LC—Q—TOF—MS结合PCC氧化反应快速鉴别熊胆粉中的2个新同分异构体(3)
Rapid identification of two new isomers in bear bile powder by
LC-Q-TOF-MS combined with PCC oxidation
JIAN Long-hai， HU Chun， YU Hong， WANG Ke， JI Shen*
(Shanghai Institute for Food and Drug Control， Shanghai 201203， China)
[Abstract] A rapid method of Liquid chromatography-quadrupole time-of-flight mass spectrometry (LC-Q-TOF-MS) combined with pyridinium chlorochromate (PCC) oxidation has been developed to determine chemical structures of two novel isomers in bear bile powder. Derivatives of ursodeoxycholic acid (UDCA) and chenodeoxycholic acid (CDCA) were semi-synthesized by PCC oxidation， then were analyzed by LC-Q-TOF-MS.Separation was carried out on a reverse column with the mobile phase of acetonitrile-0.1% formic acid (45∶55). The data of Q-TOF-MS was acquired by MS， MS/MS， positive and negative modes.Since UDCA and CDCA were stereochemical isomeric at an alcohol position， two oxidation products were same and have been confirmed by LC-Q-TOF-MS.Other two products were also determined based on the PCC oxidation theory. Samples of bear bile powder were dissolved by methanol and measured by LC-Q-TOF-MS.Two unknown peaks were found and identified by matching their retention times and accurate mass spectra ions with PCC oxidation productS.Finally， the structures of two new bile acids in bear bile powder were confirmed as 3α-hydroxy-7-oxo-5β-cholanic acid， 7α-hydroxy-3-oxo-5β-cholanic acid， respectively.
[Key words] bear bile powder； ursodeoxycholic acid； chenodeoxycholic acid； pyridinium chlorochromate； LC-Q-TOF； identification
doi：10.4268/cjcmm20131425, http://www.100md.com(简龙海 胡春 于泓 王柯 季申)
LC-Q-TOF-MS combined with PCC oxidation
JIAN Long-hai， HU Chun， YU Hong， WANG Ke， JI Shen*
(Shanghai Institute for Food and Drug Control， Shanghai 201203， China)
[Abstract] A rapid method of Liquid chromatography-quadrupole time-of-flight mass spectrometry (LC-Q-TOF-MS) combined with pyridinium chlorochromate (PCC) oxidation has been developed to determine chemical structures of two novel isomers in bear bile powder. Derivatives of ursodeoxycholic acid (UDCA) and chenodeoxycholic acid (CDCA) were semi-synthesized by PCC oxidation， then were analyzed by LC-Q-TOF-MS.Separation was carried out on a reverse column with the mobile phase of acetonitrile-0.1% formic acid (45∶55). The data of Q-TOF-MS was acquired by MS， MS/MS， positive and negative modes.Since UDCA and CDCA were stereochemical isomeric at an alcohol position， two oxidation products were same and have been confirmed by LC-Q-TOF-MS.Other two products were also determined based on the PCC oxidation theory. Samples of bear bile powder were dissolved by methanol and measured by LC-Q-TOF-MS.Two unknown peaks were found and identified by matching their retention times and accurate mass spectra ions with PCC oxidation productS.Finally， the structures of two new bile acids in bear bile powder were confirmed as 3α-hydroxy-7-oxo-5β-cholanic acid， 7α-hydroxy-3-oxo-5β-cholanic acid， respectively.
[Key words] bear bile powder； ursodeoxycholic acid； chenodeoxycholic acid； pyridinium chlorochromate； LC-Q-TOF； identification
doi：10.4268/cjcmm20131425, http://www.100md.com(简龙海 胡春 于泓 王柯 季申)