A comparative analysis of raw and processed Radix Paeoniae Alba samples using HPLC,chemometrics, and antioxidant activity

Radix Paeoniae Alba (RPA) and its processed products are commonly used in traditional Chinese medicine, but the chaos phenomenon among processed products often occurs. In this study, we used multiple chemometric methods to analyze raw and six different processed products of RPA based on HPLC fingerprinting. Heat map analysis was used to assess the changes in chemical composition. Principal component analysis was used for classification, and the samples were divided into four classes: class 1 (raw, wine-processed, and vinegar-processed products), class 2 (bran-processed and soil-processed products), class 3 (stir-fried products), and class 4 (coke products). Further, the orthogonal partial least squares discriminant analysis model was used to obtain chemical markers among different classes. The antioxidant property of RPA is an important factor responsible for its pharmacological effects, and so the antioxidant activity of RPA was also investigated. We measured 2,2-diphenyl-1-picrylhydrazyl radical (DPPH) and hydroxyl radical scavenging ability, and ferric reducing antioxidant power. The total antioxidant activity follows the order: coke > stir-fried > soil-processed > bran-processed > wine-processed > raw > vinegar-processed products. These results suggest that different processing methods affect the chemical composition and antioxidant power of RPA, and thus, different products of RPA should not be mixed.     

Comparison of the active components of Aster tataricus from different regions and related processed products by ultra‐high performance liquid chromatography with tandem mass spectrometry

We investigated crude Aster tataricus, vinegar‐processed Aster tataricus, honey‐processed Aster tataricus, and steamed Aster tataricus as a case study and developed a comprehensive strategy integrating quantitative analysis and chemical pattern recognition methods for the evaluation and differentiation of Aster tataricus from different regions, as well as related processed products. In the study, 15 batches of raw Aster tataricus collected from seven provinces were analyzed. A sensitive and rapid ultra‐high performance liquid chromatography with tandem mass spectrometry method for simultaneous determination of 15 compounds was established to evaluate the quality of raw and processed Aster tataricus. Furthermore, multivariate statistical techniques were applied to compare the differences among Aster tataricus samples. As a result, the herbs collected from seven provinces were divided into two categories, and chlorogenic acid was the most important component distinguishing between the regions. Moreover, all of the raw and processed samples were classified by partial least squares discriminant analysis based on the 15 analyzed compounds. Results showed that raw Aster tataricus, vinegar‐processed Aster tataricus, honey‐processed Aster tataricus, and steamed Aster tataricus were clustered in four different areas. Shionone, chlorogenic acid and kaempferol were the significant constituents differentiating the raw and differently processed Aster tataricus samples.     

A multi-evaluating strategy for raw and processed Veratrum nigrum L.: Fingerprinting combined with quantitative analysis based on multivariate chemometric methods

Veratrum nigrum L. (VN) is a well-known herbal medicine and rich in chemical components with multiple pharmacological activities including antihypertensive, anticancer, and antifungal effects. In the current experiment, the quality of VN from different habitats was evaluated based on combinative method of fingerprint, multi-component quantification and chemical pattern recognition. Fifteen batches of VN were collected, and intrinsic chemical composition were identified using ultra-performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry, which is a method for analyzing the similarity between samples, coupled with fingerprint of traditional Chinese medicine. The fingerprint similarity model show that 22 common peaks were selected covering 15 batches of and the similarity > 0.963. The total of 22 joint components were tentatively identified by comparison with standard substances or literature. A ultra-high performance liquid chromatography coupled with triple quadrupole mass spectrometry method for simultaneous determination of 8 compounds was established to evaluate the contents of raw and processed Veratrum nigrum L. Multivariate analysis was then applied to compare different batches of herbs based on ultra-high performance liquid chromatography coupled with triple quadrupole mass spectrometry data. All raw and processed samples were classified by partial least squares discriminant analysis based on the 8 analyzed compounds. The findings suggested that veratramine and polydatin with a variable importance for the project (VIP) > 1 were identified as significant constituents, the presence of which can be used to differentiate between raw and processed Veratrum nigrum L. samples. These results indicate that processing methods show important effects on the composition of Veratrum nigrum L..     

