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Traditional Chinese medicine (TCM) is the treasure of China, and the quality control of TCM is of crucial importance. In recent years, with the quick rise of artificial intelligence (AI) and the rapid development of hyperspectral imaging (HSI) technology, the combination of the two has been widely used in the quality evaluation of TCM. Machine learning (ML) is the core wisdom of AI, and its progress in rapid analysis and higher accuracy improves the potential of applying HSI to the field of TCM. This article reviewed five aspects of ML applied to hyperspectral data analysis of TCM: partition of data set, data preprocessing, data dimension reduction, qualitative or quantitative models, and model performance measurement. The different algorithms proposed by researchers for quality assessment of TCM were also compared. Finally, the challenges in the analysis of hyperspectral images for TCM were summarized, and the future works were prospected. [ABSTRACT FROM AUTHOR]

Traditional Chinese Medicine (TCM) formulations often contain a complex mixture of compounds, making it challenging to evaluate their quality. Buzhong Yiqi Oral Liquid (BYOL), a well-known TCM formulation, has been used to treat gastrointestinal diseases and fatigue for a long time. However, the effective substances for its therapeutic effects remain unclear. This study aimed to establish a novel quality control approach for BYOL using a multidimensional feature network to identify quality markers (Q-markers). The multidimensional characteristic network was constructed by a "Spider-Web" model, including the compatibility of ingredients, traceability of compounds from raw materials to the final product, effectiveness, measurability, and stability. Multivariate statistical analysis was applied to quantify the individual dimensions of the feature network, and candidate compounds were identified based on regression regions within the network. Using the multidimensional characteristic network, 12 components were identified as key Q-markers for BYOL, consisting of calycosin-7-O-β-D-glucoside, formononetin, astragaloside IV, liquiritin, quercetin, hesperidin, glycyrrhizic acid, isorhamnetin, liquiritin apioside, hesperidin, luteolin, and nobiletin. The identified Q-markers offered valuable insights for future research on medicinal substances and quality control of BYOL. [ABSTRACT FROM AUTHOR]

Introduction: Nonstationary, nonlinear mass transfer in traditional Chinese medicine (TCM) extraction poses challenges to correlating process characteristics with quality parameters, particularly in defining clear parameter ranges for the process. Objectives: The aim of the study was to provide a solution for quality consistency analysis in TCM preparation processes. Materials and methods: Salvia miltiorrhiza was taken as an example for 15 batches of standard decoction. Using aqueous extract, alcoholic extract, and the content of salvianolic acid B as herb material key quality attributes, multiple nonlinear regression, Gaussian process regression, and artificial neural network models were employed to predict the key quality attributes including the paste yield, the content of salvianolic acid B, and the transfer rate. The evaluation criteria were root mean square error, mean absolute percentage error, and R2. Results: The Gaussian process regression model had the best prediction effect on the paste yield, the content of salvianolic acid B, and the transfer rate, with R2 being 0.918, 0.934, and 0.919, respectively. Utilizing Gaussian process regression model confidence intervals, along with Shewhart control and intervals optimized through process capability index analysis, the quality control range of the standard decoction was determined as follows: paste yield, 25.14%–33.19%; salvianolic acid B content, 2.62%–4.78%; and transfer rate, 56.88%–64.80%. Conclusion: This study combined the preparation process of standard decoction with the Gaussian process regression model, accurately predicted the key quality attributes, and determined the quality parameter range by using process analysis tools, providing a new idea for the quality consistency standard of TCM processes. A machine learning strategy forecasts correlations between raw materials and intermediates, integrating process capability analysis to define quality parameters range, offering an innovative solution for TCM process quality analysis. [ABSTRACT FROM AUTHOR]

Red ginseng is widely used in food and pharmaceuticals due to its significant nutritional value. However, during the processing and storage of red ginseng, it is susceptible to grow mold and produce mycotoxins, generating security issues. This study proposes a novel approach using hyperspectral imaging technology and a 1D-convolutional neural network-residual-bidirectional-long short-term memory attention mechanism (1DCNN-ResBiLSTM-Attention) for pixel-level mycotoxin recognition in red ginseng. The "Red Ginseng-Mycotoxin" (R-M) dataset is established, and optimal parameters for 1D-CNN, residual bidirectional long short-term memory (ResBiLSTM), and 1DCNN-ResBiLSTM-Attention models are determined. The models achieved testing accuracies of 98.75%, 99.03%, and 99.17%, respectively. To simulate real detection scenarios with potential interfering impurities during the sampling process, a "Red Ginseng-Mycotoxin-Interfering Impurities" (R-M-I) dataset was created. The testing accuracy of the 1DCNN-ResBiLSTM-Attention model reached 96.39%, and it successfully predicted pixel-wise classification for other unknown samples. This study introduces a novel method for real-time mycotoxin monitoring in traditional Chinese medicine, with important implications for the on-site quality control of herbal materials. [ABSTRACT FROM AUTHOR]

