[Integrated smart hyperspectral imaging and CARS-based characteristic band selection for rapid determination of SO_2 content in sulphur-fumigated Achyranthis Bidentatae Radix].

In order to realize the rapid and non-destructive detection of SO_2 content in sulphur-fumigated Achyranthis Bidentatae Radix, this paper first prepared the sulphur-fumigated Achyranthis Bidentatae Radix samples with the usage amount of sulphur being 0, 2.5%, and 5% of the mass of Achyranthis Bidentatae Radix pieces. The SO_2 content in different batches of sulphur-fumigated Achyranthis Bidentatae Radix was determined using the method in Chinese Pharmacopoeia, followed by the acquisition of their hyperspectral data within both visible-near infrared(435-1 042 nm) and short-wave infrared(898-1 751 nm) regions by hyperspectral imaging. Meanwhile, the first derivative, AUTO, multiplicative scatter correction, Savitzky-Golay(SG) smoothing, and standard normal variable transformation algorithms were used to pre-process the original hyperspectral data, which were then subjected to characteristic band extraction based on competitive adaptive reweighted sampling(CARS) and the partial least square regression analysis for building a quantitative model of SO_2 content in sulphur-fumigated Achyranthis Bidentatae Radix. It was found that the accuracy of the quantitative model built depending on the visible-near infrared spectra was high, with the determination coefficient of prediction set(R■) reaching 0.900 1. The established quantitative model has enabled the rapid and non-destructive detection of SO_2 content in sulphur-fumigated Achyranthis Bidentatae Radix, which can serve as an effective supplement to the method described in Chinese Pharmacopeia.

Layer-by-layer assembly strategy for fabrication of polydopamine-polyethyleneimine hybrid modified fibers and their application to solid-phase microextraction of bioactive molecules from medicinal plant samples followed by surface plasmon resonance biosensor validation.

A solid-phase microextraction method is introduced to overcome limitations of classical phytochemical pattern of identifying bioactive compounds, including tedious and time-consuming separation and purification step and consumption of large amounts of organic solvents, which was non-environmentally- friendly. In this proposed method for solid-phase microextraction, polyvinylidene fluoride fibers@polydopamine@polyethyleneimine@receptor as a solid part of the extractors were pushed into sample solution of medicinal plants, and the procedure was followed by stirring and easily dissociation of receptor binding ligands in organic solvent through pulling out of the functionalized fibers. Xanthine oxidase was chosen as the model receptor, while isoacteoside was selected as the model inhibitor. Several effecting parameters were optimized by experimental design, including temperature, ion strength and pH. Nine bioactive components were obtained from extract of Plantago depressa by using the established solid-phase micro-extraction method. The limit of detection and limit of quantification of the nine components ranged from 0.0008 to 0.03 mg mL-1 and from 0.001 to 0.016 mg mL-1, respectively. The RSD values of intra-day and inter-day precisions ranged from 0.24% to 2.19% and 0.62%-2.84%, respectively. The average recoveries of the nine components were from 95.06 to 104.03% with relative standard deviation (RSD) values from 1.02 to 2.90% for Plantago depressa. The RSD values of stability of the nine components ranged from 1.36% to 2.74%, which satisfied the requirements of an analytical method. In addition, surface plasmon resonance biosensor was utilized to corroborate the binding affinity between these compounds and receptor. The avidity values of these ligands corresponded well with their IC50 values. The results confirmed that polydopamine and polyethyleneimine hybrid modified polyvinylidene fluoride fibers based solid-phase microextraction method was successfully utilized for locating bioactive compounds of medicinal plants.

Validation of an analytical method using UPLC-MS/MS to quantify four bioactive components in rat plasma and its application to pharmacokinetic study of traditional and dispensing granules decoction of Ziziphi Spinosae Semen.

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.

Development of an ultra-high-performance liquid chromatography coupled with triple quadrupole mass spectrometry method for comparative pharmacokinetics of six triterpenoids in rat plasma and application to different forms of Phytolacca acinosa.

