Tunable layered-magnetism-assisted magneto-Raman effect in a two-dimensional magnet CrI3.

We used a combination of polarized Raman spectroscopy experiment and model magnetism-phonon coupling calculations to study the rich magneto-Raman effect in the two-dimensional (2D) magnet CrI3 We reveal a layered-magnetism-assisted phonon scattering mechanism below the magnetic onset temperature, whose Raman excitation breaks time-reversal symmetry, has an antisymmetric Raman tensor, and follows the magnetic phase transitions across critical magnetic fields, on top of the presence of the conventional phonon scattering with symmetric Raman tensors in N-layer CrI3 We resolve in data and by calculations that the first-order A g phonon of the monolayer splits into an N-fold multiplet in N-layer CrI3 due to the interlayer coupling [Formula: see text] and that the phonons within the multiplet show distinct magnetic field dependence because of their different layered-magnetism-phonon coupling. We further find that such a layered-magnetism-phonon coupled Raman scattering mechanism extends beyond first-order to higher-order multiphonon scattering processes. Our results on the magneto-Raman effect of the first-order phonons in the multiplet and the higher-order multiphonons in N-layer CrI3 demonstrate the rich and strong behavior of emergent magneto-optical effects in 2D magnets and underline the unique opportunities of spin-phonon physics in van der Waals layered magnets.

Study on the processing chemistry of Fructus Psoraleae by a combination of untargeted and targeted metabolomics.

Fructus Psoralea is widely used to treat osteoporosis and skin inflammatory diseases. Because of the side effects on the liver, renal and cardiovascular systems, it is processed to salt-processed Fructus Psoraleae to meet the requirements of clinical use. However, the mechanisms involved in the transformation of the chemical components are unclear. In this study, ultra-high-performance liquid chromatography quadrupole time-of-flight mass spectrometry was used to analyze the chemical profiles of this herbal medicine and the chemical transformation mechanism involved during the salt processing was studied. A total of 83 compounds were identified. Principal component analysis and orthogonal partial least squares discriminate analysis were used to observe the distribution trend of all samples and visualize the difference. Raw and processed Fructus Psoraleae were clearly clustered into two groups. Furthermore, 17 marker compounds were identified as primary contributors to their differences based on t-test analysis (p < 0.01) and orthogonal partial least squares discriminate analysis (variable importance for the projection > 1). Finally, ultra-high performance liquid chromatography coupled with triple quadrupole tandem mass spectrometry was used to evaluate the quality of Fructus Psoraleae by simultaneous analysis of 13 components highly related to efficacy. There were variations in the contents of 13 chemicals of Fructus Psoraleae and salt-processed products. The results of untargeted and targeted metabolomics revealed that salt processing affected the chemical composition of Fructus Psoraleae.

[Rapid quality evaluation of Glycyrrhizae Radix et Rhizoma and Glycyrrhizae Radix et Rhizoma Praeparata Cum Melle based on color digitization and multi-component determination].

To explore the color value changes after processing and further explore the correlations between color values and internal components, we established a rapid evaluation method for the quality of Glycyrrhizae Radix et Rhizoma and Glycyrrhizae Radix et Rhizoma Praeparata Cum Melle. In this study, the color values of Glycyrrhizae Radix et Rhizoma and Glycyrrhizae Radix et Rhizoma Praeparata Cum Melle were digitized by a spectrophotometer, and the standard ranges of color values of the two herbal medicines were established. Further, a discriminant analysis model was established to quickly and accurately distinguish the two herbal medicines. The content of 9 flavonoids and 1 triterpene in Glycyrrhizae Radix et Rhizoma and Glycyrrhizae Radix et Rhizoma Praeparata Cum Melle were determined by HPLC, and Pearson correlation analysis was adopted to analyze the correlations between the color values and the content of 10 components. The standard ranges of L~*, a~*, and b~* values were 65.539 6-68.305 8, 7.296 3-8.467 3, and 29.998 8-32.212 8 for Glycyrrhizae Radix et Rhizoma, and 43.654 3-47.166 4, 14.050 0-15.133 8, and 16.424 6-20.984 8 for Glycyrrhizae Radix et Rhizoma Praeparata Cum Melle, respectively. Glycyrrhizae Radix et Rhizoma had higher L~* and b~* values and lower a~* value than Glycyrrhizae Radix et Rhizoma Praeparata Cum Melle, which indicated that processing with honey decreased the white and yellow values and increased the red value. The original and cross validation of the established discriminant analysis model met the requirements, and the external validation of the model showed the prediction accuracy of 100%. Pearson correlation analysis showed that the a~* value was positively correlated with the content of liquiritin apioside and isoliquiritin apioside(P<0.05), while the L~* and b~* values were negatively correlated with the content of the above two components(P<0.05). After processing with honey, L~* and b~* decreased while a~* increased, and the content of liquiritin apioside and isoliquiritin apioside increased, which was consistent with the content determination results. This study reveals the regularity of the color values of Glycyrrhizae Radix et Rhizoma after processing with honey roasting, as well as the correlations between color values and component content, which provides a basis for the rapid quality evaluation of Glycyrrhizae Radix et Rhizoma and Glycyrrhizae Radix et Rhizoma Praeparata Cum Melle.

