Simultaneous Profiling of Lysoglycerophospholipids in Rice (Oryza sativa L.) Using Direct Infusion-Tandem Mass Spectrometry with Multiple Reaction Monitoring.

White rice is the final product after the hull and bran layers have been removed during the milling process. Although lysoglycerophospholipids (lysoGPLs) only occupy a small proportion in white rice, they are essential for evaluating rice authenticity and quality. In this study, we developed a high-throughput and targeted lipidomics approach that involved direct infusion-tandem mass spectrometry with multiple reaction monitoring to simultaneously profile lysoGPLs in white rice. The method is capable of characterizing 17 lysoGPLs within 1 min. In addition, unsupervised and supervised analyses exhibited a considerably large diversity of lysoGPL concentrations in white rice from different origins. In particular, a classification model was built using identified lysoGPLs that can differentiate white rice from Korea, China, and Japan. Among the discriminatory lysoGPLs, for the lysoPE(16:0) and lysoPE(18:2) compositions, there were relatively small within-group variations, and they were considerably different among the three countries. In conclusion, our proposed method provides a rapid, high-throughput, and comprehensive format for profiling lysoGPLs in rice samples.

[1]  Oliver Fiehn,et al.  Mass-spectrometry-based metabolomics: limitations and recommendations for future progress with particular focus on nutrition research , 2009, Metabolomics.

[2]  G. King,et al.  Phospholipids in rice: significance in grain quality and health benefits: a review. , 2013, Food chemistry.

[3]  T. Rose,et al.  Improving phosphorus efficiency in cereal crops: Is breeding for reduced grain phosphorus concentration part of the solution? , 2013, Front. Plant Sci..

[4]  Ju Yong Lee,et al.  Simultaneous profiling of lysophospholipids and phospholipids from human plasma by nanoflow liquid chromatography-tandem mass spectrometry , 2011, Analytical and bioanalytical chemistry.

[5]  B. O. Juliano,et al.  Starch Lipids and Their Effect on Rice Starch Properties , 1980 .

[6]  E. Wat,et al.  Dietary phospholipids, hepatic lipid metabolism and cardiovascular disease , 2008, Current opinion in lipidology.

[7]  Xianlin Han,et al.  Systematic analysis of choline-containing phospholipids using multi-dimensional mass spectrometry-based shotgun lipidomics. , 2009, Journal of chromatography. B, Analytical technologies in the biomedical and life sciences.

[8]  Graham J King,et al.  Determination of starch lysophospholipids in rice using liquid chromatography-mass spectrometry (LC-MS). , 2014, Journal of agricultural and food chemistry.

[9]  Xin Lu,et al.  Metabolic profiling based on LC/MS to evaluate unintended effects of transgenic rice with cry1Ac and sck genes , 2012, Plant Molecular Biology.

[10]  U. Massing,et al.  Health effects of dietary phospholipids , 2012, Lipids in Health and Disease.

[11]  Douglas N Rutledge,et al.  PLS/OPLS models in metabolomics: the impact of permutation of dataset rows on the K-fold cross-validation quality parameters. , 2015, Molecular bioSystems.

[12]  Martin Trötzmüller,et al.  Mass Spectrometry Based Lipidomics: An Overview of Technological Platforms , 2012, Metabolites.

[13]  Richard D. Smith,et al.  Advancing the sensitivity of selected reaction monitoring‐based targeted quantitative proteomics , 2012, Proteomics.

[14]  Xianlin Han,et al.  Multi-dimensional mass spectrometry-based shotgun lipidomics and novel strategies for lipidomic analyses. , 2012, Mass spectrometry reviews.

[15]  B. O. Juliano,et al.  Lipids in developing and mature rice grain , 1980 .

[16]  P. van Hoogevest,et al.  The use of natural and synthetic phospholipids as pharmaceutical excipients , 2014, European journal of lipid science and technology : EJLST.

[17]  R. Abagyan,et al.  METLIN: A Metabolite Mass Spectral Database , 2005, Therapeutic drug monitoring.

[18]  S. Ito,et al.  Internal Lipid in Rice Starch , 1979 .

[19]  David S. Wishart,et al.  MetaboAnalyst 3.0—making metabolomics more meaningful , 2015, Nucleic Acids Res..

[20]  H. Trindade,et al.  Rice antioxidants: phenolic acids, flavonoids, anthocyanins, proanthocyanidins, tocopherols, tocotrienols, γ-oryzanol, and phytic acid , 2014, Food science & nutrition.

[21]  Age K. Smilde,et al.  UvA-DARE ( Digital Academic Repository ) Assessment of PLSDA cross validation , 2008 .

[22]  Stefan R Bornstein,et al.  A novel informatics concept for high-throughput shotgun lipidomics based on the molecular fragmentation query language , 2011, Genome Biology.

[23]  Y. Yoshimura,et al.  Distribution of lysophosphatidylcholine in the endosperm of Oryza sativa rice. , 2014, Rapid communications in mass spectrometry : RCM.

[24]  Oliver Fiehn,et al.  LipidBlast - in-silico tandem mass spectrometry database for lipid identification , 2013, Nature Methods.

[25]  Jianguo Xia,et al.  Using MetaboAnalyst 3.0 for Comprehensive Metabolomics Data Analysis , 2016, Current protocols in bioinformatics.

[26]  Christer S. Ejsing,et al.  Lipid profiling by multiple precursor and neutral loss scanning driven by the data-dependent acquisition. , 2006, Analytical chemistry.

[27]  S. Ryu,et al.  Inhibition of phospholipase D by lysophosphatidylethanolamine, a lipid-derived senescence retardant. , 1997, Proceedings of the National Academy of Sciences of the United States of America.

[28]  J. Brouwers Liquid chromatographic-mass spectrometric analysis of phospholipids. Chromatography, ionization and quantification. , 2011, Biochimica et biophysica acta.