Radix glycyrrhizae (licorice) is extensively employed in traditional Chinese medicine, and serves as a crucial raw material in industries such as food and cosmetics. The quality of licorice from different origins varies greatly, so classification of its geographical origin is particularly important. This study proposes a technique for fine structure recognition and segmentation of hyperspectral images of licorice using deep learning U-Net neural networks to segment the tissue structure patterns (phloem, xylem, and pith). Firstly, the three partitions were separately labeled using the Labelme tool, which was utilized to train the U-Net model. Secondly, the obtained optimal U-Net model was applied to predict three partitions of all samples. Lastly, various machine learning models (LDA, SVM, and PLS-DA) were trained based on segmented hyperspectral data. In addition, a threshold method and a circumcircle method were applied to segment licorice hyperspectral images for comparison. The results revealed that compared with the threshold segmentation method (which yielded SVM classifier accuracies of 99.17%, 91.15%, and 92.50% on the training set, validation set, and test set, respectively), the U-Net segmentation method significantly enhanced the accuracy of origin classification (99.06%, 94.72% and 96.07%). Conversely, the circumcircle segmentation method did not effectively improve the accuracy of origin classification (99.65%, 91.16% and 92.13%). By integrating Raman imaging of licorice, it can be inferred that the U-Net model, designed for region segmentation based on the inherent tissue structure of licorice, can effectively improve the accuracy origin classification, which has positive significance in the development of intelligence and information technology of Chinese medicine quality control. [ABSTRACT FROM AUTHOR]

There has been an increasing demand for rapid and sensitive techniques for the detection of heavy metal ions that are harmful to the human body in traditional Chinese medicine (TCM). However, the complex chemical composition of TCM makes the quantitative detection of heavy metal ions difficult. In this study, the magnetic Fe3O4@SiO2@AuNPs nanoparticles combined with a probe molecule DMcT were used for the specific enrichment and detection of Hg2+ in the complex system of licorice. The core of Fe3O4 was bonded with SiO2 to increase its stability. A layer of AuNPs was deposited to produce a "core–shell" Raman substrate with high surface-enhanced Raman spectroscopy (SERS) activity, which was surface modified by DMcT probe molecules with sulfhydryl groups. In the presence of Hg2+, Hg2+ binds to N on the amino group of DMcT to form N-Hg2+-N complexes, which induces Fe3O4@SiO2@AuNPs-DMcT clustering to enhance SERS signal. The Raman probe molecule DMcT showed an excellent linear relationship (R2 = 0.9709) between the SERS signal at 1416 cm−1 and the Hg2+ concentration (0.5~100 ng/mL). This method achieved a good recovery (89.10~111.00%) for the practical application of detection of Hg2+ in licorice extracts. The results demonstrated that the functional Fe3O4@SiO2@AuNPs-DMcT performed effective enrichment and showed high sensitivity and accurate detection of heavy metal ions from the analytes. [ABSTRACT FROM AUTHOR]

A practical, sodium trifluoromethanesulfinate‐mediated C3‐H fluoroalkoxylation of quinoxalinones with fluoroalkyl alcohols under transition‐metal‐ and additives‐free conditions had been developed, exhibitting high‐efficiency and comprehensive functional group tolerance. Various quinoxalinones could undergo this transformation smoothly and provide the corresponding products in good to excellent yields. [ABSTRACT FROM AUTHOR]

Semen of Cuscuta chinensis has been reported to have an anti‐osteoporosis effect, however, the components which account for the anti‐osteoporosis effect have not been clarified. In this work we propose a biochemometrics strategy that integrates quantitation, anti‐osteoporosis evaluation in zebrafish, and grey relationship analysis for the identification of anti‐osteoporosis components from the semen of Cuscuta chinensis. In the beginning, a precise and accurate liquid chromatography‐tandem mass spectrometry method was established for simultaneous quantitation of seven major components in crude and salt‐processed Cuscuta chinensis. The mode of multiple reaction monitoring was used. Chloramphenicol was selected as the internal standard. The method showed good linearity and repeatability. The recovery rates of each component ranged from 95.4 to 103.9%. The precisions of intra‐day and inter‐day were all within 5.0%. The method was then applied for quantitation of the seven major components in 11 batches of crude and salt‐processed Cuscuta chinensis. Subsequently, the anti‐osteoporosis effects of crude and salt‐processed Cuscuta chinensis were evaluated in zebrafish. Principle component analysis, grey relationship analysis, and partial least squares regression were applied for deciphering the relationship between the contents of seven major components and the anti‐osteoporosis effects. Hyperin, p‐hydroxycinnamic acid, and astragalin were found to be the major anti‐osteoporosis components. [ABSTRACT FROM AUTHOR]

To avoid irreversible stationary phase adsorption and tedious and time‐consuming separation steps, high‐speed countercurrent chromatography was employed for the preparative separation of anti‐tumor compound antroquinonol from solid fermentation culture of Antrodia camphorata for the first time. A Box–Behnken experimental design, based on three parameters including liquid‐to‐solid ratio, extraction time, and extraction temperature, was applied to optimize the ultrasonic extraction procedure. The optimal extraction condition was set as follows: liquid‐to‐solid ratio: 49.57:1; extraction time: 55.76 min; extraction temperature was arranged as 44.21°C. Meanwhile, an optimized solvent system containing petroleum ether, ethyl acetate, methanol, and water (4:1:4:1, v/v/v/v) was selected for the preparative separation of antroquinonol at a flow rate of 2.0 mL/min. The yield of isolated antroquinonol was determined to be 6.0 mg from 0.67 g of ethyl acetate extracts. The isolated antroquinonol was elucidated by ultra‐high‐performance liquid chromatography–tandem mass spectrometry, and NMR spectroscopy, and by comparison with literature data. The purity of isolated antroquinonol was determined to be 97.12%. This study confirmed that high‐speed countercurrent chromatography was powerful and cost‐effective for the preparative separation of the high‐potently anti‐tumor compound antroquinonol from solid fermentation culture of A. camphorata. [ABSTRACT FROM AUTHOR]

