Mixture Of Glycosides Research Articles

Electrospray-ionization mass spectrometry of mixtures of triterpene glycosides with paracetamol

Molecular complexation of paracetamol with hederagenin 3-O-α-L-rhamnopyranosyl-(1 → 2)-O-α-L-arabinopyranoside (α-hederin) and its 28-O-α-L-rhamnopyranosyl-(1 → 4)-O-β-D-glucopyranosyl-(1 → 6)-O-β-Dglucopyranosyl ether (hederasaponin C) was investigated for the first time using electrospray-ionization mass spectrometry (ESI-MS). The glycosides form complexes with paracetamol in a 1:1 molar ratio. The hederasaponin C complex is more stable. The structures of the glycosides and paracetamol are concluded to have an impact on the complexation process.

Breviscapine protects against cardiac hypertrophy through blocking PKC‐α‐dependent signaling

Breviscapine is a mixture of flavonoid glycosides extracted from the Chinese herbs. Previous studies have shown that breviscapine possesses comprehensive pharmacological functions. However, very little is known about whether breviscapine have protective role on cardiac hypertrophy. The aim of the present study was to determine whether breviscapine attenuates cardiac hypertrophy induced by angiotensin II (Ang II) in cultured neonatal rat cardiac myocytes in vitro and pressure-overload-induced cardiac hypertrophy in mice in vivo. Our data demonstrated that breviscapine (2.5-15 microM) dose-dependently blocked cardiac hypertrophy induced by Ang II (1 microM) in vitro. The results further revealed that breviscapine (50 mg/kg/day) prevented cardiac hypertrophy induced by aortic banding as assessed by heart weight/body weight and lung weight/body weight ratios, echocardiographic parameters, and gene expression of hypertrophic markers. The inhibitory effect of breviscapine on cardiac hypertrophy is mediated by disrupting PKC-alpha-dependent ERK1/2 and PI3K/AKT signaling. Further studies showed that breviscapine inhibited inflammation by blocking NF-kappaB signaling, and attenuated fibrosis and collagen synthesis through abrogating Smad2/3 signaling. Therefore, these findings indicate that breviscapine, which is a potentially safe and inexpensive therapy for clinical use, has protective potential in targeting cardiac hypertrophy and fibrosis through suppression of PKC-alpha-dependent signaling.

Effects of escin mixture from the seeds of Aesculus hippocastanum on obesity in mice fed a high fat diet

Escins, a triterpene glycoside mixture obtained from the ethanol extract of Aesculus hippocastanum L. (Hippocastanaceae) seed, was evaluated for its in vivo effects on the plasma levels of some hormones (leptin, insulin, FT3, FT4) and biochemical parameters (glucose, triglyceride, total cholesterol, HDL-C, LDL-C concentrations) in mice fed with a high fat diet for 5 weeks. A high fat diet induced a remarkable increment in the plasma leptin (p <0.01), total cholesterol (p <0.01) and LDL-C (p <0.001) concentrations compared to control group animals. Combined administration of a high-fat diet with escins decreased leptin (31.6%) (p<0.05) and FT4 (36.0%) (p<0.05) levels, increased HDL-C concentration (17.0%), while remained ineffective on LDL-C concentration in mice. Results have shown that escins may have beneficial effects in the understanding of obesity.

Gold Catalysis in Glycosylation Reactions

Glycosylation of alcohols containing acid-sensitive groups, as for example 1,2-5,6-di-O-isopropylidene-glucofuranose, Fmoc-threonine tert-butyl ester or farnesol, is achieved using gly­cosyl trichloroacetimidates activated by gold(I) chloride (5-10 mol%). While glycosylation with 2-O-acyl protected glycosyl donors proceeds with 1,2-trans-selectivity, non-neighboring group active glycosyldonors give mixtures of anomeric glycosides or α-glycosides depending upon their structure and the reactivity of the glycosyl acceptor.

Methicillin-Resistant Staphylococcus aureus (MRSA)-Active Metabolites from Platanus occidentalis (American Sycamore)

One known and three new potent, selective, and nontoxic anti-MRSA metabolites, kaempferol 3-O-alpha-l-(2'',3''-di-E-p-coumaroyl)rhamnoside (1) (IC(50) 2.0 microg/mL), kaempferol 3-O-alpha-l-(2''-E-p-coumaroyl-3''-Z-p-coumaroyl)rhamnoside (2) (IC(50) 0.8 microg/mL), kaempferol 3-O-alpha-l-(2''-Z-p-coumaroyl-3''-E-p-coumaroyl)rhamnoside (3) (IC(50) 0.7 microg/mL), and kaempferol 3-O-alpha-l-(2'',3''-di-Z-p-coumaroyl)rhamnoside (4) (IC(50) 0.4 microg/mL), were isolated from the leaves of the common American sycamore, Platanus occidentalis. Compounds 2-4 are new. Due to the unusual selectivity, potency, and safety of the pure compounds and the semipure glycoside mixture against MRSA, it is clear that this represents a viable class of inhibitors to prevent growth of MRSA on surfaces and systemically.

