Preparation Of Novel Isotope Coding Labeling Reagent And Its Application In Aldehyde Analysis

Aliphatic aldehydes as secondary products from the lipid oxidation of polyunsaturated fattyacid or enzymatic process are ubiquitous in beverage, food, atmosphere, medicine, andbiological liquid. These compounds play an important role in our life and the evaluation of itscontent was paid more and more attention. High performance iquid chromatography-tandemmass spectrometry (HPLC-MS/MS) has been widely used in every field due to its advantages inthe aspect of speed, sensitivity and selectivity. However, HPLC-MS/MS sometimes sufferedfrom the low ionization efficiency and matrix effect (the suppression or enhancement ofionization by the co-eluting compounds), and its feasibility and reliabilities was seriouslychallenged in its applications for determining trace amounts of analytes in complex samples. Thedevelopment of simple and effective way to overcome these problems is of great significance tothe HPLC-MS/MS based analytical methods. Recently, the isotope-coded derivatization reagents,as an alternative approach to introduce internal standards，has been widely used to overcome thematrix effect in HPLC-MS/MS analysis. In this paper, the new isotope-coded reagents weredesigned and synthesized and the isotope-coded derivatization method was established withHPLC-MS/MS.Chapter One: The important of detection for aliphatic aldehydes and the developingprogress and basic theory about high-performance liquid chromatography-tandem massspectrometry were simply presented. The widely used isotope derivatization reagents foraliphatic aldehyde were summarized.Chapter Two: A new pair of derivatization reagents,d0-4-(1-methyl-1H-phenanthro[9,10-d]imidazol-2-yl)phenlamine (d0-MPIA） andd3-4-(1-methyl-1H-phenanthro[9,10-d]imidazol-2-yl)phenlamine (d3-MPIA) have been designedand synthesized. It was successfully used to label aliphatic aldehydes and the aldehydederivatives were analyzed by high-performance liquid chromatography-tandem massspectrometry (HPLC–MS/MS). According to the optimization the derivatization and masscondition, a new pre-column derivatization method for aliphatic aldehydes with HPLC-MS/MSwas established. Comparing these reported method, the new established method exhibitedseveral attractive virtues such as high sensitivity, simple preparation and the reagents economicaland practical. The developed method has been applied to the quantification of aliphaticaldehydes in aquatic products with satisfied results.Chapter Three: A new pair of derivatization reagents, d0-10-methyl-9-oxo-[9,10-d]-dihydro-acridine-2-sulfonyl hydrazine (d0-MASH） and d3-10-methyl-9-oxo-[9,10-d]-dihydro-acridine-2-sulfonyl hydrazine (d3-MASH) have been designed and synthesized. It was successfully used to label aliphatic aldehydes and the aldehydederivatives were analyzed by high-performance liquid chromatography-tandem massspectrometry (HPLC–MS/MS). According to the optimization the derivatization and masscondition, a new pre-column derivatization method for aliphatic aldehydes with HPLC-MS/MSwas established. The developed method has been applied to the quantification of aliphaticaldehydes in wine with satisfied results.Chapter Four: A new pair of derivatization reagents,d0-4-(1-methyl-1H-phenanthro[9,10-d]imidazol-2-yl)phenlhydrazine (d0-MPIB） andd3-4-(1-methyl-1H-phenanthro[9,10-d]imidazol-2-yl)phenlhydrazine (d3-MPIB) have beendesigned and synthesized. It was successfully used to label aliphatic aldehydes and the aldehydederivatives were analyzed by high-performance liquid chromatography-tandem massspectrometry (HPLC–MS/MS). According to the optimization the derivatization and masscondition, a new pre-column derivatization method for aliphatic aldehydes with HPLC-MS/MSwas established. Comparing these reported method, the new established method exhibitedseveral attractive virtues such as high sensitivity, simple preparation and the reagents economicaland practical. The developed method has been applied to the quantification of aliphaticaldehydes in serum with satisfied results.