Multi-responses extraction optimization combined with high-performance liquid chromatography-diode array detection-electrospray ionization-tandem mass spectrometry and chemometrics techniques for the fingerprint analysis of Aloe barbadensis Miller.

A quality control strategy using high-performance liquid chromatography-diode array detector-electrospray ionization-tandem mass spectrometry (HPLC-DAD-ESI-MS/MS) coupled with chemometrics analysis was proposed for Aloe barbadensis Miller. Firstly, the extraction conditions including methanol concentration, extraction time and solvent-to-material ratio were optimized by multi-responses optimization based on response surface methodology (RSM). The optimum conditions were achieved by Derringer's desirability function and experimental validation implied that the established model exhibited favorable prediction ability. Then, HPLC fingerprint consisting of 27 common peaks was developed among 15 batches of A. barbadensis samples. 25 common peaks were identified using HPLC-DAD-ESI-MS/MS method by their spectral characteristics or comparison with the authentic standards. Chemometrics techniques including similarity analysis (SA), principal components analysis (PCA) and hierarchical clustering analysis (HCA) were implemented to classify A. barbadensis samples. The results demonstrated that all A. barbadensis samples shared similar chromatographic patterns as well as differences. These achievements provided an effective, reliable and comprehensive quality control method for A. barbadensis.

Natural phosphodiesterase-4 inhibitors from the leaf skin of Aloe barbadensis Miller.

The ethanolic extract of Aloe barbadensis Miller leaf skin showed inhibitory activity against phosphodiesterase-4D (PDE4D), which is a therapeutic target of inflammatory disease. Subsequent bioassay-guided fractionation led to the isolation of two new anthrones, 6'-O-acetyl-aloin B (9) and 6'-O-acetyl-aloin A (11), one new chromone, aloeresin K (8), together with thirteen known compounds. Their chemical structures were elucidated by spectroscopic methods including UV, IR, 1D and 2D NMR, and HRMS. All of the isolates were screened for their inhibitory activity against PDE4D using tritium-labeled adenosine 3',5'-cyclic monophosphate ((3)H-cAMP) as substrate. Compounds 13 and 14 were identified as PDE4D inhibitors, with their IC50 values of 9.25 and 4.42 µM, respectively. These achievements can provide evidences for the use of A. barbadensis leaf skin as functional feed additives for anti-inflammatory purpose.

One-step separation and purification of two chromones and one pyrone from Aloe barbadensis Miller: a comparison between reversed-phase flash chromatography and high-speed counter current chromatography.

INTRODUCTION: Chromones and pyrones are the major secondary metabolites of Aloe barbadensis Miller. As they are minor components of the plant, an efficient purification procedure for them is of great importance for promoting their pharmacological studies. OBJECTIVE: To develop efficient methods for one-step separation and purification of two chromones (5-((S)-2'-oxo-4'-hydroxypentyl)-2-hydroxymethylchromone (1) and 5-((4E)-2'-oxo-pentenyl)-2-hydroxymethylchromone (3)) and one pyrone (aloenin aglycone (2)) from A. barbadensis via reversed-phase flash chromatography (RP-FC) and high-speed counter current chromatography (HSCCC). METHODS: The RP-FC separation was performed using methanol:water (26:74, v/v) as the mobile phase at a flow rate of 20 mL/min. A solvent system composed of dichloromethane:methanol:water (3:1.5:1, v/v/v) was used for the HSCCC separation, at a flow rate of 2.0 mL/min. RESULTS: A one-step RP-FC operation within 110 min was successfully used for the purification of compounds 1 (27.9 mg, 96.5%), 2 (32.4 mg, 98.2%) and 3 (4.1 mg, 99.0%) from 129 mg of crude sample, and a one-step HSCCC separation within 95 min was successfully implemented for the purification of compounds 1 (31.1 mg, 97.6%), 2 (35.8 mg, 96.7%) and 3 (2.7 mg, 98.1%) from 134 mg of crude sample. CONCLUSION: The developed procedures were efficient, with low cost and high yield, which would afford sufficient amounts of high-purity compounds for chromatographic purposes and pharmacological activity screening.

Chemical constituents of Aloe barbadensis Miller and their inhibitory effects on phosphodiesterase-4D.