Comparison of the chemical profiles of fresh‐raw and dry‐processed Juglans mandshurica

The processing of Juglans mandshurica Maxim. is important to reduce its toxicity and enhance its efficacy. Simple, efficient, and sensitive ultra‐high performance liquid chromatography coupled with a time‐of‐flight mass spectrometry based chemical profiling approach was proposed to rapidly evaluate the chemical difference between fresh and dry samples. Under the optimized ultra‐high performance liquid chromatography and quadrupole time‐of‐flight tandem mass spectrometry conditions, 81 significantly different compounds were rapidly discovered using principal component analysis, and then tentatively identified by comparison with reference substances or inferred through mass spectral fragment ion analysis and literature data. These compounds included 35 naphthoquinones, 11 diarylheptanoids, nine flavonoids, eight triterpenes, 12 phenolic acids, and six aliphatics. The results demonstrated that chemical reactions occurring during processing could be used to elucidate the processing mechanism of Juglans mandshurica Maxim. This study provides a novel approach to identifying complicated components of various complex mixtures in fresh‐raw and dry‐processed traditional Chinese medicines, which could be used as a valid analytical method to further understand the processing mechanisms of these medicines, as well as providing intrinsic quality control of the medicines and their processed products.     

Chemical differentiation of volatile compounds in crude and processed Atractylodis Macrocephalae Rhizoma by using comprehensive two‐dimensional gas chromatography with time‐of‐flight mass spectrometry combined with multivariate data analysis

In the present study, comprehensive 2D GC—TOF‐MS combined with multivariate data analysis was applied to analyze the differences of the volatile components in crude and processed Atractylodis Macrocephalae Rhizoma (AMR) samples. As a result, 26 compounds that were found in crude AMR samples disappeared in processed AMR samples, and 19 compounds were newly generated and identified in AMR after processing with wheat bran. Meanwhile, principal component analysis demonstrated that there were significant chemical differences between crude and processed AMR samples, and processing procedure caused obvious quantitative and qualitative changes of volatile components in AMR. The established method could be used to explain the chemical differentiation between crude and processed AMR, and to further understand the processing mechanism of herbal medicines.     

Effect of Different Processing Methods on the Chemical Constituents of Scrophulariae Radix as Revealed by 2D NMR-Based Metabolomics

Scrophulariae Radix (SR) is one of the oldest and most frequently used Chinese herbs for oriental medicine in China. Before clinical use, the SR should be processed using different methods after harvest, such as steaming, “sweating”, and traditional fire-drying. In order to investigate the difference in chemical constituents using different processing methods, the two-dimensional (2D) ¹H-¹³C heteronuclear single quantum correlation (¹H-¹³C HSQC)-based metabolomics approach was applied to extensively characterize the difference in the chemical components in the extracts of SR processed using different processing methods. In total, 20 compounds were identified as potential chemical markers that changed significantly with different steaming durations. Seven compounds can be used as potential chemical markers to differentiate processing by sweating, hot-air drying, and steaming for 4 h. These findings could elucidate the change of chemical constituents of the processed SR and provide a guide for the processing. In addition, our protocol may represent a general approach to characterizing chemical compounds of traditional Chinese medicine (TCM) and therefore might be considered as a promising approach to exploring the scientific basis of traditional processing of TCM.     

Global detection and identification of components from crude and processed traditional Chinese medicine by liquid chromatography connected with hybrid ion trap and time‐of‐flight‐mass spectrometry

We herein present a chemical profiling method to efficiently process the information acquired by ultra fast liquid chromatography (UFLC)‐electrospray ionization source in combination with hybrid ion trap and high‐resolution time‐of‐flight mass spectrometry (UFLC‐(ESI)‐IT‐TOF/MS), facilitating the structural determination of serial components contained in crude or processed traditional Chinese medicine (TCM). Under the optimized UFLC and IT‐TOF‐MSⁿ conditions, over 39 compounds were separated and detected in crude or processed Fructus corni within 25 min. The components were identified by comparing the mass spectra and retention time with reference compounds, or tentatively assigned by elucidating low‐energy collision‐induced dissociation (CID) fragment ions and matching empirical molecular formula with that of the published compounds. Several factors in the processing procedure were examined. The experimental results demonstrate that the chemical reactions that occurred in the processing procedure can be used to elucidate the processed mechanism of F. corni, which is regularly affected by the processing conditions. This study provides a novel approach and methodology to identify the complicated components from various complex mixtures such as crude TCM, processed TCM, and biological samples. It can be used as a valid analytical method for further understanding the processing mechanism of TCM, along with the intrinsic quality control of TCM and its processed product.     

