Enhancement of the capabilities of liquid chromatography–mass spectrometry with derivatization: General principles and applications

Abstract

The integration of liquid chromatography-mass spectrometry (LC-MS) with derivatization is a relatively new and unique strategy that could add value and could enhance the capabilities of LC-MS-based technologies. The derivatization process could be carried out in various analytical steps, for example, sampling, storage, sample preparation, HPLC separation, and MS detection. This review presents an overview of derivatization-based LC-MS strategy over the past 10 years and covers both the general principles and applications in the fields of pharmaceutical and biomedical analysis, biomarker and metabolomic research, environmental analysis, and food-safety evaluation. The underlying mechanisms and theories for derivative reagent selection are summarized and highlighted to guide future studies.

Salivary Hormone Measurement Using LC/MS/MS: Specific and Patient-Friendly Tool for Assessment of Endocrine Function

“…Derivatization is the only technique that directly affects the physicochemical properties of analyte in the LC/MS/MS assay platform and is one of the most effective and reliable methods for overcoming the sensitivity problem. [7][8][9] Another disadvantage of using saliva is that the saliva flow rate may affect the salivary concentrations of some compounds. [4][5][6] If the concentration of the target hormone is dependent on the flow rate, the disease-induced alteration is difficult to find, and as a result, the saliva-based test of the hormone is of little clinical value.…”

Derivatization in liquid chromatography for mass spectrometric detection

“…So far, a number of derivatization reagents for LC/ MS/MS have been reported and they are summarized in several review papers (1)(2)(3)(4)(5)(6)(7). This review presents an overview of the derivatization reagents for LC/ESI-MS/MS that have been applied to low molecular weight compounds in biological samples in recent five years (2008-2012).…”

LC/MS/MS of Steroids Having Vicinal Diol as Electrospray-Active Boronates

“…One of the limitations in ESI-MS/MS for some steroids is the poor ionization and fragmentation behavior, leading to low sensitivity; current MS/MS instruments are extremely sensitive, but still their absolute sensitivity is analyte-dependent. To overcome this limitation, derivatization of the steroids has often been employed in LC/ESI-MS/ MS [4][5][6] ; a suitable derivatization can enhance the ionization efficiency of a poorly ionizable steroid in ESI-MS and assist fragmentation suitable for the selected reaction monitoring (SRM) mode.In most of the derivatization procedures reported until now, an ESI-active (proton-affinitive or permanently-charged) moiety is introduced to the target steroid through a hydroxyor an oxo-group. [4][5][6] These procedures have been proven to be very useful for LC/ESI-MS/MS of some steroids, but the derivatization utilizing a vicinal bifunctional group, such as vicinal diol and vicinal diketone, has not been fully examined.…”

“…To overcome this limitation, derivatization of the steroids has often been employed in LC/ESI-MS/ MS [4][5][6] ; a suitable derivatization can enhance the ionization efficiency of a poorly ionizable steroid in ESI-MS and assist fragmentation suitable for the selected reaction monitoring (SRM) mode.…”

“…One of the limitations in ESI-MS/MS for some steroids is the poor ionization and fragmentation behavior, leading to low sensitivity; current MS/MS instruments are extremely sensitive, but still their absolute sensitivity is analyte-dependent. To overcome this limitation, derivatization of the steroids has often been employed in LC/ESI-MS/ MS [4][5][6] ; a suitable derivatization can enhance the ionization efficiency of a poorly ionizable steroid in ESI-MS and assist fragmentation suitable for the selected reaction monitoring (SRM) mode.…”