Simple enzyme reactors suitable for the byproduct-free preparation of the aglycones of naturally occurring glycosides under mild conditions

Naringinase from Penicillium species—containing α-l-rhamnosidase and β-d-glucosidase activity—immobilized on silicate carriers can be used as a mild and effective means to cleave naturally occurring glycosides into their aglycones and sugar components. The procedure was tested with flavonoid-, anthraquinone-, and steroidglycosides. Since the solubility of such compounds is limited in aqueous solutions, a simple batch procedure has been developed to convert solid substrates suspended in only small amounts of buffer to the desired products with high yields.     

Towards molecular-imprint based SPE of local anaesthetics

Summary Solidago canadensis L., Canadian goldenrod (Asteraceae) has been used in European phytotheraphy for centuries as a component of urological and antiphlogistical remedies. High-performance liquid chromatography (HPLC) coupled with diode-array detection (DAD) and online mass spectrometry (MS) has been used for the separation and quantification of phenolics (chlorogenic acid, caffeic acid, kaempferol-3-O-α-L-rutinoside (nicotiflorin), quercetin-3-O-β-D-rutinoside (rutin), quercetin-3-O-β-D-galactoside (hyperoside), quercetin-3-O-β-D-glucoside (isoquercitrin), quercetin-3-O-β-D-rhamnoside (quercitrin), kaempferol-3-O-α-L-rhamnoside (afzelin) and quercetin from Solidaginis herba. Extracts have been obtained using different technologies. Three aqueous and three alcoholic extracts were studied separately. Reversedphase high-performance liquid chromatography separation of polyphenols on octadecyl sorbent Hypersil was performed, using acetonitrile: acetic acid 2.5 v/v % as eluent in gradient elution. Our results confirm previous reports concerning the presence of several flavonoids. Quantification of the main quercetin glycosides in pharmaceuticals is also reported. Presented at Balaton Symposium '01 on High-Performance Separation Methods, Siófok, Hungary, September 2–4, 2001     

Phenolic compounds from the aerial parts of Clematis viticella L. and their in vitro anti-inflammatory activities*

Phytochemical investigations on the EtOH extract of Clematis viticella led to the isolation of six flavonoid glycosides, isoorientin (1), isoorientin 3′-O-methyl ether (2), quercetin 7-O-α-L-rhamnopyranoside (3), quercetin 3,7-di-O-α-L-rhamnopyranoside (4), manghaslin (5) and chrysoeriol 7-O-β-D-glucopyranoside (6), one phenylethanol derivative, hydroxytyrosol (7), along with three phenolic acids, caffeic acid (8), (E)-p-coumaric acid (9) and p-hydroxybenzoic acid (10). The structures of the isolates were elucidated on the basis of NMR and HR-MS data. All compounds were isolated from C. viticella for the first time. Compounds 7 and 8 showed significant anti-inflammatory activity at 100 μM by reducing the release of NO in LPS-stimulated macrophages comparable to positive control indomethacin. Compounds 3 and 7 exhibited anti-inflammatory activity through lowering the levels of TNF-α while 1, 3 and 5 decreased the levels of neopterin better than the positive controls.     

Synthesis and Structure Determination of Some New N‐Glycosides of 4,5‐Disubstituted‐1,2,4‐Triazole‐3‐Thiones

Some new N‐glycosides of 4‐(2‐phenylethyl)‐5‐pyridyl‐1,2,4‐triazole‐3‐thiones were synthesised by the coupling reaction of halo sugar with 4,5‐disubstituted 3H‐1,2,4‐triazole‐3‐thiones in the presence of mercuric cyanide and dry nitromethane as solvent, followed by deprotection using dry ammonia in methanol. All of the above compounds were fully characterized by means of infrared, ¹H NMR spectroscopy, mass spectroscopy and elemental analysis.     

碳糖苷合成的新进展

本文介绍了近几年来有关碳糖苷合成的最新进展, 包括亲电取代、亲核糖取代、过渡金属催化、异头碳自由基反应、重排和环加成反应以及糖环形成反应等。     

A study for quality evaluation of Taxilli Herba from different hosts based on fingerprint-activity relationship modeling and multivariate statistical analysis

In this study, a fingerprint-activity relationship modeling between chemical fingerprints and antirheumatic activity was established, and multivariate statistical analysis was used to evaluate the quality of Taxilli Herba (TH) from different hosts. Characteristic fingerprints of 20 batches of TH samples were generated by high-performance liquid chromatography coupled with triple quadrupole-time of flight tandem mass spectrometry (HPLC-Triple TOF-MS/MS), and the similarity analysis was calculated based on thirteen common characteristic peaks by hierarchical clustering analysis (HCA). Subsequently, nine efficacy markers were discovered by combining fingerprints and antirheumatic activity through grey correlation analysis (GCA) and bivariate correlation analysis (BCA). Meanwhile, the content of 5 constituents in 9 markers was determined by high-performance liquid chromatography coupled with triple quadrupole-linear ion trap tandem mass spectrometry (HPLC-QTRAP-MS/MS). The comprehensive quality of TH was assessed using multivariate statistical analysis, including principal components analysis (PCA) and technique for order preference by similarity to ideal solution (TOPSIS). The results showed that a high dose of TH extract could markedly ameliorate arthritis damage compared to other doses, with flavonoids playing an important role in the antirheumatic activity. The comprehensive quality of samples from Morus alba L. (SS) was superior to those from Liquidambar formosana Hance (FXS). The present study will demonstrate the markers associated with efficacy, and provide an applicable strategy for more comprehensive quality control and evaluation of TH.     

