Analysis of curcuminoids and volatile components in 160 batches of turmeric samples in China by high-performance liquid chromatography and gas chromatography mass spectrometry.

Turmeric (Curcuma longa L.) is a popular herbal medicine worldwide. Curcuminoids and volatile constituents are its major bioactive components. To improve the quality control of turmeric, we determined the contents of three main curcuminoids in 160 batches of turmeric samples collected from five major production areas of China by HPLC, and analyzed the volatile components by GC/MS. The results indicated that samples with red cross sections (2.75 ±â€¯0.82 mg/g) contained significantly higher amounts of curcuminoids than samples with yellow sections (1.23 ±â€¯0.60 mg/g) (p < 0.001). This result was consistent with empirical standard of TCM pharmacists. The contents of curcuminoids in samples from Hainan (4.51±0.25%), Guizhou (3.17±0.41%), and Sichuan (2.25±0.54%) were relatively high and consistent. Moreover, the GC/MS profiles of turmeric may be affected by storage and processing. This study sets a good example for comprehensive quality control of herbal medicines.

Rapid quantitation and identification of the chemical constituents in Danhong Injection by liquid chromatography coupled with orbitrap mass spectrometry.

Danhong Injection (DHI) is a Chinese medicine patent drug to treat cardiovascular diseases. It is derived from the herbal medicines Dan-shen and Hong-hua. The bioactive compounds of DHI are polar phenolic acids and flavonoid glycosides. Thus far, the contents of major compounds in DHI are not well understood, and the identification of minor compounds lacks rapid methods. In this work, quantitative and qualitative analyses of DHI compounds were performed using ultra-high performance liquid chromatography coupled with orbitrap mass spectrometry (UHPLC/orbitrap-MS). DHI was separated on an Acquity HSS T3 column (1.8 µm, 100 mm × 2.1 mm) and eluted with acetonitrile-water (containing 0.1% formic acid) to determine the contents of 12 compounds within 6 min. The method was fully validated according to the ICH guidance. To identify the minor compounds, an ion statistics-based strategy was used to dig for 4 filtering ions and 6 diagnostic ions from 22 reference standards. A total of 117 compounds, including 76 phenolic acids, 20 flavonoids, and 21 other compounds were tentatively identified. The poor stability of salvianolic acid A upon storage was also discussed.

Simultaneous Determination and Risk Assessment of Pyrrolizidine Alkaloids in Artemisia capillaris Thunb. by UPLC-MS/MS Together with Chemometrics.

Pyrrolizidine alkaloids (PAs) are natural toxins found in some genera of the family Asteraceae. However, it has not been reported whether PAs are present in the widely used Asteraceae plant Artemisia capillaris Thunb. (A. capillaris). The purpose of this study was to establish a sensitive and rapid UPLC-MS/MS method together with chemometrics analysis for simultaneous determination and risk assessment of PAs in A. capillaris. The developed UPLC-MS/MS method was validated and was confirmed to display desirable high selectivity, precision and accuracy. Risk assessment was conducted according to the European Medicines Agency (EMA) guideline. Chemometrics analysis was performed with hierarchical clustering analysis and principal component analysis to characterize the differences between PAs of A. capillaris. Finally, PAs were found in 29 out of 30 samples and at least two were detected in each sample, besides, more than half of the samples exceeded the EMA baseline. Nevertheless, the chemometrics results suggested that the PAs contents of A. capillaris from different sources varied significantly. The method was successfully applied to the detection and risk evaluation of PAs-containing A. capillaris for the first time. This study should provide a meaningful reference for the rational and safe use of A. capillaris.

[Determination of 125 veterinary drugs residues in eggs by QuEChERS-ultra-high performance liquid chromatography-tandem mass spectrometry].

To establish a method for the determination of veterinary drug residues in eggs by ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS), samples were extracted and purified using frozen lipid filtration combined with the QuEChERS method taking advantage of dispersive solid-phase extraction (DSPE). A total of 125 veterinary drug residues in eggs were analyzed, encompassing 11 classes of drugs (nitroimidazoles, benzimidazoles, sulfonamides, quinolones, macrolides, tetracyclines, androgens, progestational hormones, glucocorticoids, estrogens, and chloramphenicols). The drugs were extracted in acetonitrile/water (70:30, v/v) containing 0.1 mol/L EDTA. The precipitation of lipids and proteins was promoted by performing the extractions at very low temperature (-20℃) for 2 h. Further purification was carried out using dispersive solid-phase extraction (DSPE) followed by dilution of the supernatant. Detection and analysis of veterinary drug residues by UHPLC-MS/MS was conducted and quantified by the external standard method. Our results showed that this method gave good linearity within a certain concentration range (relative coefficient, R2 ≥ 0.99), and the acceptable limits of quantification were determined to be 2.0-60 µg/kg for the 125 veterinary drugs. Good recovery values (60.4%-119.3%) were achieved for all the 125 veterinary drugs with RSD values ranging from 0.3% to 16.1%. This method proved suitable for the rapid determination of veterinary drug residues in eggs with a simple, accurate, and low-cost procedure.