Newly Generated Atractylon Derivatives in Processed Rhizomes of Atractylodes macrocephala Koidz

Thermally processed rhizomes of Atractylodes macrocephala (RAM) have a long history of use in traditional Chinese medicine (TCM) for treating various disorders, and have been an integral part of various traditional drugs and healthcare products. In TCM, herbal medicines are, in most cases, uniquely processed. Although it is thought that processing can alter the properties of herbal medicines so as to achieve desired functions, increase potency, and/or reduce side effects, the underlying chemical changes remain unclear for most thermally processed Chinese herbal medicines. In an attempt to shed some light on the scientific rationale behind the processes involved in traditional medicine, the RAM processed by stir-frying with wheat bran was investigated for the change of chemical composition. As a result, for the first time, five new chemical entities, along with ten known compounds, were isolated. Their chemical structures were determined by spectroscopic and spectrometric analyses. The possible synthetic pathway for the generation of such thermally-induced chemical entities was also proposed. Furthermore, biological activity evaluation showed that none of the compounds possessed cytotoxic effects against the tested mammalian cancer and noncancer cell lines. In addition, all compounds were ineffective at inhibiting the growth of the pathogenic microorganisms.     

Biologically active oligostilbenes from the stems of Vatica mangachapoi and chemotaxonomic significance

Phytochemical investigation of the stems of Vatica mangachapoi (Dipterocarpaceae) led to the isolation and structural elucidation of twenty-seven oligostilbenes (1–27), including a new natural compound 1. The structure of 1 was elucidated on the basis of spectroscopic analyses including NMR, MS and ECD data, and the known compounds were identified by comparisons with those reported in the literature. The absolute configuration of 1 was first time determined by a combination of NOESY spectrum and quantum chemical computation. Among of isolates were tested for their anti-osteoporosis and anti-HIV-1 activities in vitro by the MTT method. Moreover, the chemotaxonomic significance of these compounds was summarised.     

A Comparison of Solid-Phase Extraction Techniques for Assay of Drugs in Aqueous and Human Plasma Samples

Abstract

Six commercially available solid adsorbent materials were evaluated for their applicability as effective tools for extraction of drugs from aqueous and human plasma samples. Ten model compounds were selected as representative of the acidic, basic, amphoteric, hydrophobic, and hydrophilic drug classes. Percent recovery and precision data for each model drug on each solid adsorbent material were calculated using spiked water and/or plasma samples. Octadecylsilane materials were the best overall choice for extraction of the different chemical classes of drugs from water and plasma samples, giving both highest recovery and best reproducibility data for a majority of the drugs studied. It was also determined that good extractability for basic drugs could be obtained using either XAD-2, Clin-eht® or cyanopropyl columns. In addition, XAD-2 gave good recoveries of amphoteric compounds and Clin-elut® was good for hydrophobic drugs.     

Chemical Composition of Volatile Compounds in Apis mellifera Propolis from the Northeast Region of Pará State,Brazil

Propolis is a balsamic product obtained from vegetable resins by exotic Africanized bees Apis mellifera L., transported and processed by them, originating from the activity that explores and maintains these individuals. Because of its vegetable and natural origins, propolis is a complex mixture of different compound classes; among them are the volatile compounds present in the aroma. In this sense, in the present study we evaluated the volatile fraction of propolis present in the aroma obtained by distillation and simultaneous extraction, and its chemical composition was determined using coupled gas chromatography, mass spectrometry, and flame ionization detection. The majority of compounds were sesquiterpene and hydrocarbons, comprising 8.2–22.19% α-copaene and 6.2–21.7% β-caryophyllene, with additional compounds identified in greater concentrations. Multivariate analysis showed that samples collected from one region may have different chemical compositions, which may be related to the location of the resin’s production. This may be related to other bee products.     

