Sulfur dioxide residue in sulfur-fumigated edible herbs: The fewer, the safer?

The residual content of sulfur dioxide is frequently regarded as the exclusive indicator in the safety evaluation of sulfur-fumigated edible herbs. To examine the feasibility of such assessment criteria, here the variations in residual sulfur dioxide content during sulfur-fumigation and the potential mechanisms involved were investigated, using Angelicae Sinensis Radix (ASR) as a model herb. The residual sulfur dioxide content and ten major bioactive components in sulfur-fumigated ASR samples were dynamically examined at 13 successive time points within 72 h sulfur-fumigation. The relationship between the content variation tendency of sulfur dioxide and the ten chemicals was discussed. The results suggested that sulfur dioxide-involved chemical transformation of the original components in ASR might cause large consumption of residual sulfur dioxide during sulfur-fumigation. It implies that without considering the induced chemical transformation of bioactive components, the residual sulfur dioxide content alone might be inadequate to comprehensively evaluate the safety of sulfur-fumigated herbs.

Discovery of characteristic chemical markers for inspecting sulfur-fumigated Radix Angelicae Sinensis by ultra-high performance liquid chromatography-quadrupole/time-of-flight mass spectrometry based metabolomics and chemical profiling approach.

An UHPLC-QTOF-MS/MS based metabolomics and chemical profiling approach was developed to identify the characteristic chemical markers for inspecting sulfur-fumigated Radix Angelicae Sinensis (S-RAS). Two sulfur-containing compounds in S-RAS were discovered and deduced to be (3Z)-6-sulfite-ligustilide and (3E)-6-sulfite-ligustilide. Furthermore, utilizing extraction ion method with the typical ion (m/z 271.06) of (3Z)-6-sulfite-ligustilide/(3E)-6-sulfite-ligustilide as the diagnostic ion, another six sulfur-containing components were determined in S-RAS, and identified as 6, 8-disulfite-ligustilide and 8-sulfite-ligustilide or their isomers. The generation mechanisms of these compounds were proposed as the addition reaction of sulfurous acid with (Z)-ligustilide and/or (E)-ligustilide, two major naturally occurring components in RAS, at the double bonds of C6C7 and C3C8 positions. Using (3Z)-6-sulfite-ligustilide and (3E)-6-sulfite-ligustilide as the chemical markers, fourteen of sixteen batches of commercial RAS samples were inspected to be S-RAS, suggesting that the newly generated sulfur-containing compounds could be used as characteristic chemical markers for inspecting S-RAS among commercial RAS samples.

Effect of different drying methods on the quality of Angelicae Sinensis Radix evaluated through simultaneously determining four types of major bioactive components by high performance liquid chromatography photodiode array detector and ultra-high performance liquid chromatography quadrupole time-of-flight mass spectrometry.

In the present study, the effect of drying methods on the quality of Angelicae Sinensis Radix (DG), was evaluated by newly developed high performance liquid chromatography photodiode array detector (HPLC-DAD) and ultra-high performance liquid chromatography quadrupole time-of-flight mass spectrometry (UHPLC-QTOF-MS/MS). Ten major bioactive components including two phenolic acids, two hydroxyl phthalides, four alkyl phthalides and two phthalide dimers were selected as evaluation chemical markers and the newly-established method was qualitatively and quantitatively validated. DG slices and whole roots dried in shade, sun light, hot air, vacuum, microwave, far infrared ray and combination of microwave and far infrared ray as well as the fresh DG samples were determined by the established methods. DG slices dried in hot air kept the similar chemical composition to that of fresh DG, while DG whole roots dried in vacuum retained highest contents of the major components. Coniferyl ferulate and ligustilide degraded significantly in DG slices dried by microwave, far infrared ray and their combination. The influence of such chemical changes induced by different drying methods on the bioactivities of DG warrants further investigation, so that the optimal drying method can be obtained for the standardization of DG herb.

A high performance liquid chromatography fingerprinting and ultra high performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry chemical profiling approach to rapidly find characteristic chemical markers for quality evaluation of dispensing granules, a case study on Chuanxiong Rhizoma.

A high performance liquid chromatography-photodiode array detector (HPLC-PDA) fingerprinting and ultra high performance liquid chromatography-photodiode array detector coupled with quadrupole time-of-flight mass spectrometry (UHPLC-PDA-QTOF-MS/MS) based chemical profiling approach was developed to rapidly find characteristic chemical markers for quality control of dispensing granules, taking Chuanxiong Rhizoma (CR) as a model herb. Firstly, CR crude drugs, their traditional decoctions and CR dispensing granules were analyzed by HPLC-PDA to rapidly establish the fingerprints and thereby generate the simulative median chromatograms of CR crude drugs, decoctions and dispensing granules, and by comparing the simulative median chromatograms, major characteristic peaks of CR decoctions and dispensing granules could be determined. Secondary, UHPLC-PDA-QTOF-MS/MS was used to identify the major characteristic peaks of CR decoctions and dispensing granules. The identities of three major peaks were elucidated and confirmed to be ferulic acid (1), senkyunolide I (2) and senkyunolide H (3) by comparing the mass/UV spectra and retention times with that of the reference compounds. Thirdly, an HPLC-PDA method was validated to quantify the three characteristic components in commercial CR dispensing granules. The average contents of ferulic acid and senkyunolide H were found to be less than 1.0mg/g, whereas that of senkyunolide I was 4.40mg/g in CR dispensing granules, which indicated that senkyunolide I might be chosen as a suitable quantitative marker, while ferulic acid and senkyunolide H as qualitative markers for the quality evaluation of CR dispensing granules. It is suggested that this newly established approach could be used to practically and rapidly find suitable marker compounds for quality control of dispensing granules derived from other medicinal herbs.