Profiling and analysis of multiple constituents in Crataegi Fructus before and after processing by ultrahigh-performance liquid chromatography quadrupole time-of-flight mass spectrometry.

RATIONALE: Crataegi Fructus (CF) is one of the most commonly used herbal medicines with a long history of clinical applications. CF is often processed to minimize gastric membrane irritation, although differently processed products can have different biological effects. The purpose of this study was to comprehensively identify the chemical composition of CF, determine the changes caused by processing, and elucidate the active constituents causing the clinical effects. This study aimed to define a theoretical basis for intensive mechanistic studies of CF processing and its reasonable clinical applications. METHODS: An optimized ultrahigh-performance liquid chromatography quadrupole time-of-flight mass spectrometry (UHPLC/QqTOFMS) method in positive and negative ion modes, coupled with multivariate statistical analyses, was developed for the identification and analysis of chemical components in raw and processed products of CF. RESULTS: A total of 87 compounds were identified, including 61 marker compounds that were found to be primary contributors to the significant differences (p < 0.01) between raw and processed products using principal component analysis, t-test, and Venn analysis. The conversion mechanism for a subset of the changed compounds was inferred by analyzing 25 unique differential components between the raw and processed CF. CONCLUSIONS: A rapid and efficient analytical method for identifying the chemical components in CF before and after processing was successfully established. We show how the changes in the chemical constituents in processed CF could be investigated using multivariate statistical analysis methods, and thus facilitate understanding of the processing mechanism of CF.

Analysis of the chemical composition changes of Gardeniae Fructus before and after processing based on ultra-high-performance liquid chromatography quadrupole time-of-flight mass spectrometry.

Gardeniae Fructus, the dry fruit of Gardenia jasminoides Ellis, has been widely used for the treatment of different diseases. Although four types of processed Gardeniae Fructus products, characterized by differing effects, are available for clinical use, little is known regarding the respective processing mechanisms. In this study, ultra-high-performance liquid chromatography quadrupole time-of-flight mass spectrometry combined with multivariate statistical analysis was applied to characterize the chemical profiles of the differently processed Gardeniae Fructus products and to determine differences in their chemical compositions, thereby enabling us to identify those active compounds associated with the observed clinical effects. A total of 125 compounds were accordingly identified, among which, 56 were established as primary contributors to the significant differences (P < 0.01) between crude and processed Gardeniae Fructus, based on t-test analysis. Furthermore, the potential mechanisms underlying the chemical transformations that occurred during processing were discussed. The findings of this study may not only contribute to the more effective quality control of Gardeniae Fructus but also provide basic information for elucidating the mechanisms underlying the changes in chemical constituents in response to processing, and provide a basis for further investigations of Gardeniae Fructus processing mechanisms.

A new method for detecting Na+ , K+ -ATPase activity by ICP-MS: Quantitative analysis on the inhibitory effect of rhein on Na+ , K+ -ATPase activity by ICP-MS in HCT116 cells.

