Rapid skin biomarker discovery using hydrogel-phase sampling followed by semi-automated liquid-phase re-extraction high-resolution mass spectrometry

Decibel P Elpa; Chamarthi Maheswar Raju; Hsien-Yi Chiu; Shu-Pao Wu; Pawel L Urban

doi:10.1016/j.aca.2023.341028

Rapid skin biomarker discovery using hydrogel-phase sampling followed by semi-automated liquid-phase re-extraction high-resolution mass spectrometry

Anal Chim Acta. 2023 Apr 29:1252:341028. doi: 10.1016/j.aca.2023.341028. Epub 2023 Feb 27.

Authors

Decibel P Elpa¹, Chamarthi Maheswar Raju², Hsien-Yi Chiu³, Shu-Pao Wu⁴, Pawel L Urban⁵

Affiliations

¹ Department of Applied Chemistry, National Yang Ming Chiao Tung University, 1001 University Rd., Hsinchu, 300, Taiwan; Department of Chemistry, National Tsing Hua University, 101, Section 2, Kuang-Fu Rd., Hsinchu, 300044, Taiwan.
² Department of Chemistry, National Tsing Hua University, 101, Section 2, Kuang-Fu Rd., Hsinchu, 300044, Taiwan.
³ Department of Medical Research, National Taiwan University Hospital Hsin-Chu Branch, 25 Jingguo Road, Hsinchu, 300, Taiwan; Department of Dermatology, National Taiwan University Hospital Hsin-Chu Branch, 25 Jingguo Road, Hsinchu, 300, Taiwan; Department of Dermatology, National Taiwan University Hospital, 7 Chung Shan S. Road, Taipei, 100, Taiwan; Department of Dermatology, College of Medicine, National Taiwan University, 1 Jen Ai Road, Taipei, 100, Taiwan. Electronic address: extra.owl0430@yahoo.com.tw.
⁴ Department of Applied Chemistry, National Yang Ming Chiao Tung University, 1001 University Rd., Hsinchu, 300, Taiwan. Electronic address: spwu@nycu.edu.tw.
⁵ Department of Chemistry, National Tsing Hua University, 101, Section 2, Kuang-Fu Rd., Hsinchu, 300044, Taiwan; Frontier Research Center on Fundamental and Applied Sciences of Matters, National Tsing Hua University, 101, Section 2, Kuang-Fu Rd., Hsinchu, 300044, Taiwan. Electronic address: urban@mx.nthu.edu.tw.

PMID: 36935144
DOI: 10.1016/j.aca.2023.341028

Abstract

A facile and rapid skin metabolomics protocol is proposed. The liquid microjunction-surface sampling probe system has been partly automated, and used in conjunction with hydrogel probes for skin metabolite analysis. A control device was built to precisely control the segmented solvent flow and analyte re-extraction into the liquid microjunction. This mode provides rapid online re-extraction of the analytes from hydrogel probes. Humectant was added to the hydrogel, and moist heat treatment was used to make the hydrogel probes rugged for sampling in the clinical setting. The developed method was validated for the analysis of choline - a putative biomarker of psoriasis. A linear relationship over six calibration levels from 3.18 × 10^-5 to 3.18 × 10^-4 mol m^-2 has been obtained. The limit of detection was 6.6 × 10^-6 mol m^-2, while the recoveries range from 92 to 109%. The within-run and between-run precision were evaluated and the coefficients of variation range from 1.84 to 7.13%. Furthermore, the developed method has been used to screen patients (n = 10) and healthy participants (control group; n = 10) for psoriasis-related skin metabolites. Metabolomic profiling of the skin excretion-related signals identified potential biomarkers of psoriasis: choline, pipecolic acid, ornithine, urocanic acid, and methionine.

Keywords: High-resolution mass spectrometry; Liquid microjunction; Metabolic profiling; Skin biomarker; Skin metabolomics; Sweat.

MeSH terms

Biomarkers
Chromatography, High Pressure Liquid / methods
Humans
Hydrogels*
Mass Spectrometry / methods
Psoriasis* / diagnosis
Skin

Substances

Hydrogels
Biomarkers