An artificial accelerated aging method was adopted to simulate the photo-oxygen aging process of high-density polyethylene (PE-HD) pipes and butt fusion joints under the natural sunlight. A UVA-340 standard fluorescent ultraviolet lamp was used to simulate the aging process in the two cycle modes of light and condensation at different temperatures of 50 °C, 60 °C and 70 °C. Infrared spectroscopy was also conducted to analyze the chemical structures of the aged pipe and joint samples. The results indicated that with an increase in aging time, the joint showed higher peak intensity for the olefin and carbonyl absorption in the joint than that in the pipe due to the increase of the photo-oxidation aging degree. Meanwhile, the oxidation induction time of pipes and joints were measured with different aging time at different temperatures. The oxidation induction time and the relationship between natural sunlight and fluorescent ultraviolet lamp irradiation were fitted by means of the kinetic curve linearization method, and a life prediction model for the natural light aging of high-density polyethylene pipes was proposed. The results indicated that the lifespan of PE-HD butt fusion joints exposed to the natural environment was 33.76% shorter than that of the pipes at room temperature. [ABSTRACT FROM AUTHOR]

A novel quality evaluation method of Corydalis yanhusuo was established by researching the high‐performance liquid chromatography behavior of alkaloids under different buffer solutions and exploring the correlation between alkaloids in C. yanhusuo. The retention times of tetrahydropalmatine and corydaline were significantly influenced by pH, while the peak shape was affected by buffer types and ionic strength. The resolution of compounds in fingerprint was satisfactory under acetonitrile–0.2% phosphoric acid buffer (adjusted pH to 5.0 with triethylamine). Twelve common peaks were found by comparing 20 batches of C. yanhusuo fingerprints, and three tertiary alkaloids and four quaternary alkaloids were identified. The fingerprints were analyzed by similarity analysis, hierarchical cluster analysis, principal component analysis, and partial least squares discriminant analysis. All samples were divided into three groups, and the contents of dehydrocorydaline and coptisine from Zhejiang province were relatively higher than other origins. There were six components performing more contributions to the quality of C. yanhusuo. The correlations between alkaloids were conducted by Pearson correlation analysis and mathematical model analysis. The content correlation between palmatine and berberine was y = 0.28x2 + 0.03x + 0.03, and the dehydrocorydaline and coptisine was y = −7.54/(1 + (x/0.14)0.5) + 2.61. The established mathematical model of alkaloids provided a guiding significance for the quality control of C. yanhusuo. [ABSTRACT FROM AUTHOR]

A DDQ-mediated tandem reaction of easily available o -hydroxy-aryl enaminones and cycloheptatriene is disclosed. It provides an effective and convenient method for the synthesis of 3-(cycloheptatrienyl)-substituted chromones in moderate to excellent yields with good functional group tolerance; this reaction involves an oxidative coupling and intramolecular annulation pathway. [ABSTRACT FROM AUTHOR]

An efficient tandem oxidative annulation for the synthesis of 2,2‐disubstituted 2,3‐dihydroquinazolin‐4(1H)‐ones via DDQ‐mediated dual cross‐dehydrogenative‐coupling (CDC) reactions is described. This transformation proceeds from easily available o‐aminobenzamides and 1,3‐diarylpropenes under mild conditions, and the corresponding products are obtained in moderate to excellent yields. [ABSTRACT FROM AUTHOR]

A method for quantitative determination of the main active ingredient in traditional Chinese medicine was developed and validated, using liquid-liquid chromatography combined with high performance liquid chromatography, which was successfully applied to synephrine in Fructus Aurantii Immaturus. A biphasic solvent system composed of ethyl acetate - n-butanol - water - trifluoroacetic acid (1:2:3:0.003, v/v) was used to purify the crude extract of the samples by liquid-liquid chromatography. Then, quantitative analysis of synephrine in Fructus Aurantii Immaturus could be well determined by high performance liquid chromatography. Moreover, the collection time and retention time of synephrine could be well predicted using a continuous-stirred tank reactors model. Compared with previous studies, the present method showed advantages of good recovery, good repeatability, high selectivity to target components and simple operation. [ABSTRACT FROM AUTHOR]

In traditional Chinese therapy, the decoction of herbal products is commonly used as a therapeutic drug, which takes water as the extraction medium and contains many hydrophilic compounds. The main compounds reported in Eupatorium fortunei Turcz were volatile oils. However, polar constituents of its decoction were less studied. In this paper, polar compounds in aqueous extract of E. fortunei Turcz were isolated by counter-current chromatography combined with a macroporous resin column. By the system of n-butanol/acetonitrile/(273 mg/mL) (NH4)2SO4 solution (3:1:4.4, v/v/v), 205.0 mg of 10% ethanol fraction was separated to yield 2.4 mg of the trans-coumaric acid-3-O-β-D-glucoside with the purity of 95.0%. By the system of n-hexane/ethyl acetate/water (1:4:5, v/v/v), 92.0 mg of ethanol fraction was separated to yield 11.3 mg of trans-o-coumaric acid with a purity of 94.2%. Through the isolation and identification of compounds of characteristic peaks, it was effective to provide a theoretical basis for qualitative identification and quantitative determination of maker compounds in the research of quality assessment for E. fortunei Turcz. [ABSTRACT FROM AUTHOR]

As a liquid‐liquid partition chromatography, counter‐current chromatography has advantages in large sample loading capacity without irreversible adsorption, which has been widely applied in separation and purification fields. The main factors, including partition coefficient, two‐phase solvent systems, apparatus, and operating parameters greatly affect the separation process of counter‐current chromatography. To promote the applications of counter‐current chromatography, it is essential to develop theoretical research to master the principles of counter‐current chromatographic separations so as to achieve predictions before laborious trials. In this article, recent progress about separation prediction methods are reviewed from a point of the steady and unsteady state of the mass transfer process of counter‐current chromatography and its mass transfer characteristics, and then it is divided into three aspects: prediction of partition coefficient, modeling the thermodynamic process of counter‐current chromatography, and modeling the dynamic process of counter‐current chromatography. [ABSTRACT FROM AUTHOR]