Development and Interlaboratory Study of a Liquid Chromatography Tandem Mass Spectrometric Methodfor the Determination of Multiple Mycotoxins inCereals Using Stable Isotope Dilution.

An efficient, rapid, accurate, and cost-effective method based on stable isotope dilution and LC tandem MS was developed for the determination of multimycotoxins in cereals. The samples were extracted using acetonitrile-water-acetic acid (70 + 29 + 1, v/v/v), followed by dilution and centrifugation without any further cleanup. The mycotoxins were separated on a C18 column. Interference due to matrix effects was efficiently compensated for with [13C]-labeled stable isotope internal standards. The method demonstrated excellent linear relations, with regression coefficients above 0.999. Spiked recoveries at three different concentrations ranged from 80.9 to 115.9%, and RSDs were below 14% for all mycotoxins. The trueness of the method was also verified by participating in two proficiency tests, and satisfactory z-scores (|z| < 1.1) were obtained. In addition, an international interlaboratory study was organized to evaluate the methods. Eight laboratories characterized recovery, repeatability, and reproducibility studies in wheat, maize, and barley. The interlaboratory results were analyzed according to ISO 5725-2. Cochran and Grubbs tests were used to remove outliers. The mean recoveries of all 16 mycotoxins ranged from 87 to 111%. Repeatability, reproducibility, and Horwitz ratio values were 3.5-16.2, 5.4-33.6, and 0.16-1.65%, respectively. The results demonstrate that the method is reliable to determine multimycotoxins in cereals.

Detection of honey adulteration with starch syrup by high performance liquid chromatography.

According to saccharide profile comparison between starch syrups and pure honeys analysed through high performance liquid chromatography (HPLC), a characteristic peak was found at 15.25 min retention time in HPLC chromatogram of syrup, but no peak was observed at the same retention time in chromatogram of pure honeys. This characteristic peak for syrup was identified as an overlapping peak of oligosaccharides with more than 5 degree of polymerisation (DP) based on HPLC chromatogram comparison between starch syrup and a series of standard mono-, di- and oligosaccharides of 3-7 DP. Additionally syrup content correlated linearly with the height of the characteristic peak of syrup under different slope in two ranges 2.5-7.5% and 10-100%, respectively. Therefore, the characteristic peak at 15.25 min retention time can serve as a syrup indicator in HPLC analysis of the adulterated honeys. This new HPLC method for honey adulteration detection was further applied in an authenticity inspection on more than 100 commercial honeys. In addition to the improved accuracy of honey adulteration detection, the proposed HPLC method was simple, low cost and easy practice for honey product quality control by government department considering the popularity of HPLC device and technology.

[Analysis of tartrazine aluminum lake and sunset yellow aluminum lake in foods by capillary zone electrophoresis].

A novel analytical method for tartrazine aluminum lake and sunset yellow aluminum lake using capillary zone electrophoresis (CZE) was studied. The pigments contained in the color lakes were successfully separated from the aluminum matrix in the pre-treatment process, which included the following steps: dissolve the color lakes in 0.1 mol/L H2SO4, adjust the pH of the solution to 5.0, then mix it with the solution of EDTA x 2Na and heat it in a water bath, then use polyamide powder as the stationary phase of solid phase extraction to separate the pigments from the solution, and finally elute the pigments with 0.1 mol/L NaOH. The CZE conditions systematically optimized for tartrazine aluminum lake were: 48.50 cm of a fused silica capillary with 40.00 cm effective length and 50 microm i. d., the temperature controlled at 20.0 degrees C, 29.0 kV applied, HPO4(2-)-PO4(3-) (0.015 mol/L, pH 11.45) solution as running buffer, detection at 263 nm. The conditions for sunset yellow aluminum lake were: the same capillary and temperature, 25.0 kV applied, HPO4(2-)-PO4(3-) (0.025 mol/L, pH 11.45) solution as running buffer, detection at 240 nm. The limits of detection were 0.26 mg/L and 0.27 mg/L, and the linear ranges were 0.53-1.3 x 10(2) mg/L and 0.54-1.4 x 10(2) mg/L for tartrazine aluminum lake and sunset yellow aluminum lake, respectively. The RSDs were 4.3% and 5.7% (run to run, n = 6), 5.6% and 6.0% (day to day, n = 6) for tartrazine aluminum lake and sunset yellow aluminum lake, respectively. Further developments for this method could make it a routinely used method analyzing color lakes in foods.