Rhein is an active component from Chinese herbal medicine. It can cause diarrhea by inhibiting Na+ , K+ -ATPase activity on intestinal epithelial cells, thus decreasing the re-absorption of Na+ from intestinal tract to blood. However, when this Na+ , K+ -ATPase inhibition was quantitated by a colorimetric method that measures ATPase-catalyzed release of inorganic phosphorus, the data obtained were inconsistent and showed great variation. We developed a novel method using inductively coupled plasma mass spectrometry (ICP-MS) to quantitate the amount of intracellular Rb+ . This method largely mimics the 86 RbCl tracer flux assay, but it uses non-radioactive RbCl as a flux substrate. The results demonstrated that this method has better precision and accuracy than the conventional colorimetric method. More importantly, this method is free from radioactive substances, which is expected to make it safer and more convenient than the radioactive 86 RbCl tracer flux method. In conclusion, the ICP-MS method for Na+ , K+ -ATPase activity determination is novel and accurate. It can also provide a reference for studying the transport of other metal ions across membranes under biological conditions.

[Study on quality identification of Curcumae Rhizoma from different origins based on quantitative analysis of appearance color and content of main components].

L~*, a~* and b~* values of prepared slices of Curcumae Rhizoma were measured by spectrophotometer. SPSS 21.0 was used for discriminant analysis to establish the color range and mathematical prediction model of prepared slices of Curcumae Rhizoma. The values of L~*, a~* and b~* of kwangsiensis ranged from 58.09-62.40, 4.53-5.66 and 23.61-24.29, while the values of L~*, a~* and b~* of phaeocaulis were between 64.02-70.71,-0.89-4.13 and 44.59-54.52, respectively. The values of L~*, a~* and b~* of wenyujin were 68.55-70.99,-0.11-1.47 and 28.26-32.19, respectively. The mathematical prediction model was proved to be able to realize 100% identification of Curcumae Rhizome of different origins through original and cross validation and external samples validation. A dual wavelength HPLC was established; the contents of 9 sesquiterpenoids and 3 Curcumae Rhizomes were determined simultaneously; and the contents of Curcumae Rhizome of different origins were determined. The results showed that kwangsiensis had higher contents of neocurdione, ß-elemene and isocurcumaenol, phaeocaulis curcumin, furadienone, demethoxycurcumin and curcumin; and wenyujin mainly contained curdione, furadienes and guimarone. Pearson correlation analysis on L~*, a~*, b~* value and content of 12 components showed that curcumin, furadienone, demethoxycurcumin and curcumin had a significant positive correlation with b~* value(P<0.01). There was a significant negative correlation between neocurdione, ß-elemene and isocurcumaenol and L~* value(P<0.01). Curdione, furadienes and guimarone were significantly correlated with L~* value(P<0.01),indicating that the appearance co-lor of Curcumae Rhizoma could reflect the change of the content of the internal components. This study provided reference for the rapid recognition of Curcumae Rhizoma and the establishment of quality evaluation system.

GC-MS based metabolomics uncovers the mechanism of Curcumae rhizoma and Sparganii rhizome on blood stasis syndrome in liver dialysis.

Blood stasis syndrome (BSS) is characterized by blood retardation and is the major cause of some deadly diseases. Some factors that affect BSS have been identified. However, the small molecule that related to BSS is still largely unknown. Traditional Chinese Medicine (TCM), such as Sanleng and Ezhu, has been used for a long time in treating BSS and promising outcomes have been achieved. However, the mechanism of how they work is unclear. Thus, we constructed the Rat BSS model and treated them with Sanleng and Ezhu. Then, the liver dialysis of those rats was collected and the small molecule metabolites were analyzed by GC-MS based metabolomics approach. Our results showed after Sanleng and Ezhu treatment, several small molecule metabolites were significantly changed metabolites (VIP>1 and P<0.05). Pathway enrichment analysis also showed that Sanleng and Ezhu share the similar mechanism in treating BSS, such as regulating Glyoxylate and dicarboxylate metabolism pathway and energy metabolism. Besides, we also identified some key metabolites that were significantly correlated with BSS. In conclusion, those findings uncover the mechanism of Sanleng and Ezhu in treating BSS.

Quality evaluation of raw and processed Crataegi Fructus by color measurement and fingerprint analysis.

