CE‐electrochemiluminescence with ionic liquid for the facile separation and determination of diester‐diterpenoid aconitum alkaloids in traditional Chinese herbal medicine

Abstract

A CE-electrochemiluminescence(CE-ECL) detection system, CE/tris(2,2'-bipyridyl) ruthenium(II)ECL with ionic liquid, was established for the determination of diester-diterpenoid aconitum alkaloids (aconitine (AC), mesaconitine (MA) and hypaconitine (HA)) in traditional Chinese herbal medicine. Running buffer containing 25 mM borax-20 mM 1-ethyl-3-methylimidazolium tetrafluoroborate at pH 9.15 was used, which resulted in significant changes in separation and obvious enhancement in ECL intensity for AC, MA and HA with similar structures. End-column detection was achieved in 50 mM phosphate buffer with 5 mM Ru(bpy)₃²⁺ (pH 9.15) at applied detection voltage of 1.20 V when the distance between the Pt working electrode and outlet of capillary (50 cm × 25 μm id) was set at 150 μm. One single quantitative analysis of three alkaloids was achieved at a separation voltage of 15 kV within 10 min. Moreover, two extraction processes (ethanol extraction and ethyl ether extraction after basification) were investigated. The result showed that ethanol extraction process has higher extraction efficiency than ethyl ether extraction process. Under the optimized conditions, the detection limits of AC, MA and HA were 5.62 × 10(-8) , 2.78 × 10(-8) and 3.50 × 10(-9) mol/L (S/N=3), respectively. The method was successfully applied to determine the amounts of AC, MA and HA in the aconitum herbal samples.

Capillary electrophoresis of natural products: 2011–2012

“…When the appropriate derivatizing chemistry is attained, the sensitivity of ELCL detection in CE is on par with that of fluorescence. Tris(2,2′‐bipyridyl)ruthenium(II) (Ru(bpy) 3 2+ ) is the most common luminophore for ELCL . There were five articles pertaining to the use of ELCL as the detection method in CE and the two papers that caught our attention are discussed below.…”

“…The immobilization approach improved the ELCL signals significantly. Second, Bao et al found that addition of ionic liquid, for example, 1‐ethyl‐3‐methylimidazolium tetrafluorborate (EMImBF 4 ), enhanced ELCL sensitivity threefold . The performance of the method in terms of sensitivity, linearity, selectivity, and repeatability for the characterization of alkaloids in the Chinese herbal medicine Radix Aconiti was noteworthy.…”

“…In the next work, CE–ELCL was applied to monitor the concentration of toxic diester‐diterpenoid alkaloids in Radix Aconiti . Lastly, CZE–UV was employed for the simultaneous determination of strychnine, brucine, strychnine N ‐oxide, and brucine N ‐oxide in crude and fermented nux vomica .…”

Identification and Quantification of Aconitines and Colchicine in Serum, Urine, and Plants using MonoSpin C18 and LC-MSMS

“…The intraand inter-assay accuracy and precision (expressed as relative standard deviation, %RSD) evaluated for all compounds were within 96.7-103.2 % and 1.7-11.5 %, respectively. Detection limits and quantitation limits of aconitines and electrophoresis (CE) [6,7], high performance liquid chromatography (HPLC) [8,9], gas chromatography-mass spectrometry (GC-MS) [10,11], and liquid chromatography-tandem mass spectrometry (LC-MS/MS) [12,13] have been reported.…”

The significant inhibition on CYP3A caused by radix Aconiti single herb is not observed in the Wutou decoction: The necessity of combination therapy of radix Aconiti

“…However, WT is also a representative toxic herbal medicine that can cause adverse clinical reactions, such as severe arrhythmia and neurotoxicity if improperly used (Lu et al, 2010). Notably, diester diterpene alkaloids, including aconitine, mesaconitine (MA), and hypaconitine, are the foremost highly toxic pharmacological compounds in WT, and these compounds have a narrow therapeutic index (Bao et al, 2011). According to the theory of TCM and clinical practice, processed WT (PWT) is more often used and prepared as a decoction in combination with other herbs to achieve maximum benefits with minimal side effects.…”