High-resolution magic angle spinning nuclear magnetic resonance (HR-MAS-NMR) as quick and direct insight of almonds

Abstract

Almonds are the tasty seeds of Prunus dulcis plants globally appreciated for the pleasant palatability and remarkable nutritional value, therefore it is very spread as snack and as basic ingredient of the confectionery products. The HR-MAS-NMR is a simple spectroscopy able to directly and quickly explore the chemical composition of powdered seed samples dispersed in D₂O. ¹H spectra witness the remarkable presence of triglyceride fatty esters together with sucrose; other minor water soluble metabolites are also detectable. This very rough approach is effectively providing chemical profiles featuring almond samples. In this analysis we were able to statistically distinguish the “Avola” almonds from other marketed products submitted to the same analysis. This is just a first investigation based on the main compounds but it might pave the way toward the quantitative evaluation of many other compounds in the almond therefore implementing the HR-MAS-NMR knowledge of these precious seeds.     

Chemical constituents from the roots of <Emphasis Type="Italic">Senecio scandens</Emphasis>

The chemical constituents of the roots of Senecio scandens Buch.-Ham. grown in the Funiu mountains in China have been investigated. Four compounds were isolated and identified as β−sitosterol (1), pentacosanoic acid (2), 19α-H lupeone (3), and sucrose (4). The structures of these compounds were elucidated on the basis of chemical and spectroscopic evidence. 19α-H Lupeone (3) was isolated as a single compound and its structure established unambiguously by the spectral method for the first time, and ¹H and ¹³C NMR data were assigned wholly by 1D and 2D NMR.     

Unusual molecular pattern in Ajugoideae subfamily: the case of Ajuga genevensis L. from Dolomites

We analysed the ethanolic extract from Ajuga genevensis L. (Lamiaceae) growing in Dolomites, part of Italian Alps. Three new compounds for this species were identified: rosmarinic acid (1), oleanolic acid (2) and maslinic acid (3), representative of two different classes of chemical compounds (phenylpropanoids and pentacyclic triterpenes). A. genevensis resulted to be a valuable source of these compounds endowed with interesting biological activities (i.e. antioxidant, neuroprotective, anti-inflammatory, antiproliferative). The recognition of compounds (1), (2) and (3) may also confirm the ethnomedicinal uses of this plant. From a chemotaxonomical point of view, it is worth noting that iridoids were not evidenced in this accession. Iridoids are considered chemotaxonomic marker in Lamiales, and, in contrast with a previous study on this species, the presence of aucubin was not confirmed. In addition, the presence of large amounts of rosmarinic acid (1) was unexpected for a species that does not belong to subfamily Nepetoideae.     

Chemical constituents from the fruits of <Emphasis Type="Italic">Ligustrum lucidum</Emphasis>

One new δ-valerolactone (1) and one new natural phenolic glycoside 2, together with four known compounds 3–6, were isolated from the fruits of Ligustrum lucidum. Their structures were elucidated on the basis of spectral data. The chemical transformation from 2 to 3 was observed. The immunomodulatory activities of the compounds were also evaluated.     

Fingerprint analysis of Ligusticum chuanxiong using hydrophilic interaction chromatography and reversed-phase liquid chromatography

Fingerprint analysis is considered one of the most powerful approaches to quality control in traditional Chinese medicines (TCMs). In this study, a binary chromatographic fingerprint analysis was developed using hydrophilic interaction chromatography (HILIC) and reversed-phase liquid chromatography (RPLC) to gain more chemical information about polar compounds and weakly polar compounds. This method was used to construct a chromatographic fingerprint of Ligusticum chuanxiong. The two chromatographic methods demonstrated good precision, reproducibility, and stability, with relative standard deviations of <2% for retention time and 7% for peak area for both HILIC and RPLC separations. Data from the analysis of 14 samples by HILIC and RPLC were processed with similarity analysis, with correlation coefficients and congruence coefficients. This binary fingerprint analysis, using two chromatographic modes, is a powerful tool for characterizing the quality of samples, and can be used for the comprehensive quality control of TCMs.     

