[Chemical constituents of diterpenoids from Boswellia carterii].

This paper explored the chemical constituents of Boswellia carterii by column chromatography on silica gel, Sephadex LH-20, ODS column chromatography, and semi-preparative HPLC. The structures of the compounds were identified by physicochemical properties and spectroscopic data such as infrared radiation(IR), ultra violet(UV), mass spectrometry(MS), and nuclear magnetic resonance(NMR). Seven diterpenoids were isolated and purified from n-hexane of B. carterii. The isolates were identified as(1S,3E,7E,11R,12R)-11-hydroxy-1-isopropyl-4,8,12-trimethyl-15-oxabicyclo[10.2.1]pentadeca-3,7-dien-5-one(1),(1R,3S,4R,7E,11E)-4,8,12,15,15-pentamethyl-14-oxabicyclo[11.2.1]hexadeca-7,11-dien-4-ol(2), incensole(3),(-)-(R)-nephthenol(4), euphraticanoid F(5), dilospirane B(6), and dictyotin C(7). Among them, compounds 1 and 2 were new and their absolute configurations were determined by comparison of the calculated and experimental electronic circular dichroisms(ECDs). Compounds 6 and 7 were obtained from B. carterii for the first time.

Platelet-inhibitory phenolic constituents from the fruits of Daemonorops draco.

Eight previously undescribed phenolic compounds, dracoropins A - H (1-8), along with two known analogues (9 and 10) were isolated from the fruits of Daemonorops draco. Four pairs of isomers (1a/1b, 2a/2b, 3a/3b, and 4a/4b) were resolved by using chiral-phase HPLC separation. Their structures, including the absolute configurations of the resolved isomers, were elucidated by analysis of spectroscopic data (1D and 2D NMR, IR, and HRESIMS), single-crystal X-ray diffraction, and electronic circular dichroism (ECD) calculations. Compounds 1, 2, and 3 bear a rare 2-phenylbenzo[d]-1,3-dioxepine skeleton. All the isolates were evaluated for their inhibitory activity against ATP release in thrombin-activated platelets. Compounds 2b, 3a, and 6 could significantly inhibit ATP release in thrombin-activated platelets.

Anti-inflammatory flavonoid derivatives from the heartwood of Dalbergia odorifera T. Chen.

Two pairs of flavonoid enantiomers (1a/1b and 2a/2b) together with three known analogues (3-5) were isolated from the heartwood of Dalbergia odorifera T. Chen. Their structures were elucidated by extensive spectroscopic analysis (1 D and 2 D NMR, UV, IR, and HRMS) and experimental and calculated ECD data. Compound 2 features an unusual 2-methyl-3(2H)-furanone moiety forming the C-ring of flavonoid, and its putative biosynthetic pathway is also proposed. Compounds 3‒5 exhibited significant inhibition of nitric oxide production in lipopolysaccharide-stimulated RAW264.7 cells with IC50 values of 14.7 ± 0.3 µM, 40.2 ± 1.1 µM, and 3.2 ± 0.1 µM, respectively.

[Sesquiterpenoids from Aquilariae Lignum Resinatum].

Eight sesquiterpenoids were isolated from petroleum ether extract of Aquilariae Lignum Resinatum by various column chromatography techniques including silica gel, ODS, and semi-preparative HPLC. Their structures were identified on the basis of physicochemical properties, UV, IR, MS, and NMR spectroscopic data as(4S,5S,7R,10S)-5,7-dihydroxy-11-en-eudesmane(1),(7R,10S)-eudesma-4-en-11,15-diol(2),(2R,4S,5R,7R)-2-hydroxyeremophila-9,11-dien-8-one(3), 7α-H-9(10)-ene-11,12-epoxy-8-oxoeremophilane(4),(+)-9ß,10ß-epoxyeremophila-11(13)-en(5), 4(14)-eudesmene-8α,11-diol(6), 12,15-dioxo-selina-4,11-dien(7), and 2ß,8 aα-dihydroxy-11-en-eremophilane(8). Compounds 1 and 2 are new compounds, and their absolute configurations were determined by calculating ECD. Compounds 1, 4, and 6-8 could significantly improve taurocholic acid(TCA)-induced gastric mucosal GES-1 cell injury at a concentration of 20 µmol·L~(-1), and the cell protection rates were 23.51%±2.79%, 16.10%±1.25%, 24.45%±4.89%, 17.48%±2.93%, and 21.44%±2.39%, respectively.

