Introduction: Adulterated premixed coffees have turned into an issue in Malaysia lately and have caught the eye of the authorities due to death reports linked to these products. The major cause of this issue is reported that these premixed coffees have passed food inspection test and eventually released to the market for public consumption. These coffees were claimed to be spiked with several sexual enhancers like sildenafil, tadalafil, and vardenafill, which are common drugs used to treat erectile dysfunction. Methods: Chemometrics approach using UV-Vis spectroscopy was developed to detect the selected sexual enhancer drugs found in commercial coffees by employing SIMCA-P software for the multivariate statistical analysis. Seven brands of coffee samples were purchased from local stores, and 30 sachets each were tested, hence totalling to 210 samples. Each sample was named H, J, G, W, N, T, and K, respectively. Results: Three multivariate models were generated, namely principal component analysis (PCA), orthogonal partial least squares discriminant analysis (OPLS-DA), and partial least squares discriminant analysis (PLSDA). OPLS-DA was selected as the best model for the overall results as it displayed minimal discriminate. Sildenafil, tadalafil, and vardenafil were detected in sample H, while vardenafil in brand J, and none in samples G, W, N, T, and K. Conclusion: OPLS-DA analysis showed discrimination for the sexual enhancer drugs in two brands of premixed coffee. The UV-Vis spectroscopy-based chemometrics method proved to be reliable and efficient in determining the selected drugs, as well as in saving time and cost.
Chemometrics

OBJECTIVES: To detect the contents of Tangwei capsule main components with high performance liquid chromatography-quantitative analysis of multicomponents by single marker (HPLC-QAMS) method and to evaluate the quality with chemometrics and entropy weight-technique for order preference by similarity to an ideal solution (EW-TOPSIS). METHODS: A symmetry C₁₈ column and 0.1% formic acid-acetonitrile as mobile phase were used for HPLC of Tangwei capsule. The contents of 3'-hydroxypuerarin, puerarin, 3'-methoxypuerarin, methylnissolin-3-O-glucoside, calycosin, formononetin, rosmarinic acid, salvianolic acid B, dihydrotanshinone Ⅰ, cryptotanshinone, tanshinone Ⅰ, tanshinone ⅡA and cucurbitacin B in 15 batches of Tangwei capsule were determined simultaneously. The quality differences of 15 batches of samples were analyzed by chemometrics and EW-TOPSIS. RESULTS: The HPLC-UV showed that 13 components had good linear relationships in corresponding concentration ranges (r≥0.9991). The relative standard deviations (RSD) of precision, repeatability and stability were all less than 2.00%. The average recovery rates were between 96.86% and 100.13%, and RSD were all less than 2.00%. Cluster analysis showed that 15 batches of samples were clustered into 3 groups. Partial least squares-discriminant analysis showed that salvianolic acid B, formononetin, puerarin, 3'-methoxypuerarin and rosmarinic acid were the main potential markers affecting the quality of Tangwei capsule. EW-TOPSIS analysis showed that the quality of S12-S15 was superior. CONCLUSIONS The analytical method established in this study can be used for the comprehensive evaluation of the quality of Tangwei capsule to provide laboratory support for its quality control and overall evaluation.
Drugs, Chinese Herbal ; Chromatography, High Pressure Liquid/methods* ; Chemometrics ; Entropy

Forsythiae Fructus is the dried fruit of Forsythia suspensa and the volatile compounds are its main bioactive components. According to the different harvest periods, F. suspensa can be divided into Qingqiao(mature F. suspensa) and Laoqiao(ripe F. suspensa). To investigate dynamic changes of volatile components in Qingqiao and Laoqiao samples collected at different periods, the present study extracted and analyzed the total volatile oils in Qingqiao and Laoqiao samples(four harvest periods for Qingqiao and two for Laoqiao) by steam distillation method. The results indicated that the content of volatile oils in F. suspensa samples at different harvest periods was significantly different. The content of volatile oils in Qingqiao samples(except those harvested in the first period) was higher than that of Laoqiao, and the content of volatile oils in both Qingqiao and Laoqiao increased with the harvest period. Furthermore, volatile compounds in F. suspensa were qualitatively analyzed by the gas chromatography-mass spectrometry(GC-MS), and 28 volatile compounds were identified. Chemometrics analyses including principal component analysis(PCA) and partial least squares discriminant analysis(PLS-DA) were further applied to explore differential markers and dynamic changes of volatile components in Qingqiao and Laoqiao samples at different harvest periods. Finally, four volatile compounds, including α-pinene, sabinene, β-pinene, and 4-terpenol were selected as potential differential markers. The relative content of α-pinene and 4-terpenol was consistent with that of total volatile oils in the changing trend.
Chemometrics ; Forsythia ; Fruit ; Gas Chromatography-Mass Spectrometry ; Oils, Volatile