Crataegi Fructus and its processed products have been used as a traditional medicine for a long time, and numerous active components are responsible for their curative effects. However, a comprehensive and fast method for the quality control of its processed products is still lacking. In this study, two analytical methods based on color measurements and fingerprint analysis are established. In the color measurements, the color values of the peel and flesh of Crataegi Fructus were evaluated spectrophotometrically. Based on the results, a color reference range was established using percentiles, and the standard color difference value was established using the median color values. Then, the color values of Crataegi Fructus and its processed products were analyzed using Bayes linear discriminant analysis and mathematical functions were built in order to predict the degree of processing. Moreover, high-performance liquid chromatography fingerprint analysis was performed on a Hibar C18 column, and a high-performance liquid chromatography fingerprint pattern was obtained, from which nine peaks were identified. Chemometric methods were successfully applied to differentiate raw and processed Crataegi Fructus.

[Problems and solutions in modern research of traditional Chinese herbal pieces processing technology].

Chinese medicine processing is the main feature that distinguishes traditional Chinese medicine from natural medicine and plant medicine, and is the main feature in clinical medication of traditional Chinese medicine. The research of Chinese medicine processing technology is an important link to realize standardization and standardization of Chinese herbal pieces, with urgent need to attract high attention. At present, there are still many problems in the research of processing technology of Chinese herbal pieces, mainly including inconsistent processing technology, large differences in process technology parameters, and unstable production technology of Chinese herbal pieces, resulting in uncontrollable quality of Chinese herbal pieces and affecting the clinical efficacy of Chinese medicine. This paper focused on the establishment of a unified standard processing technology, and put forward the countermeasures for the processing technology of Chinese medicine based on a comprehensive analysis of the current situations of the processing technology of Chinese herbal pieces, with significance for guiding the establishment of a standardized processing technology of Chinese medicine.

Study of organic acids in Schisandrae Chinensis Fructus after vinegar processing.

The ripened fruit of Schisandrae Chinensis Fructus has unique medical properties in Chinese medicine. It is commonly used after vinegar steaming. Vinegar steaming changes the color of Schisandrae Chinensis Fructus from red to black and enhances its acidic and astringent properties. Lignans are the well-investigated components in this herb. However, Schisandrae Chinensis Fructus is acidic in the theory of Chinese medicine, and whether vinegar processing changes its organic acid components remains largely unknown. In this study, the organic acids in this herb were derived by the method of methyl esterification, and further analyzed by gas chromatography with mass spectrometry. A total of 39 organic acid compounds were identified. Interestingly, Schisandrae Chinensis Fructus after vinegar processing showed a significant increase in the content of levulinic acid as compared to the unprocessed ones. Pharmacological experiments demonstrated that levulinic acid inhibited the contractility of isolated intestine and had an inhibitory effect on the excessive hyperfunction of small intestinal propulsion. Moreover, the extracts of vinegar-processed Schisandrae Chinensis Fructus had a stronger inhibitory on the excessive hyperfunction of small intestinal propulsion than that of unprocessed ones. Taken together, this study offers novel insight into the effect of Schisandrae Chinensis Fructus after vinegar processing.

Qualitative analysis of multiple compounds in raw and prepared Semen Cassiae coupled with multiple statistical strategies.

In China, Semen Cassiae is used clinically to improve eyesight, relieve constipation, and to treat headache and dizziness. Prepared Semen Cassiae is obtained by stir-frying raw Semen Cassiae until it turned dark brown, micro dilatancy, and overflow aroma. After processing, the therapeutic effects change-the purgation effect is alleviated and the hepatoprotective effect is enhanced. To explore the changes in chemical compositions of Semen Cassiae after processing and clarify the material basis of the changed therapeutic effects, an ultra-high performance liquid chromatography with quadrupole time-of-flight mass spectrometry coupled with automated data analysis software and statistical strategy was developed. As a result, 53 compounds in raw Semen Cassiae and 43 compounds in prepared Semen Cassiae were found, a total of 55 chemical compounds were identified. Principle component analysis and t-test were processed by Markerview 1.2.1 software. Finally, 39 peaks were found to be the main contributors to the significant difference (p < 0.05) between raw and prepared Semen Cassiae. Compared with raw Semen Cassiae, 19 peaks showed a higher intensity in prepared Semen Cassiae, while the contents of 20 compounds in prepared Semen Cassiae were lower, most of which belonged to naphthopyrones glycosides and anthraquinone glycosides.

