Chromatographic studies of unusual on-column degradation of cefaclor observed in the impurity separation by HPLC

J Pharm Biomed Anal. 2019 Nov 30:176:112818. doi: 10.1016/j.jpba.2019.112818. Epub 2019 Aug 19.

Abstract

An unpredictable ghost peak was intermittently observed during the impurity separation of cefaclor and formulation by high performance liquid chromatography (HPLC) with a content from below the reported threshold to approximately 0.3% in different laboratories. Through a series of investigations, the ghost peak was identified as an unusual on-column degradant of cefaclor formed under elevated column temperature but was not an actual sample impurity. The chemical structure of the degradant was determined by spectroscopic methods, including high resolution mass spectrometry (HRMS) and 1H-NMR. Consequently, the unknown peak was identified as a C-4 oxidative decarboxylation analog of cefaclor. The formation mechanism of the analog is proposed, and it is suggested that elevated column temperature during HPLC analysis has a profound effect on the degradation. Dissolved oxygen in the mobile phase may promote the formation of the ghost peak. The degradation can be suppressed by using a column temperature below 30 °C. Moreover, several other prevention measures are suggested based upon the results of the investigation.

Keywords: Cefaclor; Degradation; Ghost peak; HPLC; Impurity; Oxidative decarboxylation.

MeSH terms

  • Anti-Bacterial Agents / analysis*
  • Anti-Bacterial Agents / chemistry
  • Cefaclor / analysis*
  • Cefaclor / chemistry
  • Chromatography, High Pressure Liquid / instrumentation
  • Chromatography, High Pressure Liquid / methods
  • Decarboxylation
  • Drug Compounding / instrumentation
  • Drug Compounding / methods*
  • Drug Compounding / standards
  • Drug Contamination / prevention & control
  • Mass Spectrometry / methods
  • Oxidation-Reduction
  • Proton Magnetic Resonance Spectroscopy
  • Temperature

Substances

  • Anti-Bacterial Agents
  • Cefaclor