Despite the recent increase in the development of bioactive molecules in the drug industry, the enormous chemical space and lack of productivity are still important issues. Additional alternative approaches to screen and locate bioactive molecules are urgently needed. Label‐free bio‐affinity mass spectrometry (BA‐MS) provides opportunities for the discovery and development of innovative drugs. This review provides a comprehensive portrayal of BA‐MS techniques and of their applications in screening and locating bioactive molecules. After introducing the basic principles, alongside some application notes, the current state‐of‐the‐art of BA‐MS‐assisted drug discovery is discussed, including native MS, size‐exclusion chromatography‐MS, ultrafiltration‐MS, solid‐phase micro‐extraction‐MS, and cell membrane chromatography‐MS. Finally, several challenges and limitations of the current methods are summarized, with a view to potential future directions for BA‐MS‐assisted drug discovery. © 2019 John Wiley & Sons Ltd. Mass Spec Rev [ABSTRACT FROM AUTHOR]

A simple, efficient, and sensitive strategy by coupling matrix solid‐phase dispersion with ultra high performance liquid chromatography quadrupole time‐of‐flight mass spectrometry was proposed to extract and determine three types of components (including seven analytes) in Chinese patent medicines Chenxiangqu. The highly ordered mesoporous material Fe‐SBA‐15 synthesized under weakly acidic conditions was selected as a dispersant in matrix solid phase dispersion extraction for the first time. Several parameters including the mass ratio of sample to dispersant, the type of dispersant, the grinding time, and the elution condition were investigated in this work. Under the optimized conditions, 20 compounds were identified by quadrupole time‐of‐flight mass spectrometry and seven analytes were quantified. The results demonstrated that the developed method has good linearity (r > 0.9995), and the limits of detection of the analytes were as low as 0.55 ng/mL. The recoveries of all seven analytes ranged from 97.6 to 104.6% (relative standard deviation < 3.4%). Finally, the improved method was successfully applied to determination of five batches of Chenxiangqu samples, which provided a robust method in quality control of Chinese patent medicines Chenxiangqu. The developed strategy also shows its great potential in analysis of complex matrix samples. [ABSTRACT FROM AUTHOR]

An oxidative annulation for the synthesis of 2,4-diarylquinolines from o -allylanilines is disclosed that uses recyclable reagent Chloranil- as the oxidant. The corresponding products are obtained in moderate to excellent yields. Furthermore, a one-pot access to 2,4-di-aryl-quinolines from easily available anilines and 1,3-diarylpropenes is described as a highly atom-efficient protocol that involves oxidative coupling, rearrangement, and oxidative annulation. [ABSTRACT FROM AUTHOR]

Electrokinetic supercharging, a convenient and powerful online preconcentration technique in capillary electrophoresis, was introduced and evaluated for the determination of two alkaloids, berberine and jatrorrhizine, in mice fecal samples for the first time. The method depended on using a bare fused silica capillary (50 cm × 50 μm i.d.) and applying the voltage of 25 kV with UV detection at 205 nm. Parameters that affect the separation and preconcentration efficiency have been optimized. The optimum conditions used were as follows: background electrolyte consisting of 40mM sodium dihydrogenphosphate containing 30% methanol (v/v); hydrodynamic injection of 20mM KCl (50 mbar × 150 s) as the leading electrolyte; electrokinetic injection of the sample (+15 kV, 120 s) followed by the hydrodynamic injection of 30mM dodecyl trimethyl ammonium chloride (50 mbar × 12 s) as the terminating electrolyte. The results showed that the detection sensitivity of berberine and jatrorrhizine was, respectively, improved up 2740‐ and 2928‐fold compared with normal injection, providing limits of detection lower than 3 ng/mL with good repeatability in areas (relative standard deviation < 3%). In summary, the developed method proved its ability in analyzing trace alkaloids in complicated biological samples. [ABSTRACT FROM AUTHOR]

A rapid and sensitive UPLC–MS/MS method was established for the simultaneous quantification of 6′′′‐feruloylspinosin, spinosin, jujuboside A, and jujuboside B in rat plasma after the oral administration of traditional and dispensing granules (DG) decoction of Ziziphi Spinosae Semen (ZSS). The four components were separated using 0.1% formic acid and acetonitrile as a mobile phase by gradient elution at a flow rate of 0.3 mL/min equipped with a C18 column (2.1 × 50 mm, 1.7 μm particle size, Acquity BEH C18). The mass spectrometer was operated under multiple reaction monitoring mode. An aliquot of 100 μL rat plasma was deproteinized by 300 μL methanol. The supernatant was injected into the UPLC–MS/MS system for analysis. The calibration curves displayed good linearity. The intra‐day and inter‐day precisions (RSD) were less than 7.3%. The accuracies ranged from −1.3 to 6.1%. The extraction recoveries ranged from 95.8 to 101.9%, and the matrix effects were satisfactory. For DG, half‐life values (t1/2) of 6′′′‐feruloylspinosin and Cmax of jujuboside A were elevated remarkably. MRT0–t of jujuboside B was significantly increased. No significant variation was observed for the pharmacokinetic parameters of spinosin. The results could provide a scientific basis for the clinical application of traditional and DG decoction of ZSS. [ABSTRACT FROM AUTHOR]