Identification of volatile aroma compounds in processed cheese analogues based on different types of fat

The simple and rapid solid-phase micro-extraction method using gas chromatography was used for the identification and quantification of volatile aroma compounds in various types of processed cheese analogues produced from different types of fat (butter, butter oil, coconut oil, palm oil, and sunflower oil). In total, 31 organic compounds belonging to five chemical groups were identified, with the alcohols and fatty acids quantitatively predominant. The contents of the aroma compounds (the so-called aroma profiles) of the analogues and corresponding fats used as raw materials were compared. Significant differences (p < 0.05) were found between samples. The highest total content of aroma compounds was found in coconut oil analogue ((547.30 ± 9.82) mg kg^?1), the lowest in palm oil analogue ((372.01 ± 16.16) mg kg^?1). The concentrations of aroma compounds in fats were substantially lower (p < 0.05) than in analogues. Hence, the largest number of aroma analogues came from Edam cheese used for production as a protein source.     

Two new spongian diterpene analogues isolated from the marine sponge Acanthodendrilla sp

Abstract

Two new marine natural compounds, 3β-acetoxy-15-hydroxyspongia-12-en (1) and 3-methylspongia-3,12-dien-16-one (2), were isolated from the marine sponge Acanthodendrilla sp., collected in Pulau-Pulau. Compounds 1 and 2 represent new chemical entities of the known spongian diterpene family. Compound 1 is a new 3-acetoxyspongia and compound 2 presents an unreported rearranged 3-methylspongia-3-en. Their structures, including relative configurations, were fully elucidated based on 1D and 2D NMR analyses, as well as HRESTOFMS experiments. No significant bioactivities were found for these compounds. This work reports two new chemical structures, compounds 1 and 2, together with the first isolation of spongian diterpenes from Acanthodendrilla genus.     

Identifying the chemical markers in raw and wine-processed Scutellaria baicalensis by ultra-performance liquid chromatography/quadrupole time-of-flight mass spectrometry coupled with multiple statistical strategies

Herb processing is a typical pharmaceutical preparation process for traditional Chinese medicine. After processing, its clinical applications and pharmacological effects vary greatly, which is most commonly attributed to the changing chemical properties between raw herb and processed products. In this work, a total of 53 chemical compounds were detected, among which 17 compounds were identified as discriminatory chemicals between raw and wine-processed Scutellaria baicalensis, and 10 components were identified as chemical markers with a cumulative content contribution of 88.75%. In addition, this work revealed that the best wine-processed time was 18 min by investigating the changes of chemical markers in S. baicalensis during processing. This work demonstrated that ultra-performance liquid chromatography/quadrupole time-of-flight mass spectrometry coupled with multiple statistical strategies is an effective approach for screening and identifying discriminatory chemical markers in complex traditional Chinese medicine.     

不对称苯并菲盘状液晶的合成及取代基对介晶性的影响

合成了一系列新型含间位二硝基苯甲酸酯不对称苯并菲盘状液晶化合物2-(3,5-二硝基苯甲酰氧基)-3,6,7,10,11-五烷氧基苯并菲(3a～3f). 通过偏光显微镜(POM)和差示扫描量热计(DSC)对其介晶性进行了研究. 结果显示: 此类化合物有高的清亮点, 稳定的六方柱状相以及较宽的介晶相范围, 且随着软链碳原子数的增加, 化合物的熔点和清亮点均出现下降趋势, 但六方柱状相的有序性却没有发生很明显的变化. 同时通过与其它三类苯并菲盘状液晶2-苯甲酰氧基-3,6,7,10,11-五烷氧基苯并菲(4a～4f), 2-二茂铁甲酰氧基-3,6,7,10,11-五烷氧基苯并菲(5a～5f), 2,3,6,7,10,11-六烷氧基苯并菲(6a～6f)的对比研究, 探讨了酯基, 强吸电子基团, 以及取代官能团体积对介晶性的影响. 证实了苯并菲化合物中分子结构小的变化将引起介晶性大的改变.