Journal of Analytical Methods in Chemistry最新文献

Pyrrolizidine alkaloids (PAs) constitute a class of phytotoxin which demonstrates strong hepatotoxicity. In China, many plants containing PAs are used as traditional medicines or medicinal preparations, which could harm human health and safety. Xiaoyao Tablet (XYT) is an antidepressant drug registered in the European Union (EU), Compound Danshen Dropping Pills (CDDP) is a commonly used drug for coronary heart disease, and phase III clinical study is ongoing in the United States. The purpose of this study is to provide data to support the use of Chinese medicine preparations internationally and to establish analytical methods for 32 PAs in XYT and CDDP. The extraction parameters that were optimized include solid-phase extraction (SPE) cartridge, extraction method, and extraction solvent. Then ultra-performance liquid chromatography coupled with triple-quadrupole linear ion-traptandem mass spectrometry (UPLC-MS/MS) was developed to effectively and efficiently quantify the 32 PAs of the XYT and CDDP. The analytical methods for XYT and CDDP were verified respectively. For XYT, the analytical method for 32 PAs was linear, and the correlation coefficient r was greater than 0.994; the recovery (REC%) at 10-2000 μg/kg was 73.3%-118.5%, and the relative standard deviation (RSD%) was 2.1%-15.4%. The CDDP REC% was 71.8%-112.0%, and the RSD% was 2.0%-17.1%. This study provides technical and data support for the registration of Chinese patented medicines in the EU, controls quality and ensures safety, and is committed to the internationalization and standardization of Chinese patented medicines.

Hyperoside is a natural flavonol glycoside, which has antioxidation, antitumor, and anticancer activities together with other healthy effects like improving cardiovascular function, protecting the liver, and regulating the immune system. It is a popular compound used in the traditional Chinese medicine and different studies on hyperoside are present in the literature. However, studies on the metabolism of hyperoside in vivo were not comprehensive. In this study, UPLC-Q-Exactive Orbitrap MS technology was used to establish a rapid and comprehensive analysis strategy to explore the metabolites and metabolic process of hyperoside in rats. The metabolites of hyperoside were systematically identified in rat plasma, urine, and feces. According to the hyperoside standard substance and relevant works of literature, a total of 33 metabolites were identified, including 16 in plasma, 31 in urine, and 14 in feces. Among them, the metabolites quercetin and dihydroquercetin were unambiguously confirmed by comparison with standard substances. In addition, 13 metabolites had not been reported in hyperoside metabolism-related articles at present. The metabolic reactions of hyperoside in vivo were further explored, including phase I metabolism (hydroxylation, dehydroxylation, glycoside hydrolysis, hydrogenation, and hydration) and phase II metabolism (methylation, acetylation, sulfation, and glucuronide conjugation). The fragment ions of hyperoside and its metabolites were usually produced by glucoside bond hydrolysis, the neutral loss of (CO + OH), COH, CO, O, and Retro-Diels Alder (RDA) cleavage. In conclusion, this study comprehensively characterized the metabolism of hyperoside in rats, providing a basis for exploring its various biological activities.

Asari Radix et Rhizoma (AR) is a widely-used Chinese herbal medicine containing multiple active lignans and rare nephrotoxic components-aristolochic acids derivatives (AAs). However, the current quality control method carried out by Chinese Pharmacopoeia has defects in trace AAs detection and insufficient marker ingredients, which is unable to comprehensively evaluate the efficacy and safety of AR. To improve the quality control method of AR, a rapid, sensitive, and reliable chromatographic analytic method based on ultra-high-performance liquid chromatography-triple quadrupole tandem mass spectrometry (UHPLC-QqQ-MS) was established for the simultaneous analysis of multiple AAs and lignans in AR samples. Positive electrospray ionization mode with multiple reaction monitoring (MRM) was applied for the detection of the eight analytes. The method showed available linearity (R ² ≥ 0.991), the limit of quantification (2-5 ng/mL), precision (RSD <8.12%), and accuracy (89.78-112.16%). A total of 6 AAs and 2 lignans were quantified for their content in 15 AR samples. The content of AA-IVa, AA-VIIa, and aristololactam I (AL-I) was much higher than the AA-I controlled by pharmacopoeia. Considering the potential toxicity of AAs, AA-IVa, AA-VIIa, and AL-I should also be controlled in AR. A considerable amount of active sesamin was detected in AR, suggesting that it could be added as a quality marker for the quality control of AR. The newly developed analytical method could be applied for the fast evaluation of toxic AA's content and quality during quality control of AR or preparations containing AR.