[Chemome profiling of Qijiao Shengbai Capsules by UPLC-IT-TOF-MS].

Qijiao Shengbai Capsules(QJ) are a common Miao medicine serving as an adjuvant cancer therapy in clinical practice.QJ consists of seven medicinal materials such as Astragalus membranaceus and Lespedeza buergeri.Its chemical components have not been clarified and the quality control needs to be improved.In this study, LC-IT-TOF-MS was used to comprehensively collect MS~1 and MS~2 fragment information of QJ and rapidly identify the chemical compositions.The chromatographic separation was performed on the Capcell core ADME column(2.1 mm×150 mm, 2.7 µm) with 0.1% formic acid aqueous solution(A) and acetonitrile(B) as mobile phases for gradient elution.High-resolution mass spectrometric information was obtained by scanning in the positive and negative ion ESI modes.A total of 107 compounds were structurally identified according to the deduced MS fragmentation patterns and comparison with standards and data reported in the literature, including 54 flavonoids, 16 phthalides, 13 alkaloids, 12 phenolic acids, 7 saponins, 2 coumarins, 2 condensed tannins, and 1 purine.This study clarified the chemical composition of QJ and provided references for the improvement of its quality standards and the elucidation of its medicinal substances.

[Rapid chemome characterization of Pien-Tze-Huang by DI-MS/MS~(ALL)].

Pien-Tze-Huang, one of the most famous and widely used Chinese medicinal prescriptions in China, consists of Notoginseng Radix et Rhizoma, Bovis Calculus, Fel Serpentis, and Moschus.The prescription can clear heat and remove toxin, cool blood and resolve blood stasis, and relieve swelling and pain.Characterizing the chemical composition can facilitate the construction of the quality standard and the research on the effective compounds and action mechanism of Pien-Tze-Huang.Therefore, this study used direct infusion(DI)-MS/MS~(ALL) method to rapidly and accurately reveal the chemical composition of Pien-Tze-Huang.The principle of chemical composition profiling of Chinese medicinal prescriptions lies in the MS~1-MS~2 dataset construction, followed by structural annotation based on MS/MS spectra and summarizing of mass fragmentation pathways.MS/MS~(ALL) owns unique mass spectrometric separation ability via applying gas phase fractionation which enables MS~1 ion cohort successively enter the collision cell and acquire MS~2 spectrum for each precursor ion current with a width of m/z=1.Because DI can provide desired measurement time, MS/MS~(ALL) is able to acquire MS~2 spectrum for each compound individually except for the compounds which share identical nominal molecular weight, even isomers.A total of 52 compounds were identified in Pien-Tze-Huang, including 16 saponins, 24 bile acids, 9 fatty acids, 2 saccharides, and 1 other compound.DI-MS/MS~(ALL) can simultaneously identify the compounds with different polarities in a short time, which is superior to LC-MS.This study provides a powerful tool for the rapid chemome profiling of Chinese medicinal prescriptions.

[Quality standard of Lobeliae Chinensis Herba].

In light of related methods in Chinese Pharmacopoeia(2020 edition), this study established the quality standard for Lobeliae Chinensis Herba. The TLC identification method was established with silica gel GF_(254) thin layer plate, diosmin standard, linarin standard, and the reference material of Lobeliae Chinensis Herba. The loss on drying, total ash, acid-insoluble ash, and ethanol-soluble extracts of 18 batches of Lobeliae Chinensis Herba samples were determined according to the general principles in Chinese Pharmacopoeia. Then, HPLC was adopted in the establishment of characteristic chromatogram and content determination. The results showed that the established method can achieve good separation for diosmin, linarin, and lobetyolin. Based on the results of detection for 18 batches of Lobeliae Chinensis Herba samples, the draft quality standard was established, which was expected to provide reference for the revision of this medicinal herb in Chinese Pharmacopoeia.

