Analysis of 9-fluorenylmethyloxycarbonyl derivatives of catecholamines by high performance liquid chromatography, liquid chromatography/mass spectrometry and tandem mass spectrometry

Abstract

9-Fluorenylmethyloxycarbonyl (FMOC) derivatives of catecholamines, including dopamine (DA; 3,4-dihydroxyphenethylamine), norepinephrine (NE; 2-amino-1-(3,4-dihydroxyphenyl)ethanol) and epinephrine (EPI; 1-phenyl-1-hydroxy-2-methylaminopropane) as well as 3, 4-dihydroxybenzylamine (DHBA) have been analyzed using high performance liquid chromatography coupled to fluorometric detection and atmospheric pressure chemical ionization mass spectrometry at low femtomole levels. Structures of the derivatives have also been characterized by liquid chromatography/atmospheric pressure chemical ionization mass spectrometry and electrospray/tandem mass spectrometry. Protonated molecules of FMOC-DA and FMOC-DHBA as well as [M + H - H(2)O](+) ions of FMOC-NE and FMOC-EPI appear in their conventional mass spectra, and abundant fragments characteristic of catecholamines dominated the spectra. Structurally diagnostic ions using several hundred femtomoles of the FMOC derivatives of catecholamine were observed. Collision-induced dissociation (CID) of electrospray-generated protonated molecules of FMOC-DA and FMOC-DHBA as well as [M + H - H(2)O](+) ions of FMOC-NE and FMOC-EPI produced diagnostic product ion spectra. Liquid chromatography/atmospheric pressure chemical ionization mass spectrometric analysis of the FMOC derivatives of catecholamines and DHBA should prove useful in the separation and characterization of these compounds from biological materials.

The mass spectrometric study on aminohydroxamic acids-based metallacrowns

“…The characteristic losses of 178.08 Da ( z value 2+) and 44.00 Da ( z value 2+) (cumulatively 222.06 Da) correspond to a gradual elimination of dibenzofulvene and carbon dioxide. The fragmentation pathway of the Fmoc group is in good agreement with that previously described in the literature . The further fragmentation results from the elimination of C 3 H 8 N 2 O (88.06 Da; z value 2+).…”

Mass Spectrometry in the Clinical Laboratory

“…For example, GC/MS has been used to analyze dopamine , in research and clinical investigations of Parkinson's disease. Recently, LC-MS methods have been used to analyze neurogenic amines and include thermospray and electrospray MS , applications.…”

Derivatization in Mass Spectrometry—2. Acylation

“…Some acyl derivatives can enhance the separation and characterization of compounds by liquid chromatography/ mass spectrometry (LC/MS). For example, 9-fluorenylmethoxycarbonyl derivatives prepared by reaction with N-(9-fluorenylmethoxycarbonyl)succinimide have been used for the determination of catecholamines in biological materials by LC/atmospheric pressure chemical ionization (APCI)-MS. 52 The APCI mass spectra of the derivatives appear to be rather characteristic and contain [M + H] + ions and some diagnostically important fragments (Figure 7).…”