Simultaneous quantification of six indicator compounds in Wen-Qing-Yin by high-performance liquid chromatography-diode array detection.

A simple gradient high-performance liquid chromatography with diode array detection (HPLC-DAD) method was used to simultaneously to analyze characteristics of six indicator compounds in the traditional Chinese medicine (TCM) formulation Wen-Qing-Yin (WQY). Separate optimization was performed using a Cosmosil C18 column gradient method with 0.1% formic acid in both mobile phases of aqueous and acetonitrile (ACN), at a flow rate, detection wavelength, and sample volume of 1.8 mL/min, 268 nm, and 10 µL, respectively. The linear regression of six active compounds berberine (BER), baicalin (BAI), ferulic acid (FER), geniposide (GEN), hydorxymethoxylfurfural (HMF), and paeoniflorin (PAE) was produced at the concentration range of 10-2000 µg/mL. The method validation revealed an acceptable precision (intra- and inter-day precision < 3.39% and 4.11%, respectively) and recovery (85.60-110.45% and 86.58-110.90%), a recovery range of 86.61-109.42%, and sensitivity (limit of detection [LOD] and limit of quantification [LOQ] values were in the range of 0.03-3.13, and 0.08-9.38 µg/mL, respectively) while the calibration curves were linear with a correlation coefficient (R2) ranging from 0.9966 to 0.9989. The qualitative and quantitative analyses were performed by direct comparison of the peaks of the WCY extract to retention times of reference standards. Additionally, principal component analysis (PCA) successfully discriminated four purchased commercial samples of all six indicator constituents, and the present results indicate their comprehensive potential usefulness for qualitative and quantitative analyses of the WQY decoction and its commercial products.

Identification of a new type tadalafil analogue in a supplement product.

A novel compound structurally similar to tadalafil was found in a dietary supplement by adulterants screening test and isolated by column chromatography. After analysis by accurate mass, nuclear magnetic resonance (NMR) and X-ray, the structure of this novel tadalafil analogue was determined as (5R, 16R)-5-(1,3-benzodioxol-5-yl)-2- (3-ethypentan-3-yl)-15,16-dihydro(1H-imidazo[1,5-a]pyrido)[3,4-b]indol-1,3-dion.

Isolation and identification of a novel sildenafil analogue adulterant in herbal products.

A novel sildenafil analogue found in herbal products by a routine drug-adulteration screening programme was isolated by column chromatography. On the basis of extensive 1D- and 2D-nuclear magnetic resonance (NMR) spectroscopy and mass spectral analysis, the structure of a new compound YJ-07 was established as 1-[4-ethoxy-3-(6,7-dihydro-1-methyl-7-oxo-3-propyl-1H-pyrazolo[4,3-d]pyrimidin-5-yl) benzenesulfonamide. It common name is aminosildenafil.

Identification of a new sildenafil analogue adulterant, desethylcarbodenafil, in a herbal supplement.

In a maca-containing herbal supplement claimed to remedy erectile dysfunction, a new sildenafil analogue was found using adulterant screening with TLC, GC-MS and LC-MS/MS. This compound was isolated by column chromatography and HPLC, and identified by extensive 1D- and 2D-NMR and mass spectral analyses. The structure of this new compound was established as 5-[2-ethoxy-5-(piperazine-1-carbonyl) phenyl]-1-methyl-3-propyl-1,6-dihydro-pyrazolo[4,3-d]pyrimidin-7-one, and was named desethylcarbodenafil.

Identification of a new tadalafil analogue, dipropylaminopretadalafil, in a dietary supplement.

A novel tadalafil analogue in a dietary supplement was found by drug-adulteration screening and isolated by column chromatography and HPLC. Based on extensive 1D- and 2D-NMR and mass spectral analyses, the structure of this new compound was determined as 2-(N,N-dipropyl acetyl) 3-methyl 1-(benzo[d][1,3]dioxol-5-yl)-3,4-dihydro-1H-pyrido[3,4-b]indole-3-carboxylate - its common name is dipropylaminopretadalafil.

Differentiating parts of Cinnamomum cassia using LC-qTOF-MS in conjunction with principal component analysis.

Cinnamon bark (Rou Gui in Chinese), cinnamon twig (Gui Zhi) and shaved cinnamon bark (Gui Sin) have been widely used as spices and in traditional Chinese medicine since ancient times. On-going issues related to quality and authenticity necessitate the development of analytical methods capable of providing an objective evaluation of samples. In this study, chemical fingerprints of cinnamon bark, cinnamon twigs and shaved cinnamon bark were established using liquid chromatography quadruple time-of-flight mass spectrometry in conjunction with principal component analysis (PCA). From 125 samples of cinnamon, we identified the following eight compounds and their the detection ratios: coumarin, cinnamaldehyde, cinnamyl alcohol, cinnamic acid, 2-hydroxycinnamaldehyde, 2-hydroxycinnamic acid, 2-methoxycinnamaldehyde and 4-methoxycinnamaldehyde. Of these, 4-methoxycinnamaldehyde presented the largest variations in detection ratio, making up 64.0, 97.4 and 50.0% in cinnamon bark, cinnamon twig, and shaved cinnamon bark, respectively. The quantities of cinnamyl alcohol, coumarin and cinnamaldehyde also varied between the three parts of the plant. Chemical fingerprints of the three cinnamon samples were established using principal component analysis, the results of which indicate that cinnamon bark and shaved cinnamon bark could be easily differentiated, despite a marked similarity in outward appearance. Cinnamon twig was also shown to depart from the other clusters. The proposed method provides a fast and efficient means of identifying cinnamon herbs for quality control purposes. Copyright © 2016 John Wiley & Sons, Ltd.

Separation and identification of a novel tadalafil analogue adulterant in a dietary supplement.

A novel tadalafil analogue found in a dietary supplement by routine drug-adulteration screening was isolated by column chromatography and HPLC. On the basis of extensive 1D- and 2D-nuclear magnetic resonance (NMR), infrared (IR) and mass spectral analyses, the structure of the new compound YJ-02 was established as 6-(benzo[d][1,3]dioxol-5-yl)-2,3,6,7,12,12a-hexahydro-2-(1E,2E)-3-phenylallylidene)amino)pyrazino[1',2':1,6]pyrido[3,4-b]indole-1,4-dione. Its common name is N-phenylpropenyltadalafil.

Identification and quantification of Cu-chlorophyll adulteration of edible oils.

Cu-pyropheophytin a, the major Cu-pigment of Cu-chlorophyll, was determined in edible oil by high-resolution mass spectrometry with a high-performance liquid chromatography-quadrupole (HPLC-Q)-Orbitrap system and by HPLC coupled with a photodiode-array detector. Respective limit of detection and limit of quantification levels of 0.02 µg/g and 0.05 µg/g were obtained. Twenty-nine commercial oil products marked as olive oil, grapeseed oil and blended oil, all sourced directly from a food company that committed adulteration with Cu-chlorophyll, were investigated. In this company, four green dyes illegally used in oils were seized during factory investigation by the health authorities. The food additive Cu-pyropheophytin a was found in all confiscated samples in concentrations between 0.02 and 0.39 µg/g. Survey results of another 235 commercial oil samples manufactured from other companies, including olive pomace oil, extra virgin olive oil, olive oil, grapeseed oil and blended oil, indicated high positive incidences of 63%, 39%, 44%, 97% and 8%, respectively, with a concentration range between 0.02 and 0.54 µg/g. High Cu-chlorophyll concentrations are indications for fraudulent adulteration of oils.