Trimeric chalchonoids from the total phenolic extract of Chinese dragon's blood (the red resin of Dracaena cochinchinensis).

Four new chalchonoid trimers, named cochinchinenins N-Q (1-4), along with a pair of known enantiomers (5-6), were isolated from the total phenolic extract of Chinese dragon's blood (the red resin of Dracaena cochinchinensis). The planar structures of 1-4 were elucidated by extensive spectroscopic analysis including HRESIMS and 1D/2D NMR. The absolute configurations of new compounds were established by ECD data. Compound 1 exhibited significant inhibition of nitric oxide production in lipopolysaccharide-stimulated BV-2 microglial cells with IC50 value of 11.5 ± 1.7 µM.

[Condensed tannins from roots of Indigofera stachyodes].

Eleven condensed tannins were isolated from the roots of Indigofera stachyodes by various column chromatography techniques including silica gel, octadecyl silica(ODS), Sephadex LH-20, and semi-preparative high performance liquid chromatography(HPLC). These compounds were identified on the basis of physicochemical properties, nuclear magnetic resonance(NMR) and mass spectrometry(MS) data as stachyotannin A(1), epicatechin-(2ß→O→7,4ß→8)-epiafzelechin-(4ß→8)-catechin(2), cinnamtannin D1(3), cinnamtannin B1(4), epicatechin-(2ß→O→7,4ß→8)-epiafzelechin-(4α→8)-epicatechin(5), gambiriin C(6), proanthocyanidin A1(7), proanthocyanidin A2(8), aesculitannin B(9), proanthocyanidin A4(10), and procyanidin B5(11). Compound 1 is a new compound. Compounds 2-11 were isolated from Indigofera for the first time. Furthermore, compounds 1, 2, and 4-11 showed inhibitory effects on thrombin-induced ATP release in platelets.

[One new cembranoid diterpene from gum resin of Boswellia carterii].

This study aims to study the chemical components from the gum resin of Boswellia carterii. Five cembranoid diterpenes were isolated from the gum resin of B. carterii by various of column chromatographies including silica gel, Sephadex LH-20, and semi-preparative HPLC. Their structures were identified on the basis of physicochemical properties, mass spectrometry(MS), nuclear magnetic resonance(NMR), Ultraviolet(UV) and infrared(IR) spectroscopic data. These compounds were identified as(1S,2E,4R,5S,7E,11E)-4-methoxy-5-hydroxycembrane(1),(1R~*,4R~*,5E,8E,12E,15E)-4-hydroxycembra-5,8,12,15-tetraene(2), cembrene A(3),(3S,4S,7R)-4-hydroxycembrane(4), and pavidolide D(5). Compound 1 was a new compound. Compounds 2, 4, and 5 were obtained from the gum resin of B. carterii for the first time. Compound 2 showed weak inhibition on the human liver cancer cell line HepG2.

[Two new phenylpropanoid amide glycosides from whole plants of Corydalis racemosa].

Two new phenylpropanoid amide glycosides and ten analogues were isolated from the CH_2Cl_2 layer of 95% ethanol extract of the whole plants of Corydalis racemosa by using various chromatographic techniques, including silica gel, Sephadex LH-20, ODS column chromatographies, and semi-preparative HPLC. Their structures were identified on the basis of physicochemical properties, MS, NMR, and IR spectroscopic data as N-cis-sinapoyltyramine-4'-O-ß-glucoside(1), N-cis-sinapoyl-3-methoxytyramine-4'-O-ß-glucoside(2), N-cis-sinapoyltyramine(3), N-cis-feruloyltyramine(4), N-trans-cinnamoyltyramine(5), N-trans-feruloylphenethylamine(6), N-trans-p-methoxycinnamoyl-3-hydoxyoctopamine(7), N-cis-feruloyl-3-methoxytyramine(8), N-trans-feruloyltyramine(9), N-trans-feruloyl-3-methoxytyramine(10), N-trans-sinapoyltyramine(11), and N-trans-p-coumaroyltyramine(12). Compounds 1 and 2 are new compounds. Compounds 3-7 are obtained from the plants of Papaveraceae for the first time, and compounds 8-12 are firstly isolated from C. racemosa.