A study on the influence of the structure of the glycosyl acceptors on the stereochemistry of the glycosylation reactions with 2-azido-2-deoxy-hexopyranosyl trichloroacetimidates

The stereochemical outcome of glycosylations with 2-azido-2-deoxy-D-gluco- and D-galactopyranosyl trichloroacetimidates as glycosyl donors has been investigated by using a series of chiro-inositol derivatives as glycosyl acceptors. The influence of the absolute configuration, the conformation and the conformational flexibility of the glycosyl acceptor has been studied by using different glycosyl donors under similar pre-established experimental conditions. Although the structure of the acceptor may play a role in governing the stereochemistry of these glycosylations, the results show that, in general terms, the relative influence of these factors is difficult to evaluate. For a given set of experimental conditions, the stereochemical course of these glycosylations depends on structural features of both glycosyl donor and glycosyl acceptor. It is a balance of these factors, where the structure of the glycosyl donor always plays a major role, which determines the stereochemistry of the coupling reaction. Therefore, the examples reported in the literature in which the structure of the glycosyl acceptor appears to be crucial in determining the stereochemistry of the reaction constitute particularly favorable cases which do not presently allow any further generalization.     

Intramolecular C-glycosylation of 2-O-benzylated pentenyl mannopyranosides: remarkable 1,2-trans stereoselectivity

The IDCP-promoted intramolecular C-glycosylation of pentenyl α-mannopyranosides carrying, at O-2, an activated benzyl group gave, unexpectedly, the 1,2-trans-fused bicyclic product which corresponds to an α-C-aryl mannopyranose derivative. This remarkable, strained C-glycosyl compound was rapidly epimerized to the more stable 1,2-cis product on treatment with BF₃·Et₂O. The IDCP-reaction product could be elaborated into a 2-(α-C-mannopyranosyl)-3,4,5-trimethoxybenzyl alcohol derivative.     

Anti-Inflammatory,Antidiabetic Properties and In Silico Modeling of Cucurbitane-Type Triterpene Glycosides from Fruits of an Indian Cultivar of Momordica charantia L.

Diabetes mellitus is a chronic disease and one of the fastest-growing health challenges of the last decades. Studies have shown that chronic low-grade inflammation and activation of the innate immune system are intimately involved in type 2 diabetes pathogenesis. Momordica charantia L. fruits are used in traditional medicine to manage diabetes. Herein, we report the purification of a new 23-O-β-d-allopyranosyl-5β,19-epoxycucurbitane-6,24-diene triterpene (charantoside XV, 6) along with 25ξ-isopropenylchole-5(6)-ene-3-O-β-d-glucopyranoside (1), karaviloside VI (2), karaviloside VIII (3), momordicoside L (4), momordicoside A (5) and kuguaglycoside C (7) from an Indian cultivar of Momordica charantia. At 50 µM compounds, 2–6 differentially affected the expression of pro-inflammatory markers IL-6, TNF-α, and iNOS, and mitochondrial marker COX-2. Compounds tested for the inhibition of α-amylase and α-glucosidase enzymes at 0.87 mM and 1.33 mM, respectively. Compounds showed similar α-amylase inhibitory activity than acarbose (0.13 mM) of control (68.0–76.6%). Karaviloside VIII (56.5%) was the most active compound in the α-glucosidase assay, followed by karaviloside VI (40.3%), while momordicoside L (23.7%), A (33.5%), and charantoside XV (23.9%) were the least active compounds. To better understand the mode of binding of cucurbitane-triterpenes to these enzymes, in silico docking of the isolated compounds was evaluated with α-amylase and α-glucosidase.     

α-Tetralone glycosides from the green walnut husks of Juglans mandshurica Maxim. and their cytotoxic activities

Abstract

Five new α-tetralone glycosides, juglanbiosides A-E (1–5), together with an α-tetralone derivative (15) and nine known 1,4-naphthoquinones (6–14) were isolated from the 95% EtOH extract of green walnut husks of Juglans mandshurica Maxim. Their structures were elucidated by comprehensive spectroscopic methods (¹H, ¹³C NMR, DEPT, HSQC, HMBC, CD, HR-ESI-MS). In vitro cytotoxicities of all the isolated compounds were evaluated against BGC-823, HCT-15 and K562 cancer cell lines.