Acetyltropic acid is an important synthetic intermediate for preparation of tropane alkaloid derivatives, which can be used as anticholinergic drugs, deliriants, and stimulants. In the present work, acetyltropic acid was successfully enantioseparated by countercurrent chromatography using sulfobutyl ether‐β‐cyclodextrin as chiral selector. A biphasic solvent system composed of n‐butyl acetate/n‐hexane/0.1 mol/L citrate buffer at pH = 2.2 containing 0.1 mol/L of sulfobutyl ether‐β‐cyclodextrin (7:3:10, v/v) was selected, which produced a suitable distribution ratio DS = 1.14, DR = 2.31 and a high enantioseparation factor α = 2.03. Baseline separation was achieved for preparative enantioseparation of 50 mg of racemic acetyltropic acid. A method for chiral analysis of acetyltropic acid by conventional reverse phase liquid chromatography with hydroxylpropyl‐β‐cyclodextrin as mobile phase additive was established, and formation constants of inclusion complex were determined. It was found that different substituted β‐cyclodextrin should be selected for enantioseparation of acetyltropic acid by countercurrent chromatography and reverse phase liquid chromatography. [ABSTRACT FROM AUTHOR]

A DDQ‐mediated tandem reaction of 1,3‐diarylpropenes and β‐enaminoesters/4‐aminocoumarins is disclosed. It involves oxidative coupling, intramolecular annulation and dehydro‐aromatization reaction, which provides an efficient and mild method for the synthesis of polysubstituted and fused pyridines under metal‐free conditions. [ABSTRACT FROM AUTHOR]

Introduction: Germacrone, furanodiene and β‐elemene are the representative bioactive compounds in Curcuma species. The conventional extraction methods of these three sesquiterpenes are usually time‐consuming and require a large volume of hazardous organic solvents. Thus, a fast and reliable method for extracting these sesquiterpenes from Curcuma plant is required urgently. Objective: To establish a novel and simple extraction method for quantitative analysis of small amounts of sesquiterpenes in C. wenyujin plant. Methodology: A method using microwave‐assisted ionic liquid‐micelle extraction combined with dispersive micro‐solid‐phase extraction (DMSPE) has been proposed for the extraction of three sesquiterpenoids in Curcuma plant. Fluorinated carbon nanotubes (FCNTs) were used as an adsorbent in DMSPE for the first time. Parameters concerning the microwave‐assisted extraction (MAE) conditions and the DMSPE were investigated and evaluated to achieve optimum extraction efficiency of target analytes. Results: The final conditions of ionic liquid‐micelle based MAE were selected to be 0.25 M of 1‐decyl‐3‐vinylimidazolium bromide as the extraction solvent, microwave irradiation for 10 min at 60°C. And the optimal DMSPE conditions were found to be 2 μg/mL of FCNTs as the adsorbent, extraction time of 2 min and 100 μL of acetonitrile as the elution solvent. The developed method exhibited good linearities (R > 0.9990), high repeatability and recoveries. The proposed method has been successfully applied in determination of sesquiterpenes in C. wenyujin samples. Conclusion: The work shows a potential in analysing small amounts of sesquiterpenes in complex samples and represents the first attempt of using FCNTs as an adsorbent for the microextraction mode. A novel, simple and reliable extraction method which adopts microwave‐assisted ionic liquid‐micelle extraction combined with dispersive micro‐solid‐phase extraction using trace fluorinated carbon nanotubes was successfully established and applied for quantitative analysis of small amounts of sesquiterpenes in Curcuma wenyujin plant samples. The developed method exhibited good linearities (R > 0.9990), high repeatability and recoveries. This work shows a potential in analysing small amount of sesquiterpenes in complex samples matrix. [ABSTRACT FROM AUTHOR]

A novel on‐line synergistic proconcentration strategy coupling field‐amplified sample stacking and micelle to cyclodextrin stacking for cationic analytes in capillary zone electrophoresis has been proposed and applied for the separation and determination of two alkaloids, matrine, and oxymatrine in complicated matrix samples. The approach was performed by the long injection of sample in a low‐conductivity sodium dodecyl benzene sulfonate solution followed by the injection of hydroxypropyl‐β‐cyclodextrin solution in higher conductivity. The stacking mechanism of this method has been expounded and parameters affecting stacking effect have been optimized in our study. Under the optimum experimental conditions, 169‐ and 218‐fold sensitivity improvements were achieved for matrine and oxymatrine when compared with normal injection. Analytical indicators including linearity, limits of detection, and reproducibility (intra‐ and inter‐day relative standard deviations) were evaluated. Moreover, sample matrix effect was studied using compound flavescent sophora and salicylic acid powder and spiked urine samples. The developed method is an attempt for the combination of micelle to cyclodextrin stacking with other stacking methods. It could be a good alternative choice for the determination of alkaloids in a complex sample matrix. [ABSTRACT FROM AUTHOR]

Four stereoisomeric components were produced during the synthesis of the antidepressant drug (1S, 4S)‐sertraline hydrochloride due to the two chiral carbon centers in its chemical structure, including (1S, 4S), (1R, 4R), (1S, 4R), and (1R, 4S)‐isomer. Stereoselective separation of the target isomer (1S, 4S)‐sertraline from the medicinal reaction mixtures by countercurrent chromatography using hydroxypropyl‐β‐cyclodextrin as the stereoselective selector was investigated. A biphasic solvent system composed of n‐hexane/0.20 mol/L phosphate buffer solution with pH 7.6 containing 0.10 mol/L of hydroxypropyl‐β‐cyclodextrin (1:1, v/v) was selected for separation of cis‐sertraline and trans‐sertraline using reverse phase elution mode and (1S, 4S)‐sertraline was separated with (1R, 4R)‐sertraline using recycling elution mode. A fabricated in‐house analytical countercurrent chromatographic apparatus was used for optimization of the separation conditions. Stationary phase retention and peak resolution were investigated for separation of cis‐sertraline and trans‐sertraline by the analytical apparatus. [ABSTRACT FROM AUTHOR]