[Chemome profiling of Citri Reticulatae Pericarpium using UHPLC-IT-TOF-MS].

Citri Reticulatae Pericarpium(CRP, Chinese name: Chenpi) is one of the most famous edible traditional Chinese medicines(TCMs). CRP was first recorded as top grade TCM in Shennong Bencao Jing attributing to the benefits such as regulating Qi, tonifying spleen, eliminating dampness and eliminating phlegm, and has been widely utilized for the treatments of abdominal fullness and distention, vomiting and diarrhea, as well as phlegm cough. CRP is also widely popular as spice in food industry. Because of the wide cultivation, a number of brands that exhibit extensive price range can be found in the market, resulting in a great challenge for grading. Herein, an attempt was made to in-depth chemome profiling for the sake of providing meaningful information of the universal quality control of CRP. A new core-shell column packed with adamantylethyl substituted silica gel particles was deployed for chromatographic separations and IT-TOF-MS that is advantageous at providing abundant high resolution molecular and fragment ions was employed for qualitative detection. A total of 62 components were observed and 61 ones were structurally annotated according to proposing mass fragmentation patterns, matching with reference compounds and relevant databases, and the chemical families included flavone, limonin, etc. In particular, ten compounds bearing 3-hydroxy-3-methylglutarate substitute were detected from CRP for the first time. Above all, the chemical profile of CRP was characterized and the findings are meaningful for the in-depth quality assessment and efficacy material clarification of CRP.

[A new nor-sesquiterpene glycoside from Corydalis edulis].

This study is to investigate the chemical constituents from the whole plant Corydalis edulis. The chemical constituents were separated and purified by macroporous resin D101, silica gel, Sephadex LH-20, ODS, and semi-preparative HPLC. Their structures were determined by physicochemical properties and spectroscopic data. Four compounds were isolated from the dichloromethane and water extracts of the whole plant C. edulis, and identified as 6'-ß-D-xylosylicariside B2(1),(3S,5R,6S,7E)-5,6-epoxy-3-hydroxy-7-megastigmen-9-one(2), loliolide(3), and 5,5'-dimethoxybiphenyl-2,2'-diol(4), respectively. Compound 1 is a new compound, of which the absolute configuration was established by electronic circular dichroism(ECD) calculations. Compound 4 is obtained from the plants of Papaveraceae family for the first time. Compounds 2 and 3 are firstly isolated from the Corydalis genus.

Phenolic constituents, pharmacological activities, quality control, and metabolism of Dracaena species: A review.

ETHNOPHARMACOLOGICAL RELEVANCE: Dragon's blood (Chinese name: Xuejie), which comprises red resins obtained from several plants (27 species from 4 families), is drawing worldwide interests in medicinal applications owing to its broad pharmacological spectrum such as promoting blood circulation, regenerating muscle, relieving swelling and pain, maintaining hemostasis, etc. AIM OF THE STUDY: This work aims to evaluate current research progress on phenolic constituents, pharmacological activities, quality control, and metabolism of six Dracaena plants, namely, Dracaena cochinchinensis (Lour.) S.C.Chen, D. cambodiana Pierre ex Gagnep., D. cinnabari Balf. f., D. draco (L.) L., D. loureiroi Gagnep., and D. schizantha Baker, figure out the shortcomings of existing studies, and provide meaningful guidelines for future investigations. METHODS: Extensive database retrieval, such as SciFinder, PubMed, CNKI, ChemSpider, etc., was performed by using the keywords "Dracaena," "dragon's blood," as well as the Latin names of the six Dracaena species. In addition, relevant textbooks, patents, reviews, and documents were also employed to ensure sufficient information is collected. RESULTS: Flavonoids and their oligomers are the primary chemical clusters distributed in Dracaena plants. Pharmacological activities including analgesic, anti-inflammatory, antibacterial, hypolipidemic, hypoglycemic, and cytotoxic effects; bi-directional regulation effects on hemorheology; and cardiovascular and cerebrovascular effects have been disclosed by modern pharmacological evaluations. The chemical and metabolic profiles after oral administration of dragon's blood extract were preliminarily characterized. However, some of the pharmacological investigations reported only elementary methodologies and unreliable findings, and even worse, some important aspects were questionable or missing in these articles. CONCLUSIONS: Dragon's blood is a valuable source of bioactive compounds, mainly flavonoids and their oligomers. Its potential therapeutic effects on different diseases are attractive, such as the notable effect on cardiovascular diseases. In future studies, there is an urgent need to test the effect of this extract on appropriate cell lines and animal models to analyze its ethnopharmacological applications; moreover, "composition-effect correlation" methods and omics technologies are demanded for identifying the effective material basis and therapeutic mechanisms before entering into clinical trials. Moreover, attention should be paid to the chemical profiling and quality evaluation of this precious herbal medicine.