Aloe barbadensis Mill has been used as food and medicine for a long time. In order to investigate the chemical constituents of A. barbadensis and their inhibitory activities towards phosphodiesterase-4D (PDE4D), 70% methanol extract of the dried A. barbadensis powder was employed. Phytochemical investigation has led to the isolation of three new chromones, 5-(hydroxymethyl)-7-methoxy-2-methylchromone (4), 5-((4E)-2'-oxo-pentenyl)-2-hydroxymethylchromone (6), and 7-hydroxy-5-(hydroxymethyl)-2-methylchromone (7), together with eighteen known compounds. Their chemical structures were determined based on spectroscopic methods including UV, IR, 1D and 2D NMR, and HRMS spectrometry. In addition, their inhibition against PDE4D was evaluated using tritium-labeled adenosine 3',5'-cyclic monophosphate ((3)H-cAMP) as the substrate. Inhibition was calculated by the variation of radioactivity after the reaction, and compounds 1-4, 10, and 21 exhibited certain inhibitory activities towards PDE4D, which can provide an explanation why A. barbadensis can serve as anti-inflammatory agents.

[A novel naphthalene derivative from Aloe barbadensis].

To investigate the chemical constituents of A. barbadensis, aqueous extract of the plant was subjected to preparative medium pressure liquid chromatography (MPLC). The chemical structures were mainly determined by spectroscopic evidences (UV, IR, HR-MS, 1H NMR, 13C NMR, HSQC, 1H-1H COSY and HMBC) and chemical methods. A new O, O, O-triglucosylated naphthalene derivative, together with two known 6-phenyl-2-pyrone derivatives and four 5-methylchromones, were isolated and identified as 1-((3-((4- O-beta-D-glucopyranosyl)-beta-D-xylopyranosyloxymethyl)-1-hydroxy-8-alpha-L-rhamnopyranosyloxy)naphthalene-2-y])-ethanone (1), 10-O-beta-D-glucopyranosyl aloenin (2), aloenin B (3), aloesin (4), 8-C-glucosyl-(R)-aloesol (5), 8-C-glucosyl-7-O-methyl-(S)-aloesol (6), and isoaloeresin D (7). Compound 1 is a novel naphthalene derivative and named as aloveroside B, compounds 2-3 are isolated from this Aloe species for the first time.

Simultaneous qualitative and quantitative determination of phenolic compounds in Aloe barbadensis Mill by liquid chromatography-mass spectrometry-ion trap-time-of-flight and high performance liquid chromatography-diode array detector.

An effective and comprehensive method was developed for the simultaneous analysis of phenolic compounds in the dried exudate of Aloe barbadensis Mill by liquid chromatography-mass spectrometry-ion trap-time-of-flight (LCMS-IT-TOF) and high performance liquid chromatography-diode array detector (HPLC-DAD). Qualitative analysis of all the compounds presented in A. barbadensis Mill was performed on LCMS-IT-TOF, and the diagnostic fragmentation patterns of different types of phenolic compounds (chromones, phenyl pyrones, naphthalene derivative, anthrones and anthraquinones) were discussed on the basis of ESI-IT-TOF MS of components in A. barbadensis Mill and eleven authentic standards. Under the optimal HPLC-DAD chromatographic conditions, quantification of 11 typical phenolic compounds in 15 batches of A. barbadensis Mill was achieved on an Agilent TC-C18 column using gradient elution with a solvent system of methanol and water at a flow rate of 1.0mLmin(-1) and detected at 230nm. All calibration curves exhibited good linear relationship (r(2)>0.9991). The relative standard deviation values for intraday precision were less than 2% with accuracies between 98.21% and 104.57%. The recoveries of the eleven analytes ranged from 97.53 to 105.00% with RSDs less than 2%. This is the first simultaneous characterization and quantitative determination of multiple phenolic compounds in A. barbadensis Mill from locally grown cultivars in China by LCMS-IT-TOF and HPLC-DAD, which can be applied to standardize the quality of A. barbadensis Mill and the future design of nutraceutical and cosmetic preparations.

Mushroom tyrosinase inhibitors from Aloe barbadensis Miller.

Two new chromones, 5-((S)-2'-oxo-4'-hydroxypentyl)-2-(ß-glucopyranosyl-oxy-methyl)chromone (1) and 5-((S)-2'-oxo-4'-hydroxypentyl)-2-methoxychromone (2), together with four known analogues, 8-C-glucosyl-7-O-methyl-(S)-aloesol (3), isoaloeresin D (4), 8-C-glucosyl-(R)-aloesol (5), and aloesin (6) were isolated from the aqueous extract of Aloe barbadensis Miller. Their structures were determined on the basis of spectroscopic evidences (1-D and 2-D NMR, HRMS, UV, and IR data), chemical methods and the literature data. The Mosher's method was applied to establish the absolute configuration of compounds 1 and 2. The inhibitory effects of these chromones on the activity of mushroom tyrosinase were examined, and compound 6 was identified as a noncompetitive tyrosinase inhibitor with an IC(50) value of 108.62µg·mL(-1).