2-Hydrazinoterephthalic Acid as a Novel Negative-Ion Matrix-Assisted Laser Desorption/Ionization Matrix for Qualitative and Quantitative Matrix-Assisted Laser Desorption/Ionization–Mass Spectrometry Analysis of N-Glycans in Peach Allergy Research

Abstract

Glycans recently attracted considerable attention as the proposal of cross-reactive carbohydrate determinants for food allergy. Matrix-assisted laser desorption/ionization–mass spectrometry (MALDI–MS) is powerful in analyzing biomolecules, while its applications in glycans are still challenging. Herein, a novel reactive matrix-assisted laser desorption/ionization (MALDI) matrix, 2-hydrazinoterephthalic acid, was rationally designed and synthesized. It provides uniform co-crystallization with glycans and only produces deprotonated ions with high intensities in the negative-ion mode. In combination with sinapic acid, a rapid and high-throughput method was established for on-target analysis of glycans with a superior limit of detection at the femtomole level and a good linearity (R 2 > 0.999). Furthermore, the established method was successfully applied to quantify N-glycans in different cultivars and tissues of peach [Prunus persica (L.) Batsch]. Our work suggests the potential role of N-glycans as biomarkers for food-borne allergy and lays a methodological foundation for the elucidation of the possible relationship between carbohydrate epitopes and food allergy.

Mass Spectrometry-Based Biosensing and Biopsy Technology

“…Research on the use of MALDI to measure biomolecules dates back to the 1990s [13] and was awarded the Nobel Prize in 2002. Over the next 30 years, a number of variants of the technique were developed, and they are used in various biochemical analyses [14][15][16]. With the development of laser desorption-based mass spectrometry, researchers have found that the use of microarray biochips can effectively target and detect biomolecules, including DNA, RNA, peptides, sugars, proteins, etc.…”

“…Bogusiewicz et al first used SPME probe MS technology for biopsy sampling of the human brain, followed by metabolic and lipidomic analysis, demonstrating higher concentrations and diversity of metabolites in the white matter [70]. Mendes et al performed direct analysis of fruit and mouse brains using inexpensive and environmentally friendly pencil graphite rods as probes for mass spectrometry biosensing [15]. Cheng et al coupled SPME with nanoESI-MS, achieved by surface-coated acupuncture needles, for the in vivo detection of small molecules, proteins, and peptides in plants [71].…”

“…For example, microfluidic chips are widely used in conjunction with nano ESI to provide excellent performance in reaction monitoring, sensitivity enhancement, biomolecule extraction, etc. [15,[97][98][99][100]. Surface acoustic wave (SAW) devices are used for sample delivery and assisted ionization to enable a real-time, high-throughput quantitative and qualitative analysis of heavy metals and various biomolecules in human serum [101,102].…”