paternò-Büchi (PB) reactions, 13,15,24,25 ozonolysis, 26,27 meta-chloroperoxybenzoic acid (m-CPBA)-epoxidation, 28,29 and plasma/electrochemical induced epoxidation, [30][31][32][33] have been utilized to induce structurally informative dissociation of FAs in CID MS/MS in recent years. Additionally, covalent adduct chemical ionization (CACI) GC MS/MS 34 and gas-phase ion/ion reactions 35 have been adopted for the characterization of isomeric FAs.…”

Recent Advances of In‐Source Electrochemical Mass Spectrometry

“…The electrode oxide showed high catalytic activities to the epoxidation of C=C bonds, allowing the differentiation of unsaturated fatty acid isomers in serum of complex matrix. [54] In addition to the electrolysis of metal electrode, nanoESI emitters can be used as an electrochemical microprobe for profiling bulk alloys based on the electro-dissolution of a metal surface. Chen et al conducted the target metal/alloy and the nanoESI electrode by the minute electrolyte at the emitter tip.…”

“…Recently, Badu‐Tawiah group observed in situ oxide formation (IrO 2 ) on the surface of pure Ir and Ru, or Ir/Pt alloy wire via electro‐oxidation in nanoESI. The electrode oxide showed high catalytic activities to the epoxidation of C=C bonds, allowing the differentiation of unsaturated fatty acid isomers in serum of complex matrix [54] …”

Review of Recent Advances in Lipid Analysis of Biological Samples via Ambient Ionization Mass Spectrometry

“…The method shows great potential in point-of-care (POC) clinical diagnosis with fast and high-throughput features [55]. Unlike LTP oxidation, an integrated electrocatalytic nESI-MS platform that utilizes non-inert metal electrodes (e.g., Ir and Ru) has achieved a rapid quantification of FAs isomers from raw serum sample [74].…”