In this study, 280 batches of Zingiberis Rhizoma samples from nine producing areas were analyzed to obtain infrared spectral information based on near-infrared spectroscopy(NIRS). Pluralistic chemometrics such as principal component analysis(PCA), partial least squares-discriminant analysis(PLS-DA), orthogonal partial least squares-discriminant analysis(OPLS-DA), K-nearest neighbors(KNN), support vector machine(SVM), random forest(RF), artificial neural network(ANN), and gradient boosting(GB) were applied for tracing of origins. The results showed that the discriminative accuracy of the spectral preprocessing by standard normal variate transformation coupled with the first derivative was 93.9%, which could be used for the construction of the discrimination model. PCA and PLS-DA score plots showed that samples from Shandong, Sichuan, Yunnan, and Guizhou could be effectively distinguished, but the remaining samples were partially overlapped. As revealed by the analysis results by machine learning algorithms, the AUC values of KNN, SVM, RF, ANN, and GB algorithms were 0.96, 0.99, 0.99, 0.99, and 0.98, respectively, with overall prediction accuracies of 83.3%, 89.3%, 90.5%, 91.7%, and 89.3%. It indicated that the developed model was reliable and the machine learning algorithm combined with NIRS for origin identification was sufficiently feasible. OPLS-DA showed that Zingiberis Rhizoma from Sichuan(genuine producing areas) could be significantly distinguished from other regions, with good discriminative accuracy, suggesting that the NIRS established in this study combined with chemometrics can be used for the identification of Zingiberis Rhizoma from Sichuan. This study established a rapid and nondestructive identification and reliable data analysis method for origin identification of Zingiberis Rhizoma, which is expected to provide a new idea for the origin tracing of Chinese medicinal materials.
Algorithms ; Chemometrics ; China ; Ginger ; Least-Squares Analysis ; Plant Extracts ; Principal Component Analysis ; Support Vector Machine

The present study developed an ultra-fast liquid chromatography coupled with triple quadrupole-linear ion trap composite mass spectrometry(UHPLC-QTRAP-MS) to simultaneously determine the content of potential active components in Scutellariae Barbatae Herba and also to provide a reference approach for screening out the differential quality control components among different batches of Scutellariae Barbatae Herba. Chromatographic separations were conducted on a Thermo Acclaim~(TM) RSLC 120 C_(18) column(3.0 mm×100 mm, 2.2 μm) in a gradient program. The mobile phase consisted of 0.1% aqueous formic acid and acetonitrile, and the column temperature was maintained at 40 ℃. The flow rate was 0.4 mL·min~(-1) and the injection volume was 2 μL. The targeted compounds were monitored in the multiple reaction monitoring(MRM) mode. The acquired data were processed by hierarchical cluster analysis(HCA) and partial least square discriminant analysis(PLS-DA). Sixteen compounds all showed good linear relationship within the corresponding linear ranges and the R~2 values were all higher than 0.993 2. The RSDs of precision, repeatability, and stability were less than or equal to 3.7%. Mean recovery rates were in the range of 95.67% and 104.8% with RSDs≤3.2%. According to HCA and PLS-DA, all samples were clustered into four categories. Scutellarin, acteoside, scutellarein, and scutebarbatine X(VIP>1) were considered as differential chemical markers in the four categories. In conclusion, the developed method can be used for the simulta-neous determination of the multiple components and quality control of Scutellariae Barbatae Herba.
Chemometrics ; Chromatography, High Pressure Liquid/methods* ; Chromatography, Liquid ; Scutellaria ; Tandem Mass Spectrometry/methods*