[Rapid chemical profiling of Artemisiae Scopariae Herba using reversed phase liquid chromatography-hydrophilic interaction liquid chromatography-predictive multiple reaction monitoring].

Chemical profiling of a given herbal medicine( HM) is the prerequisite for clarifying the effective material basis and therapeutic mechanisms,and it is an important integral part of traditional Chinese medicine chemical biology( TCMCB). In current study,we aimed to propose a new strategy for fast chemical characterization of HM by using reversed phase liquid chromatography-hydrophilic interaction chromatography-predictive multiple reaction monitoring( RPLC-HILIC-p MRM),and Artemisiae Scopariae Herba was employed in this study to illustrate the entire strategy. In response to wide polarity spanning of the diverse chemical clusters in Artemisiae Scopariae Herba,RPLC and HILIC were coupled in series to retain and separate hydrophilic and hydrophobic components simultaneously by identifying the characteristics of chromatographic separation. Most of the chemical constituents in traditional Chinese medicine can be predicted by summarizing the results of chemical constituents of the same genera and introducing primary metabolites and possible substitution reaction types. Therefore,we constructed predictive ion pairs to rapidly identify the chemical constituents of Artemisiae Scopariae Herba. After comparison with control products,discussion on fragmentation pattern,and access to relevant information from literature and databases,a total of 139 components were detected and structurally annotated by matching the obtained spectral data with the information of authentic compounds. Above all,RPLC-HILIC-p MRM could be used as an eligible analytical tool for the chemical profiling of HMs.

[LC-MS guided isolation of two anti-inflammatory cyclic dihydrochalcane trimers from Chinese dragon's blood].

As an important integral part of traditional Chinese medicine chemical biology( TCMCB),it is of great importance to rapid isolate,and reliably identify the chemical components in herbal medicines. Phytochemical studies on the anti-inflammatory active part of Chinese dragon's blood,the red resin of Dracaena cochinchinensis,resulted in the isolation of two compounds,nordracophane( 1) and dracophane( 2),using LC-MS and chromatographic techniques( Silica gel,ODS and preparative HPLC). The structures,cyclic dihydrochalcane trimers,were elucidated on the basis of 1 D and 2 D NMR,MS,IR and UV spectral analysis. Compound 1 is a new compound,and 2 is isolated from D. cochinchinensis for the first time. Both compounds exhibited significant inhibition of nitric oxide production in lipopolysaccharides( LPS)-stimulated RAW264. 7 cells with IC50 values of( 14. 9±4. 50) and( 9. 0±0. 7) µmol·L-1.

[Inhibitory effect of BF523 from Ilex hainanensis on ox LDL-induced foam cells formation].

Cardio-cerebral vascular disease induced by atherosclerosis is a serious cause of human health. The pathogenesis of AS is very complex,and the oxidized low-density lipoprotein( ox LDL) induced foam cells formation is considered to be the most important cytological change in AS. Based on the definition of " TCM chemical biology",we clarified the chemical composition of Ilex hainanensis,the effective substances of I. hainanensis on the activity of anti-AS were screened. Then we found that saponin BF523 had the good inhibitory effect on foam cell formation. In this research,we studied the BF523 as the research object to clarify the molecular target of the active compound of I. hainanensis by foam cell formation model. The results showed that BF523 significantly inhibited the oxidation of ox LDL-induced macrophage foaming and decreased the lipid content in macrophages. BF523 had inhibited the phagocytosis of ox LDL in macrophages by reducing the mRNA and protein levels of scavenger receptor CD36,thereby inhibiting the occurrence and development of AS. These findings not only clarified the mechanism of the inhibition of foam cell formation by saponin BF523,but also provided a useful exploration for the enrichment of the theory of " TCM chemical biology".