Antimitotic action of glycosides of Nerium oleander L.

The effects of mixtures of glycosides from Nerium oleander L. on root tips of Allium cepa L. and endosperm of Haemanthus katherinae Bak. were studied. The root tips were exposed to the solutions for different time intervals (6 to 48 hours) and their recovery in tap water was also observed. Disturbances in Allium were studied exclusively by means of the squash preparation technique. Endosperm of Haemanthus was studied both in vitro and in the electron microscope. The following disturbances were found: (1) Disturbances in the formation of a normal bi-polar mitotic spindle. Distinct continuous fibers are not present although kinetochore-fibers are well developed. It is suggested that continuous microtubules arranged as distinct bundles are necessary for a normal bipolar anaphase. Irregularities at anaphase resulted in: a) Formation of restitution nuclei from whole chromosomes (kinetochore regions unsplit) or chromatids. b) Separation of chromosomes or chromatids into a few irregular groups which form restitution nuclei of different sizes. (2) Disturbances in phragmoplast development, often leading to the formation of multipolar phragmoplasts and a branched cell plate. During recovery in tap water, aberrant mitoses are gradually replaced by normal ones both in polyploid and hypoploid nuclei (even those containing only two chromosomes).

Pharmacology and Chemistry of a Potent Hepatoprotective Compound Picroliv Isolated from the Roots and Rhizomes of Picrorhiza kurroa Royle ex Benth. (Kutki)

Natural products from plants are of major pharmaceutical and therapeutic importance, several of which are often obtained from the underground parts of the concerned plants. Deviation from standard rules in modern medicines, where instead of a single isolated fraction, a group of naturally occurring components exerts the desired therapeutic effect, was noted in case of Picroliv or Kutkin of Picrorhiza kurroa. "Picroliv" mainly a glucoside, is one such compound, normally obtained from 3 - 4 years old roots and rhizomes of an endangered medicinal plant - Picrorhiza kurroa (kutki) and constitute an important component of many Indian herbal preparations, used mainly for the treatment of a variety of liver ailments. It is an iridoid glycoside mixture containing 60% picroside I and kutkoside in the ratio of 1:1.5. Picroliv has shown efficacy comparable to silymarin in rodent models of galactosamine, paracetamol, thioacetamide and CCl(4) induced hepatic damage. Picroliv has also shown cholerectic effect in rats and anti-cholestatic effect in rats, guinea pigs and cats treated with paracetamol and ethinyl estradiol. It has also anti-viral and immune-stimulant activities and is devoid of any significant CNS and CVS, autonomic and other systemic activity. Because of its apparent ability as a strong hepato-protective and immune-modulatory compound, it is in high demand in both national and international markets. The review discusses the potential of Picrorhiza in various hepatic diseases as well as the chemistry and activity of individual compound of crude drug Picroliv.

Simultaneous Analysis of a Mixture of Iridoids in Water Extracts of Plantago asiatica L. by LC

A simple liquid chromatographic method using an ultraviolet detector was developed for the simultaneous quantification of a mixture of iridoid glycosides, catalpol, aucubin, and geniposidic acid. By adding a minute amount of trifluoroacetic acid into the conventional aqueous acetonitrile mobile phase, the unstable resolution arising from the tautomeric rearrangements in the carboxylic group at the 11 position of geniposidic acid could be solved, resulting in a clear separation profile of the catalpol, aucubin, and geniposidic acid peaks. We were able to quantify the contents of catalpol, aucubin, and geniposidic acid contained in the leaves and seeds of P. asiatica.