The tandem reaction of enaminones with 1,3‐diarylpropenes mediated by 2,3‐dichloro‐5,6‐dicyano‐1,4‐benzoquinone (DDQ) is reported, which involves the oxidative coupling and the intramolecular cyclization reactions. It provides a convenient, efficient and metal‐free method for the synthesis of 3‐allylated chromones and quinolone with potential biological activities. [ABSTRACT FROM AUTHOR]

Ecdysterone and saponins are the most characteristic components of Radix Achyranthes bidentate, which acts on the human body to promote collagen synthesis and stimulates cell growth. However, the relationship between these components and the differentiation of MC3T3‐E1 osteoblastic cells is unknown. We developed a rapid ultra high performance liquid chromatography with triple quadrupole tandem mass spectrometry method for direct determination of one ecdysterone and four saponins in crude and salt‐processed Radix Achyranthes bidentate. The method was interrogated in terms of linearity, intra‐ and inter‐day precision, repeatability, stability and recovery. The method was linear within the concentration ranges of 0.003–336 μg/mL for β‐ecdysterone, 0.0035–130 μg/mL for 25S‐inokosterone, 0.004–423 μg/mL for ginsenoside Ro, 0.0036–66 μg/mL for chikusetsusaponin IV and 0.0044–111 μg/mL for chikusetsusaponin IVa. The intra‐ and inter‐day precisions were all within 2.7%. The standard addition method determined recovery rates for each component (98.7–102.5%). The method was successfully applied to simultaneously quantify five components in ten batches of crude and salt‐processed Radix Achyranthes bidentate. Subsequently, the examination of these extracts on the differentiation of MC3T3‐E1 osteoblastic cells were carried out. Finally, the relationships between the contents of five components and their anti‐osteoporosis effect were investigated by using canonical correlation analysis. [ABSTRACT FROM AUTHOR]

A novel analytical quality by design approach for developing a chromatographic fingerprint was established for analyzing complex traditional Chinese medicine, using a licorice standard decoction as an example. Considering the characteristics of integrity and ambiguity, the resolution of eight common peaks, total peak number, capacity factor distributions, and peak purity were selected as potential critical method attributes for assessing the quality of the chromatographic fingerprint. A central composite design was used to evaluate the relationship between critical method attributes and critical method parameters, including column temperature, wavelength, flow rate, formic‐acid concentration, and gradient parameters. A standard probability method was employed to calculate the design space of the fingerprint analysis parameters and evaluate the robustness of the methodology. The optimized high‐performance liquid chromatography fingerprint conditions were acetonitrile and 0.1% formic acid water gradient elution (0‐5 min, 5–19% A; 5–10 min, 19% A; 10–50 min, 19–42% A; 50–54 min, 42–100% A; 54–60 min, 100% A), column temperature 25±5°C, detection wavelength 265 nm. The design space of fingerprint analytical method based on the analytical quality by design approach not only met the requirements of the fingerprint analysis, but also improved the robustness and applicability of the fingerprint method. [ABSTRACT FROM AUTHOR]

The nitromethylation of 1,3‐diarylpropenes via 2,3‐dichloro‐5,6‐dicyano‐1,4‐benzoquinone (DDQ) mediated C−H oxidative activation is reported, in which N,N‐dimethyl‐2‐nitroethyleneamine is used as a nitromethane equivalent. The precedent method for the synthesis of 1,3‐diaryl‐2‐propenylnitromethanes is safe and easy to work‐up. Oxidative coupling: The nitromethylation of 1,3‐diarylpropenes was mediated by DDQ using N,N‐dimethyl‐2‐nitroethyleneamine as a nitromethane equivalent. It provides a safe and convenient method for the synthesis of 1,3‐diaryl‐2‐propenylnitromethanes. [ABSTRACT FROM AUTHOR]

A simple, convenient, and sensitive method that involves combining matrix solid‐phase dispersion extraction with field‐amplified sample stacking in capillary electrophoresis has been developed for the determination of organic acids in a complex solid matrix. Mesoporous molecular sieve, MCM‐48, was synthesized by a hydrothermal method and selected as the adsorbent in matrix solid‐phase dispersion. After fast extraction, the enriched analytes were back‐extracted into a basic aqueous solution for field‐amplified sample stacking in capillary electrophoresis. Parameters that affect extraction efficiency and sample stacking were optimized. Under the optimal conditions, approximately 42‐, 49‐, and 56‐fold sensitivity enhancements were achieved for danshensu, protocatechuic acid, and cinnamic acid, respectively, when compared to normal injection. A satisfactory correlation coefficient (r > 0.99) was obtained. Both intra‐ and interday precision were lower than 2.53%. And the limits of detection of the three organic acids ranged between 0.01 and 0.029 μg/mL. Finally, the newly proposed method was successfully applied to the determination of organic acids in Fufang Danshen tablets, which indicates its great potential in analyzing organic acids in a complex matrix. [ABSTRACT FROM AUTHOR]

Objective: To establish a quantitative analysis of multi-components by single marker (QAMS) method for the determination of triterpenoids and distinction of Ganoderma and related species. Methods: Ten ganoderma triterpenoids were determined by HPLC in addition to a QAMS method. On the basis of QAMS, principal component analysis (PCA) and cluster analysis (CA) were used to distinguish Ganoderma samples. Results: Ten types of ganoderma triterpenoids had good linearity of regression coefficients (R2 ≥ 0.9992). Relative correction factors (RCFs) of lucideric acid C, lucideric acid LM1, ganoderic acid G, lucideric acid B, lucideric acid A, ganoderenic acid D, ganoderic acid D, lucideric acid D and ganoderic acid F with reference to ganoderic acid A were 0.929, 1.011, 0.608, 1.041, 0.997, 2.464, 0.891, 0.826 and 0.722, respectively. Ten types of ganoderma triterpenoids in twenty-nine batches of Ganoderma and related species were determined by QAMS. Nineteen batches of samples containing ganoderma acid A were roughly divided into three categories by PCA and CA. Conclusion: The developed QAMS method, in combination with PCA and CA, served as an accurate method for the rapid evaluation and authenticity identification of Ganoderma. [ABSTRACT FROM AUTHOR]