[Anti-tumor activity of HIS-4,a biflavonoid from Resina draconis,on human hepatoma HepG2 and SK-HEP-1 cells].

The research of anti-hepatocellular carcinoma(HCC) drug has attracted more and more attention. Natural products are the important source of active compounds for cancer treatment. A biflavonoid HIS-4 was isolated from Resina draconis in our previous study. MTT assay, hoechst staining, and flow cytometry analysis were used to investigate the effects of HIS-4 on the proliferation and apoptosis of human hepatoma HepG2 and SK-HEP-1 cells. Moreover, the effects of HIS-4 on the migration and invasion ability of HepG2 and SK-HEP-1 cells were evaluated by wound healing assay and Transwell assay. In addition, MTT assay, flow cytometry analyses, Hoechst staining, wound healing assay, Transwell assay, and tube formation assay were used to explore the anti-angiogenic activity of HIS-4 in human umbilical vein endothelial cells(HUVECs). Mechanistically, the HIS-4 regulatory of signal pathways in H9 epG2 and SK-HEP-1 cells were analyzed by Western blot. This results showed that HIS-4 suppressed the proliferation of human hepatoma HepG2 and SK-HEP-1 cells. Moreover HIS-4 induced their apoptosis of HepG2 and SK-HEP-1 cells. HIS-4 inhibited the migration and invasion of HepG2 and SK-HEP-1 cells. Additionally, HIS-4 exhibited angiogenesis effects. Mechanistically, up-regulation of MAPK signaling pathway and down-regulation of mTOR signaling pathway may be responsible for anti-hepatoma activity of HIS-4. Therefore, HIS-4 may be a promising candidate drug for HCC treatment.

LC-MS-guided isolation of anti-inflammatory 2-(2-phenylethyl)chromone dimers from Chinese agarwood (Aquilaria sinensis).

Fifteen previously undescribed 2-(2-phenylethyl)chromone dimers, along with two known analogues were isolated from Chinese agarwood (Aquilaria sinensis) by a LC-MS-guided fractionation procedure. Their structures were elucidated on the basis of spectroscopic and spectrometric data (1D and 2D NMR, IR, and HRESIMS). The isolated compounds exhibited significant inhibition of nitric oxide production in lipopolysaccharide-stimulated RAW264.7 cells with IC50 values in the range 0.6-37.1 µM.

[Chemical characterization for flowers and lignified stems of Cistanche deserticola].

As a holoparasitic plant, Cistanche deserticola is one of the two original sources of Cistanches Herba that is one of the most famous tonic medicines, in Chinese Pharmacopoeia. The succulent stems are used for medicinal usage, whereas those lignified stems as well as flowers of less pharmacological importance are usually deserted, suggesting extensive resource waste. Herein, chemical characterization of the flowers along with lignified stems was conducted using HPLC-IT-TOF-MS aiming to explore the medicinal valu of those non-medicinal parts. Following ultrasonication-assisted extraction with 50% aqueous methanol, either flower or lignified stem extract was subjected onto LC-IT-TOF-MS equipped with a Capcell core ADME column to acquire both MS¹ and MSº spectra, and gradient elution was carried out with combinatory 0.1% aqueous formic acid and acetonitrile. Both positive and negative ionization polarities were deployed, resulting in the observation of 62 components, in total. Thirty-nine signals were structurally annotated, including phenylethanoid glycosides, iridoids, lignans and saccharides according to matching with authentic components and literature information, as well as applying the proposed mass fragmentation rules. A total of 62 ones were putatively identified. Above all, lignified stems and flowers should not the qualified substitutes for the succulent stems attributing to the significant differences between the medicinal portion and those parts with less medicinal values.