高等学校化学学报2026，Vol.47Issue(2)：36-46,11.DOI:10.7503/cjcu20250195
在线固相萃取净化-液相色谱-高分辨质谱法测定海洋沉积物中的L型和D型氨基酸
Determination of L-and D-Amino Acids in Marine Sediments Using Online Solid-phase Extraction Cleanup Coupled with Liquid Chromatography-high-resolution Mass Spectrometry
摘要
Abstract
Amino acids(both L-and D-enantiomers)serve as crucial biomarkers for indicating the sources of organic matter and diagenetic processes within marine sedimentary environments.Consequently,developing methods for their precise detection in marine sediments is of significant importance.This study established a novel method for the simultaneous determination of 17 L-amino acids and 7 D-amino acids in marine sediments using online solid-phase extraction(SPE)coupled with liquid chromatography-time-of-flight mass spectrometry(LC-TOF/MS).A C18 guard column served as the online SPE column,while an ultra-high-performance reversed-phase C18 analytical column(1.8 µm particle size)was employed for separation.Utilizing dual acidic and alkaline mobile phase systems,efficient separation of various L-and D-amino acids was achieved.Detection was performed online using high-resolution electrospray ionization TOF/MS in full scan mode.The results demonstrate that accurate quantification of various L-and D-amino acids can be achieved by direct injection analysis using online SPE-LC-TOF/MS following hydrochloric acid hydrolysis of marine sediment samples,5-fold dilution,and derivatization.The spiked recoveries for the various amino acids ranged from 66.1%to 106.8%,with relative standard deviations(RSD)between 2.40%and 12.3%.The method exhibited wide linear ranges,and all correlation coefficients(R²)were greater than 0.990.Compared to conventional liquid chromatography methods,this approach requires only a small sediment sample amount(0.01-0.10 g),making it an effective method for detecting chiral amino acid biomarkers in deep-sea and oceanic hydrothermal vent sediments.Applying this method to analyze L-and D-amino acids in surface sediments from the Western Indian Ocean revealed the presence of all 17 L-amino acids and 7 D-amino acids in all samples,with total concentrations ranging from 1.69 to 19.30 µmol/g(dry weight).Furthermore,the analysis indicated that submarine hydrothermal activity significantly influences the cycling of organic carbon and nitrogen in the deep-sea sedimentary environment.关键词
在线固相萃取/高分辨质谱/海洋沉积物/D-氨基酸/深海热液喷口Key words
Online solid phase extraction/High resolution mass spectrometry/Marine sediment/D-amino acid/Deep-sea hydrothermal vent分类
化学化工引用本文复制引用
何秀平,李芳,陈军辉,辛明,王保栋..在线固相萃取净化-液相色谱-高分辨质谱法测定海洋沉积物中的L型和D型氨基酸[J].高等学校化学学报,2026,47(2):36-46,11.基金项目
全球变化与海气相互作用(二期)专项基金(批准号:GASI-01-ATP-STwin)资助. Supported by the Fund of the Global Change and Air-Sea Interaction II,China(No.GASI-01-ATP-STwin). （二期）