Abstract: Three key intermediates in the preparation of the nonsteroidal anti‐inflammatory drug naproxen were successfully separated and purified with high purity from synthetic mixtures by countercurrent chromatography with a selected biphasic solvent system. The biphasic solvent system composed of n‐hexane/ethyl acetate/methanol/water (9:1:9:1, v/v/v/v) was selected according to partition performance of the three components using thin‐layer chromatography. Fifty milligrams of the synthetic mixture after the three‐step reaction was injected into a preparative countercurrent chromatography separation column and yielded 3.5, 14.0, and 8.0 mg of three key intermediates with 95.0, 99.0, and 98.0% purity, and the recovery of each component was 65.2, 71.2, and 69.6%, respectively. The results indicated that countercurrent chromatography is an efficient alternative and economical method for the separation and purification of intermediate components from synthetic mixtures. [ABSTRACT FROM AUTHOR]

Abstract: Recycling countercurrent chromatography was successfully applied to the resolution of 2‐(4‐bromomethylphenyl)propionic acid, a key synthetic intermediate for synthesis of nonsteroidal anti‐inflammatory drug loxoprofen, using hydroxypropyl‐β‐cyclodextrin as chiral selector. The two‐phase solvent system composed of n‐hexane/n‐butyl acetate/0.1 mol/L citrate buffer solution with pH 2.4 (8:2:10, v/v/v) was selected. Influence factors for the enantioseparation were optimized, including type of substituted β‐cyclodextrin, concentration of hydroxypropyl‐β‐cyclodextrin, separation temperature, and pH of aqueous phase. Under optimized separation conditions, 50 mg of 2‐(4‐bromomethylphenyl)propionic acid was enantioseparated using preparative recycling countercurrent chromatography. Technical details for recycling elution mode were discussed. The purities of both the S and R enantiomers were over 99.0% as determined by high‐performance liquid chromatography. The enantiomeric excess of the S and R enantiomers reached 98.0%. The recovery of the enantiomers from eluted fractions was 40.8–65.6%, yielding 16.4 mg of the S enantiomer and 10.2 mg of the R enantiomer. At the same time, we attempted to enantioseparate the anti‐inflammatory drug loxoprofen by countercurrent chromatography and high‐performance liquid chromatography using a chiral mobile phase additive. However, no successful enantioseparation was achieved so far. [ABSTRACT FROM AUTHOR]

Triterpenoids are the major secondary metabolites and active substances in Ganoderma, considered as the “marker compounds” for the chemical evaluation or standardization of Ganoderma. A response surface methodology was used to optimize the ultrasonic-assisted extraction of triterpenoids. The extraction rate was 7.338 ± 0.150 mg/g under the optimum conditions: 87% ethanol, ratio of solid to liquid (w : v) 1 : 28, and ultrasound extraction time 36 min. Based on the high sensitivity and selectivity of HPLC-LTQ-Orbitrap-MSn, 24 components of triterpenoids were tentatively identified in the negative mode. Then, the global chemical profiling consisting of HPLC and TLC fingerprints generated by ChemPattern™ software was developed for evaluation of Ganoderma species. For fingerprint analysis, 11 peaks of triterpenoids were selected as the characteristic peaks to evaluate the similarities of different samples. The correlation coefficients of similarity were greater than 0.830. The cluster analysis showed a clear separation of three groups, and 11 peaks played key roles in differentiating these samples. The developed global chemical profiling method could be applied for rapid evaluation, quality control, and authenticity identification of Ganoderma and other herbal medicines. [ABSTRACT FROM AUTHOR]

Abstract: The tandem reaction of 3‐morpholinoacrylonitrile with sulfonyl hydrazides mediated by I2/benzoyl peroxide (BPO) is reported, which offers an efficient approach for the synthesis of sulfonated 5‐aminopyrazoles. It can bear a large scope of the substrates, and be used for the synthesis of aromatic, heteroaromatic and aliphatic sulfonated 5‐aminopyrazoles. [ABSTRACT FROM AUTHOR]

Abstract: Shenqi Jiangtang Granule, a well‐known traditional Chinese herbal preparation, has been widely used for the treatment of type II diabetes mellitus. In this work, an ultrafiltration liquid chromatography with quadrupole time‐of‐flight mass spectrometry method was proposed for the rapid identification of bioactive ingredients from Shenqi Jiangtang Granule using α‐glucosidase as an example. First, the chemical profile of this preparation was clarified, including 37 saponins, 17 flavonoids, 37 lignans, and seven other compounds. After incubation with α‐glucosidase in vitro, the methanol extract with an IC50 value of 0.19 mg/mL exhibited significant inhibitory activity. Then, 18 specific binding peaks were screened, and 15 peaks were identified. Among these, ten compounds were reported to have potential α‐glucosidase inhibitory activity for the first time. Subsequently, the inhibitory activities of these active compounds were evaluated by ultraviolet spectrophotometry with p‐nitrophenyl α ‐d‐glucopyranoside as a substrate. As a result, gomisin J and gomisin D exhibited stronger α‐glucosidase inhibitory activities than other active compounds with IC50 values of 77.69 and 133.85 μM, respectively. The results demonstrated that the integrated ultrafiltration liquid chromatography with mass spectrometry method was an effective and powerful tool for the discovery of active ingredients in Shenqi Jiangtang Granule. [ABSTRACT FROM AUTHOR]