[Simultaneous determination of 3 benzalkonium chloride homologs in cosmetics by high performance liquid chromatography].

An analytical method based on high performance liquid chromatography with a diode array detector (HPLC-DAD) has been established for the simultaneous determination of 3 benzalkonium chloride homologs (n-C12H25-C9H13NCl, n-C14H29-C9H13NCl, n-C16,H33-C9H13NCl) in cosmetics. The sample was extracted with methanol (including 0.5% formic acid) under ultrasonic operation, the HPLC separation was carried out on a CAPCELL PAK SCX column (250 mm x 4.6 mm, 5 microm), the mobile phases were 40 mmol/L ammonium acetate solution (including 0.1% triethylamine) and acetonitrile with gradient elution, the flow rate was 1.0 mL/min, the detection wavelength was 260 nm, the column temperature was 25 degrees C, and the injection volume was 20 microL. The limit of detection was 50.0 mg/kg and the quantitation limit was 200.0 mg/kg for 3 benzalkonium chloride homologs in cosmetics. The linear plots were obtained between 5.0 mg/L and 3000.0 mg/L. Overall recoveries were between 92.5% and 102.1% with the relative standard deviations (RSDs) between 3.81% and 6.66%. The method is simple, rapid, accurate and suitable for the determination of 3 benzalkonium chloride homologs in cosmetics.

Simultaneous determination of chloramphenicol and aflatoxin M1 residues in milk by triple quadrupole liquid chromatography-tandem mass spectrometry.

A reliable, rapid, and sensitive liquid chromatography-tandem mass spectrometry (LC-MS/MS) method for simultaneous determination of chloramphenicol and aflatoxin M(1) in milk has been developed. This method includes simple extraction of sample with acetonitrile, separation on a MGIII-C(18) column using 5 mM ammonium acetate aqueous solution/methanol (60:40, v/v) as mobile phase, and MS/MS detection using multiple reaction monitoring mode. The method was validated according to Commission Decision 2002/657/EC. The limits of detection (LODs) were 0.05 µg/kg for chloramphenicol and 0.005 µg/kg for aflatoxin M(1.) The limits of quantification (LOQs) were 0.2 µg/kg for chloramphenicol and 0.02 µg/kg for aflatoxin M(1). The recovery values ranged from 88.8% to 100.6%, with relative standard deviation lower than 15% in all cases, when samples were fortified at three different concentrations. The decision limits (CCα) and detection capability (CCß) of the method were also reported. This method has been successfully applied for simultaneous analysis of chloramphenicol and aflatoxin M(1) residues in milk from local supermarkets in China.

[Studies on the chemical constituents from Inula cappa (II)].

OBJECTIVE: To study the chemical constituents of the root of Inula cappa. METHOD: The compounds were isolated and purified by recrystallization and chromatography with silica gel column and Sephadex LH-20 column. Their structures were identified by physico-chemical properties and spectral analysis. RESULTS: Seven compounds were isolated as scopolin (I), octacosanoic acid (II), tritriacontane (III), (2S,3S,4R,8E)-2-[(2'R)-2'-hydroxydocosanosylamino]-octadecane-1,3,4-triol(IV),(2S,3S,4R,8E)-2-[(2'R)-2'-hydroxytricosanosylamino]-octadecane-1,3,4-triol(V), (2S,3S,4R,8E)-2-[(2'R)-2'-hydroxytetracosanosylamino]-octadecane-1,3,4-triol(VI), (2S,3S,4R,8E)-2-[(2'R)-2'-hydroxypentacosanosylamino]-octadecane-1,3,4-triol(VIII), (2S,3S,4R,8E)-2-[(2'R)-2'-hydroxyhexacosanosylamino]-octadecane-1,3,4-triol(VIII). CONCLUSION: All compounds were isolated from Inula cappa for the first time.

[Studies on chemical constituents in fruit of Rubus chingii].

OBJECTIVE: To study the chemical constituents of the fruit of Rubus chingii. METHOD: The compounds were isolated and purified by recrystallization and chromatography with silica gel column and Sephadex LH-20 column. Their structures were identified by physicochemical properties and spectral analysis. RESULT: Eleven compounds were isolated as oleanic acid (I), ursolic acid (II), maslinic acid (III), 2alpha-hydroxyursolic acid (IV), arjunic acid (V), hexacosyl p-coumarate (VI), tiliroside (VII), stearic acid (VIII), lacceroic acid (IX), beta-sitosterol (X), daucosterol (XI). CONCLUSION: Compounds I, II, III, IV, V, VI, VIII, IX, XI were isolated from R. chingii for the first time.