Phytolacca acinosa is an herb for treatment of ascites and tumor. Two forms of P. acinosa, i.e. raw and vinegar-processed herb, have been used in clinic. However, pharmacokinetic difference between the two forms of P. acinosa has not been fully understood. Herein, a comparative pharmacokinetic method based on liquid chromatography with tandem mass spectrometry was developed for quantification of six bioactive triterpenoids, including esculentoside H, esculentoside T, esculentoside A, esculentoside B, phytolaccagenic acid, and phytolaccagenin in rat plasma after oral administration of different forms of P. acinosa. Separation was performed on an Acquity BEH C18 column (1.7 µm, 2.1 mm × 50 mm). The method was validated over a linear range of 2.0-5000 ng/mL. Intraday and interday bias were within ±5%. Besides, all triterpenoids were stable in plasma during different storage conditions. The described method was successfully applied to a comparative pharmacokinetic study of raw and vinegar-processed P. acinosa in rats. Notably, double peak phenomenon for six triterpenoids of P. acinosa was observed for the first time. AUC0→t and Cmax values of esculentoside H, esculentoside T, phytolaccagenic acid, and phytolaccagenin were significantly lower in vinegar-processed group than that of raw group, indicating the oral bioavailability of the four triterpenoids was decreased after vinegar processing.

A biochemometrics strategy combining quantitative determination, bioactivity evaluation and relationship analysis for identification of analgesic alkaloids of raw and vinegar-processed Corydalis turtschaninovii.

A biochemometrics strategy combining quantitative determination, bioactivity evaluation, and relationship analysis was proposed for identification of analgesic components of herbs. First, a robust liquid chromatography tandem mass spectrometry method was developed for simultaneous determination of nine major alkaloids in crude and vinegar-processed Corydalis turtschaninovii. Nine alkaloids were separated on a BEH C18 column with a mobile phase consisting of acetonitrile and water spiked with 0.1% formic acid and then detected by multiple reactions monitoring in the positive ion mode. Nitidine chloride was employed as the internal standard. The method displayed good linearity and the precisions of intra-day and inter-day were all within 3.0%. The recovery rates of each alkaloid ranged from 97.1 to 102.9%. The method was successfully applied for quantitative analysis of nine alkaloids in ten batches of crude and vinegar-processed Corydalis turtschaninovii. Second, the analgesic effects of crude and vinegar-processed Corydalis turtschaninovii were evaluated in mice. Third, principle component analysis, canonical correlation analysis, and partial least squares regression were used to analysis the relationship between the contents of nine major alkaloids and the analgesic effect of different crude and vinegar-processed samples. Tetrahydropalmatine, coptisine, and dehydrocorydaline have a close positive correlation with the analgesic effect.

A biochemometrics strategy for tracing diuretic components of crude and processed Alisma orientale based on quantitative determination and pharmacological evaluation.

We proposed a biochemometrics strategy for tracing diuretic components of herbs based on quantitative determination and pharmacological evaluation. First, a sensitive and robust liquid chromatography coupled with tandem mass spectrometry approach was established for simultaneous quantification of six major triterpenoids in crude and salt-processed Alisma orientale. The separation of triterpenoids was achieved on a BEH C18 column with a mobile phase consisting of acetonitrile and water spiked with 0.1% formic acid. Six major triterpenoids were detected by multiple reaction monitoring in the negative ion mode. Glycyrrhetinic acid was used as the internal standard. The approach showed good linearity. Intra- and inter-day precisions were all within 2.9%. The recovery rates of each triterpenoid ranged from 97.9% to 103.2%. The approach was then successfully employed for quantitative analysis of six triterpenoids in ten batches of crude and salt-processed A. orientale. Second, the diuretic effects of crude and salt-processed A. orientale were evaluated in mice. Third, principal component analysis and canonical correlation analysis were used to uncover the relationship between the contents of six major triterpenoids and the diuretic effect of different crude and salt-processed samples. Alisol B, alisol F, and alisol A have a close positive correlation with the diuretic effect.