DECOCTION PROCESS OPTIMIZATION AND QUALITY EVALUATION OF YI-HUANG DECOCTION BY HPLC FINGERPRINT ANALYSIS.

Yi Huang decoction (YHD) has been used as one of famous traditional formula because of its unique effectiveness against gynecological diseases. YHD is composed of five herbs, including the rootstock of Dioscoma opposita Thunb. (Dioscoreaceae), the kernel of Etayale ferx Salisb. (Nymphaeaceae), the bark of Phellodendron chinense Schneid. (Rutaceae), the seed of Plantago asiatica L. (Plantaginaceae), and the seed of Ginkgo biloba L. (Ginkgoaceae). To effectively control the quality, the processing method for YHD was optimized by means of single factor test as well as orthogonal test in this study. A completely validated method based on HPLC coupled with diode array detector was performed on a Kromasil C(18) column at 30° with mobile phase of 0.1% aqueous phosphoric acid and acetonitrile. As a result, HPLC fingerprint on the basis of the chromatographic data from 32 batches of samples was obtained, which contained 44 common peaks. Among these common peaks, 6 peaks were identified as geniposidic acid, berberine hydrochloride, palmatine hydrochloride, phellodendrine chloride, magnoflorine, and verbascoside, respectively, based on their retention time relative to the standards. Meanwhile, the contents of these 6 compounds were also simultaneously examined. In sum, this study offered valuable information for the proper processing and quality control for YHD.

Quality control of processed Crataegi Fructus and its medicinal parts by ultra high performance liquid chromatography with electrospray ionization tandem mass spectrometry.

Crataegi Fructus, an edible food, has been used as a traditional medicine to treat diseases for many years. There is substantial evidence that multiple constituents are responsible for the beneficial effects of Crataegi Fructus. To effectively control the quality of this herbal medicine, we developed an ultra high performance liquid chromatography with electrospray ionization tandem mass spectrometry protocol to simultaneously quantify ten compounds (chlorogenic acid, procyanidin B2, l-epicatechin, glucosylvitexin, vitexin-2-O-rhamnoside, vitexin, rutin, hyperoside, isoquercitrin, and quercetin) in Crataegi Fructus. Multiple-reaction monitoring was used for the quantification in the negative mode for 8 min. This proposed method is simple, reliable, sensitive, and specific. Further, the quantification parameters, including linearity, limit of detection, limit of quantification, precision, reproducibility, stability, and accuracy were optimized. The quality of the processed samples of Crataegi Fructus was evaluated using this method. Additionally, the method was successfully used to distinguish the medicinal components, including peel, kernel, and flesh. The data described in this study offer valuable information for the quality control and proper use of Crataegi Fructus.

Quality assessment of raw and processed Arctium lappa L. through multicomponent quantification, chromatographic fingerprint, and related chemometric analysis.

In traditional Chinese medicine, raw and processed herbs are used to treat different diseases. Suitable quality assessment methods are crucial for the discrimination between raw and processed herbs. The dried fruit of Arctium lappa L. and their processed products are widely used in traditional Chinese medicine, yet their therapeutic effects are different. In this study, a novel strategy using high-performance liquid chromatography and diode array detection coupled with multivariate statistical analysis to rapidly explore raw and processed Arctium lappa L. was proposed and validated. Four main components in a total of 30 batches of raw and processed Fructus Arctii samples were analyzed, and ten characteristic peaks were identified in the fingerprint common pattern. Furthermore, similarity evaluation, principal component analysis, and hierachical cluster analysis were applied to demonstrate the distinction. The results suggested that the relative amounts of the chemical components of raw and processed Fructus Arctii samples are different. This new method has been successfully applied to detect the raw and processed Fructus Arctii in marketed herbal medicinal products.

[Fingerprint of Vinegar Processed Genkwa Flos Based on Improving Euclidean Distance].