This research established a high-performance liquid chromatography(HPLC) method for simultaneous determination of isoorientin, orientin, vitexin, and isovitexin in Commelina communis to conduct content difference analysis and quality evaluation of 62 batches of C. communis from different origins. The HPLC content determination was performed on a Dikma Platisil ODS chromatographic column(4.6 mm×250 mm, 5 μm), with acetonitrile-0.1% formic acid(14∶86) as the mobile phase. The detection wavelength was set at 348 nm, the flow rate was 1.0 mL·min~(-1), and the column temperature was 35 ℃. The differences in origins and quality of 62 batches of C. communis were studied by chemometrics. The results showed that the determination of four components mani-fested a good linear relationship in the range of mass concentration(r>0.999 9), and the average recovery rate was 96.17%-103.0%. The relative standard deviations(RSDs) of precision, stability, and repeatability were all less than 2.0%. The content of four components from high to low was isoorientin>isovitexin>orientin>vitexin. Forty-seven batches of C. communis with clear origins were classified into six categories by chemometrics. C. communis from different origins had different qualities. Generally, C. communis from Western China, Central China, and South of China had superior qualities. The HPLC method established in this study is specific, simple, and efficient, which provides references for the comprehensive evaluation of the quality of C. communis. The chemometrics shows that the qualities of C. communis from different origins are largely different. Isoorientin can be used as an index to determine the content of C. communis, and its content limit should be set no less than 0.023%.
Commelina ; Chemometrics ; Drugs, Chinese Herbal/chemistry* ; China ; Chromatography, High Pressure Liquid/methods*

Artemisiae Argyi Folium is commonly used in clinical practice. Artemisiae Verlotori Folium, the dried leaves of Artemisia verlotorum, is often used as a folk substitute for Artemisiae Argyi Folium in Lingnan area. In this study, gas chromatography-triple quadrupole mass spectrometry(GC-MS) was used to detect the volatile oil components of 27 samples of Artemisiae Verlotori Folium and 13 samples of Artemisiae Argyi Folium, and the volatile components were compared between the two species. The internal standard method was combined with multi-reaction monitoring mode(MRM) to determine the content of six major volatile components. Hierarchical clustering analysis(HCA) and orthogonal partial least squares-discriminant analysis(OPLS-DA) were carried out for the content data. The results showed that the Artemisiae Argyi Folium samples had higher content and more abundant volatile oils than the Artemisiae Verlotori Folium samples. Artemisiae Argyi Folium mainly had the components with lower boiling points, while Artemisiae Verlotori Folium mainly had the components with higher boiling points. Terpenoids were the main volatile components in Artemisiae Verlotori Folium(mainly sesquiterpenoids) and Artemisiae Argyi Folium(monoterpenoids). In addition, Artemisiae Argyi Folium had higher content of oxygen-containing derivatives than Artemisiae Verlotori Folium. Furthermore, the stoichiometric analysis showed that the two species could be distinguished by both HCA and OPLS-DA, indicating that the volatile components of the two were significantly different. This study can provide a scientific basis for the quality evaluation and data support for the local rational application of Artemisiae Verlotori Folium in Lingnan.
Gas Chromatography-Mass Spectrometry ; Chemometrics ; Oils, Volatile ; Drugs, Chinese Herbal ; Plant Leaves ; Artemisia

Evaluating the consistency of herb injectable formulations could improve their product quality and clinical safety, particularly concerning the composition and content levels of trace ingredients. Panax notoginseng Saponins Injection (PNSI), widely used in China for treating acute cardiovascular diseases, contains low-abundance (10%-25%) and trace saponins in addition to its five main constituents (notoginsenoside R₁, ginsenoside Rg₁, ginsenoside Re, ginsenoside Rb₁, and ginsenoside Rd). This study aimed to establish a robust analytical method and assess the variability in trace saponin levels within PNSI from different vendors and formulation types. To achieve this, a liquid chromatography-triple quadrupole mass spectrometry (LC-MS/MS) method employing multiple ions monitoring (MIM) was developed. A "post-column valve switching" strategy was implemented to eliminate highly abundant peaks (NR₁, Rg₁, and Re) at 26 min. A total of 51 saponins in PNSI were quantified or relatively quantified using 18 saponin standards, with digoxin as the internal standard. This study evaluated 119 batches of PNSI from seven vendors, revealing significant variability in trace saponin levels among different vendors and formulation types. These findings highlight the importance of consistent content in low-abundance and trace saponins to ensure product control and clinical safety. Standardization of these ingredients is crucial for maintaining the quality and effectiveness of PNSI in treating acute cardiovascular diseases.
Ginsenosides ; Saponins ; Chemometrics ; Panax notoginseng ; Cardiovascular Diseases ; Chromatography, Liquid ; Tandem Mass Spectrometry