A novel, metal-free cross-dehydrogenative coupling (CDC) reaction of C( sp2)-H bonds of enamines and α-oxo ketene dithioacetals with C( sp3)-H bonds of 1,3-diarylpropenes mediated by 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) is reported. The α-alkylation products are obtained with moderate to good yields. The method provides an efficient and alternative strategy for the synthesis of the corresponding products. [ABSTRACT FROM AUTHOR]

The separation of ten epimeric aromatic acid (−)-menthol esters by countercurrent chromatography with hydroxypropyl-β-cyclodextrin as the mobile phase additive was investigated, and methods for the analysis of all the epimeric esters by reversed-phase high-performance liquid chromatography were established. A biphasic solvent system composed of n-hexane/20-70% methanol containing 50 mmol/L of hydroxypropyl-β-cyclodextrin (1:1, v/v) was selected, which provided high separation factors for five of the epimeric esters, and successful separations by countercurrent chromatography were achieved. The complete separation of five pairs of epimeric ester was obtained with the purity being over 98% for each peak fractions, as determined by high-performance liquid chromatography. The recovery of each analyte from the eluted fractions reached around 80-88%. [ABSTRACT FROM AUTHOR]

3-Phenyllactic acid is an antimicrobial compound with broad-spectrum activity against various bacteria and fungus. The observed difference in pharmacological activity between optical isomeric 3-phenyllactic acid necessitates a method for enantioseparation. Chiral ligand exchange countercurrent chromatography was investigated for the enantioseparation of 3-phenyllactic acid with a synthesized chiral ligand. A two-phase solvent system was composed of n-butanol/hexane/water (0.4:0.6:1, v/v/v) to which N- n-dodecyl- l-hydroxyproline was added to the organic phase as chiral ligand and cupric acetate was added in the aqueous phase as a transitional metal ion. The influence factors were optimized by enantioselective liquid-liquid extraction. Baseline enantioseparation of racemic 3-phenyllactic acid by analytical high-speed countercurrent chromatography was achieved. The optical purities of enantiomeric 3-phenyllactic acid reached 99.0%, as determined by chiral high-performance liquid chromatography. [ABSTRACT FROM AUTHOR]

This paper concentrates on the enantioseparation of racemic 2-(substituted phenyl)propanoic acids by high-speed countercurrent chromatography with substituted β-cyclodextrin as the chiral selector, and an investigation of the influence of the substituent on the benzene ring in enantiorecognition between the chiral selector and enantiomer of each racemate is presented. This is an extension research of our previous work on the enantioseparation of 2-phenyl propanoic acid derivatives, to investigate the relationship between the value of enantioseparation factor and the different substituent on the benzene ring. In total, ten racemic 2-(substituted phenyl)propanoic acids were investigated, of which four including 2-(4-nitrophenyl)propanoic acid, 2-(4-methylphenyl)propanoic acid, 2-(4-hydroxyphenyl)propanoic acid, and 2-(4-chlorophenyl)propanoic acid, were studied by countercurrent chromatography for the first time, and two racemates were successfully enantioseparated. The distribution ratio and enantioseparation factor for all the ten racemates were determined by enantioselective liquid-liquid extraction. The results showed that an electron-donating group on the benzene ring presents a higher enantiorecognition induced by chiral selector than that of racemates with an electron-withdrawing group on the benzene ring. [ABSTRACT FROM AUTHOR]

In this work, a simple and efficient protocol for the rapid separation of two pairs of isomeric monoterpenes from Paeoniae Alba Radix was developed by combining macroporous resin and elution-extrusion counter-current chromatography. The crude extract was firstly subjected to a D101 macroporous resin column eluted with water and a series of different concentrations of ethanol. Then, effluents of 30 and 95% ethanol were collected as sample 1 and sample 2 for further counter-current chromatography purification. Finally, a pair of isomers, 96 mg of compound 1 and 48 mg of compound 2 with purities of 91.1 and 96.2%, respectively, was isolated from 200 mg of sample 1. The other pair of isomers, 14 mg of compound 3 and 8 mg of compound 4 with purities of 93.6 and 88.9%, respectively, was isolated from 48 mg of sample 2. Their purities were analyzed by high-performance liquid chromatography, and their chemical structures were identified by mass spectrometry and 1H NMR spectroscopy. Compared to a normal counter-current chromatography separation, the separation time and solvent consumption of elution-extrusion counter-current chromatography were reduced while the resolutions were still good. The established protocol is promising for the separation of natural products with great disparity of content in herbal medicines. [ABSTRACT FROM AUTHOR]

The chromatographic retention mechanism describing relationship between retention factor and concentration of Cu2+( l-phenylalanine)2 using chiral ligand mobile phase was investigated and eight mandelic acid derivatives were enantioseparated by chiral ligand exchange chromatography. The relationship between retention factor and concentration of the Cu2+( l-phenylalanine)2 complex was proven to be in conformity with chromatographic retention mechanism in which chiral discrimination occurred both in mobile and stationary phase. Different copper(II) salts, chiral ligands, organic modifier, pH of aqueous phase, and conventional temperature on retention behavior were optimized. Eight racemates were successfully enantioseparated on a common reversed-phase column with an optimized mobile phase composed of 6 mmol/L of l-phenylalanine or N, N-dimethyl- l-phenylalanine and 3 mmol/Lof copper(II) acetate or copper(II) sulfate aqueous solution and methanol. [ABSTRACT FROM AUTHOR]