OBJECTIVE: To improve the traditional fingerprint method to distinguish vinegar processed Genkwa Flos from raw Genkwa Flos. METHODS: Ten batches of Genkwa Flos were collected, processed with vinegar through a standard method, and then analyzed under the optimum HPLC condition. Based on the chromatographic data obtained, a common model of vinegar processed Genkwa Flos fingerprints, including 11 common peaks and the components genkwanin, hydroxygenkwanin, luteolin, apigenin and yuanhuacin were identified, was established. The peak of baicalein, an exogenous component added quantitatively to the samples as an internal standard, was served as the reference peak. The similarity between the test samples and the common model was computed using the improved Euclidean distance method developed in this paper. RESULTS: The similarities between vinegar processed Genkwa Flos samples and the common model were higher than 0.9, whereas those between raw Genkwa Flos and the common model were lower than 0.9. CONCLUSION: The proposed method thus effectively provides a clear distinction between vinegar processed and raw Genkwa Flos samples. The result is helpful to ensure the safe clinical use of the plant and expand the application field of fingerprinting technology.

Comparative pharmacokinetics and tissue distribution of schisandrin, deoxyschisandrin and schisandrin B in rats after combining acupuncture and herb medicine (schisandra chinensis).

Recently, combination therapy with acupuncture and medicine as a practical strategy to treat diseases has gained increasing attention. The present study aimed to investigate whether acupuncture stimulation at ST.36 had a potential impact on the pharmacokinetics and tissue distribution of lignans. An HPLC-ESI/MS analytical method was established and successfully applied to a comparative study of drug concentration in plasma and tissues of three lignans. The parameters area under the plasma concentration-time curve from time zero to the final measurable point and from time zero to infinity, and peak concentration were significantly increased, with a prolonged mean residence time and a corresponding decrease in clearance in comparision with the Schisandra-alone group. Additionally, tissue concentrations of three lignans were improved in the group with acupuncture, especially in liver. The results indicated that acupuncture has a synergistic effect on the pharmacokinetics and tissue distribution of the three lignans, which could postpone their elimination, resulting in a longer blood circulating time in rat plasma and prolonged residence time in target tissues, leading to higher tissue concentration. The findings provide some scientific evidence for the mechanism of the combined use of acupuncture and herbal medicine. Furthermore, we suggest that acupuncture and its combination with herbal medicine should be investigated further as a possible adjuvant therapy in clinical treatment for liver injury.

[Research on chemical reactions during ginseng processing].

As a kind of commonly used traditional Chinese medicine, ginseng has a high reputation at home and abroad. The research of ginseng has been expanded to medicine, pharmacy, biology, food science and other fields, with great achievements in recent years. Ginseng contains ginsenosides, volatile oil, carbohydrates, amino acids, polypeptides, inorganic elements and othser chemical constituents. Each component has extensive physiological activity, and is the base of ginseng's effect. After processing, the complicated changes are taken place in the constituents of ginseng, and some new substances produced. This paper aims to review the studies on chemical constituents and their mechanisms during ginseng processing, and the ideas, methods and the direction of the development of traditional Chinese medicine processing in the future.

[Progress of sulfur fumigation and modern processing technology of Chinese traditional medicines].

Infestation, moldy and other phenomenon in the processing and storage of Chinese herbal medicines is a problem that faced in the production of Chinese traditional medicine. The low productivity of traditional processing methods can not guarantee the quality of Chinese herbal medicines. Sulfur fumigation is the first choice of grassroots to process the Chinese herbal medicine with its low cost and easy operation. Sulfur fumigation can solve some problems in the processing and storage of Chinese herbal medicines, but modern pharmacological studies show that long-term use of Chinese traditional medicine which is fumigated by sulfur can cause some serious harm to human liver, kidney and other organs. This paper conducts a review about the application history of sulfur fumigation, its influence to the quality of Chinese herbal medicines as well as domestic and foreign limits to sulfur quantity, and a brief introduction of the status of modern processing technologies in the processing of food and some Chinese herbal medicines, the problems ex- isting in the Chinese herbal medicines processing, which can provide a reference basis for the further research, development and application of investigating alternative technologies of sulfur fumigation.

[Research situation of effects of sulfur fumigation on quality of traditional Chinese medicine].

Sulfur fumigation (SF) is a universal phenomenon in primary processing of Traditional Chinese Medicine (TCM) in modern times. In the process, fumigation, sulfur or both of them act on the TCMs. Some active components of TCMs change quantitatively or qualitatively during the processing. At the same time, the sulfur dioxide and heavy metal would remain and cause a serious influence on quality and future development of TCM. This article reviews the chemical compositions change after SF to study the change law and their influence on quality. This article provide references for SF in TCMs' processing for a better and safer quality.