The use of doping by athletes to improve performance is prohibited. Therefore, doping testing is an important step to ensure fairness in sports. Doping is gradually metabolized in the body and is therefore difficult to detect immediately by a common method. At the same time, the emergence of new doping agents poses a challenge for highly sensitive detection. Electrochemical sensors are a fast, highly sensitive, and inexpensive analytical detection technology. It provides qualitative and quantitative determination of analytes by altering the electrochemical signal of the analyte or probe at the electrode. In this min-review, we summarized the different electrochemical sensing strategies for sterol doping detection. Some of the representative papers were interpreted in detail. In addition, we compare different sensing strategies.

The HPTLC method is widely used in the field of quality evaluation and component analysis of traditional Chinese medicine (TCM). This work developed an HPTLC method to determine the five effective components of osthole, columbianadin, isoimperatorin, oxypeucedanin, and imperatorin in Angelicae Pubescentis Radix (APR) from twelve different origins, and the quality difference was analyzed by comprehensive factor analysis and cluster analysis. The results showed that the calibration curves of five components exhibited good linearity within the linear ranges (0.8-4.0 μg). The RSD of precision was 1.06%-1.21%, and the repeatability and stability tests were good. The results of cluster analysis showed that the APR from 12 different areas was divided into two categories, and at the same time, it was found that the quality of Dazhou in Sichuan and Huating in Gansu was better than in other areas. In this study, a simple, rapid, and efficient method for quality evaluation of TCM was established by the HPTLC method.

Berberidis Cortex is rich in alkaloids, and many of them have antibacterial, anti-inflammatory, and hypoglycemic activities. However, few research studies have focused on the quantitative analysis of multiple components from Berberidis Cortex. In this study, a new quality evaluation strategy for Berberidis Cortex was developed and validated by high-performance liquid chromatography (HPLC), which involved single marker, fingerprint, and stoichiometric methods. Using berberine hydrochloride as an internal reference, the relative correction factors of palmatine hydrochloride, magnoline, and jatrorrhizine hydrochloride were 2.4537, 0.9783, and 1.0035, respectively, and their durabilities were also well performed. In addition, both methods mentioned above were used to compare the mass fractions of four isoquinoline alkaloids in ten batches of Berberidis Cortex from different origins. These results indicated that the approach applied in this study was accurate and feasible. The fingerprints of these ten batches of Berberidis Cortex were established, and eleven components were identified with the similarity greater than 0.993. Both cluster and principal component analysis were carried out based on the peak area of these components, the results demonstrated that these ten batches of Berberidis Cortex were divided into two groups and the distribution of the medicinal material was basically consistent. Therefore, quantitative analysis of multicomponents by single marker (QAMS) can be widely used in the quality control of Berberidis Cortex as theoretical basis.

An experimental procedure using ¹H NMR was developed and validated to quantify 5-hydroxymethyl-2(5H)-furanone, a valuable chemical synthon ((S)-enantiomer), in a dichloromethane extract of Helleborus lividus subsp. corsicus leaves. This method, using vanillin as the internal standard, exhibited a perfect linearity of measurements (R ² = 1) associated with very good accuracy (relative errors comprised between -1.62% and 4.25%) and precision (reproducibility 30.51 mg ± 0.4%). The limit of detection and the limit of quantitation have been measured at 0.14 mg and 0.59 mg, respectively. The experiment time is very short since a single analysis is at the minute level. 5-Hydroxymethyl-2(5H)-furanone accounted for nearly 85% in the dichloromethane extract of H. lividus subsp. corsicus leaves (1.7% of the mass of fresh leaves). This plant represents an important and natural source of (S)-5-hydroxymethyl-2(5H)-furanone (main enantiomer; determined using a GC chiral analysis).

Color pigments from plant, animal, or mineral sources can be identified, separated, and quantified for various purposes. It is expected that pigments from Beta vulgaris L. peels and pomaces could be used to develop natural dyes that can find applications in areas such as food or textile dyeing industries. This work aimed at identifying and quantifying the pigment in the B. vulgaris L. peels and pomaces extracts as well as validating the method by high-performance liquid chromatography combined with ultraviolet spectroscopy (HPLC-UV) and ultra-high-performance liquid chromatography coupled with triple quadrupole (TSQ) mass spectrometry (UHPLC-MS/MS). Column chromatography was used to isolate compounds after methanolic solvent extraction. Identification and quantification of the pigments in the extract were achieved using reverse-phase HPLC with a UV detector (538 nm). The UHPLC-MS/MS was used for further confirmation of colored compounds in the extract. Method validation included the use of betanin standard (betanidin 5-β-D-glucopyranoside), determination of repeatability (precision), calibration curve linearity, and sensitivity (LOD and LOQ) tests. Betanin was detected in the sample at retention times of 7.699 and 7.71 minutes, respectively, which closely matched the tR (7.60 min) of the standard, according to HPLC-UV and LC-MS/MS data. The average betanin concentration was 3.81 0.31 mg/g of dry weight, according to the HPLC-UV analysis. The LC-MS/MS data revealed the existence of several compounds, including betanin (4.31 ± 2.15 mg/g), isobetanin (1.85 ± 2.20 mg/g), 2, 17-bidecarboxy-neobetanin (0.71 ± 0.02 mg/g), betanidin (0.71 ± 0.03 mg/g), 2-O-glucosyl-betanin (0.40 ± 0.10 mg/g), and isobetanidin (0.36 ± 1.26 mg/g), among other compounds whose yields were too low. In conclusion, the peels and pomaces of B. vulgaris L. can be a useful source for the extraction of a red dye for use in coloring, such as the dyeing of textile substrates.

Background: Naolingsu capsule (NLSC) is a well-known traditional Chinese medicine (TCM) prescription in China. It is widely used to treat neurasthenia, insomnia, cardiovascular and cerebrovascular disease, and other diseases. However, its inalienable chemical groups have not been carried out.

Methods: We first established the nontargeted investigation based on fingerprinting coupled with UHPLC-Q/TOF-MS/MS. Second, the quantitative methods based on HPLC-DAD and LC-MS/MS were connected to the synchronous quantitative assurance of eleven and fourteen marker compounds. Finally, the quantitative information was processed with SIMCA-P for differentiating the distinctive bunches of samples to screen the foremost appropriate chemical markers.

Results: The similarity of HPLC fingerprints of 24 batches of NLSC samples was 0.645-0.992. In total, 37 flavonoids, 21 organic acids, 22 lignans, 13 saponins, and 20 other compounds were recognized in NLSC by the UHPLC-Q/TOF-MS/MS method. The quantitative determination was approved for linearity, discovery limits, accuracy, repeatability, soundness, and precision. Principal component analysis (PCA) and partial least squares discriminant analysis (PLS-DA) models accomplished the great classification of the samples from the five enterprises, respectively. Rehmannioside D (RD), methylophiopogonanone A (MPA), 3,6'-disinapoyl sucrose (DS), schisandrin B (SSB), epimedin C (EC), icariin (ICA), and jujuboside B (JB) were considered as the potential chemical markers for NLSC quality control.

Conclusion: The experimental results illustrated that the combinative strategy was valuable for quick pharmaceutical quality assessment, which can potentially differentiate the origin, decide the realness, and assess the overall quality of the formulation.

A method based on elemental fingerprint, stable isotopic analysis and combined with chemometrics was proposed to trace the geographical origins of Licorice (Glycyrrhiza uralensis Fisch) from 37 producing areas. For elemental fingerprint, the levels of 15 elements, including Ca, Cu, Mg, Pb, Zn, Sr, Mn, Se, Cd, Fe, Na, Al, Cr, Co, and K, were analyzed by inductively coupled plasma atomic emission spectrometry (ICP-AES). Three stable isotopes, including δ ¹³C, δ ¹⁵N, and δ ¹⁸O, were measured using an isotope-ratio mass spectrometer (IRMS). For fine classification, three multiclass strategies, including the traditional one-versus-rest (OVR) and one-versus-one (OVO) strategies and a new ensemble strategy (ES), were combined with two binary classifiers, partial least squares discriminant analysis (PLSDA) and least squares support vector machines (LS-SVM). As a result, ES-PLSDA and ES-LS-SVM achieved 0.929 and 0.921 classification accuracy of GUF samples from the 37 origins. The results show that element fingerprint and stable isotope combined with chemometrics is an effective method for GUF traceability and provides a new idea for the geographical traceability of Chinese herbal medicine.