Batatinosides II−VI, Acylated Lipooligosaccharides from the Resin Glycosides of Sweet Potato

Sweet potato ( Ipomoea batatas) belongs to the Convolvulaceae (morning glory family) and is native to Mexico and Central America. Its edible tuberous roots have been much appreciated since pre-Hispanic times in Mesoamerica and now play an important role as a basic diet staple and a medicinal plant worldwide. The hexane-soluble extract from roots, through preparative-scale recycling HPLC, yielded five new lipophilic oligosaccharides of jalapinolic acid, batatinosides II-VI ( 1- 5), as well as the known pescapreins I ( 6) and VII ( 7) and murucoidin I ( 8), which are part of the purgative resin glycoside mixture. NMR spectroscopy and FAB mass spectrometry were used to characterize their structures. Compounds 1 and 2 are tetraglycosidic lactones of operculinic acid C. The pentasaccharide structures for compounds 3 and 4 were confirmed to be macrolactones of simonic acid B, and that characterized for 5 was derived from operculinic acid A. The lactonization site of the aglycone was placed at C-3 of the second saccharide unit in all compounds except 4, where it was placed at C-2. All compounds contain an esterifying residue that is composed of a long-chain fatty acid, n-decanoic acid (capric) or n-dodecanoic acid (lauric). In compound 3, an additional short-chain fatty acid, (2 S)-methylbutyric acid, was also identified.

Three New Pentasaccharide Resin Glycosides from the Roots of Sweet Potato (Ipomoea batatas)

Three new pentasaccharide resin glycosides, batatosides III-V (1-3), were isolated from the roots of Sweet potato (Ipomoea batatas). Saponification of the crude resin glycoside mixture yielded substituents and simonic acid B. The structures of the isolated compounds (1-3) were established through spectroscopic analyses, including high field NMR spectroscopy and HR-ESI-MS, and chemical correlation. The major characteristics of 3 are the presence of three different substituents, especially the substituent of cinnamic acid was seldom. The monosaccharides of 1-3 were proved by GC-MS and the absolute configuration of aglycone was further established as S by Mosher's method with R-methyloxyphenylacetic acid (MPA) and S-MPA.

Solasodine glycoalkaloids: a novel topical therapy for basal cell carcinoma. A double‐blind, randomized, placebo‐controlled, parallel group, multicenter study

To assess the safety and efficacy of a 0.005% mixture of solasodine glycosides (Zycure) in the treatment of basal cell carcinoma. Design Double-blind, randomized, and vehicle-controlled, parallel group study. Ten centers in the United Kingdom. Participants Male, n = 50; female, n = 44; age range, 32-95 years (Table 1). Ninety-four patients were randomized on a 2 : 1 ratio (n = 62, Zycure; n = 32, vehicle). Histologically confirmed lesions were treated double blinded, twice daily under occlusion with Zycure or vehicle for 8 weeks. Patients were reviewed fortnightly for adverse effects and overall response. Successfully treated patients were followed up at six-month intervals for a year. The primary efficacy endpoint was histologically confirmed clearance of the basal cell carcinoma (2-mm punch biopsy) at the end of 8-week treatment. Efficacy (intention-to-treat population) at 8 weeks was 66% (41/62) in the Zycure group, compared to 25% (8/32) in the vehicle group (P < 0.001; Cochran-Mantel-Haenszel test). Ninety percent (37/41) of the Zycure group completed follow-up at six-month intervals for 1 year, of whom 78% (29/37) had no recurrence. There were no major treatment-related adverse effects, although 10 patients in Zycure group did not complete the treatment protocol for various reasons. We conclude that the solasodine glycoside cream Zycure is a safe therapy for basal cell carcinoma, with a cure rate of 66% at 8 weeks and 78% at 1 year follow-up.

Subtype-specific activation of estrogen receptors by a special extract of Rheum rhaponticum (ERr 731®), its aglycones and structurally related compounds in U2OS human osteosarcoma cells

The special extract ERr 731 from the roots of Rheum rhaponticum is the major constituent of Phytoestrol N which is used for the alleviation of menopausal symptoms. Recently, we demonstrated that ERr 731 and its aglycones trans-rhapontigenin and desoxyrhapontigenin as single test substances do not activate the estrogen receptors-alpha (ERalpha) in human endometrial adenoarcinoma cells. However, these substances together with the structurally related hydroxystilbenes cis-rhapontigenin, resveratrol and piceatannol activated the ERbeta-dependent reporter gene activity. To investigate if these substance are tissue selective ER activators, ERr 731 and the single test substances were examined in bone-derived U2OS cells stably expressing ERalpha or transiently expressing ERbeta. In the ERalpha expressing U2OS cells, a weak, but statistically significant ERalpha-coupled luciferase activity was detected with ERr 731 and desoxyrhapontigenin which was 10-times lower than with 10(8) M 17 beta-estradiol. In the ERbeta test system, all test substances significantly induced the luciferase activity in a magnitude comparable to 17beta-estradiol. All effects were abolished with the pure ER antagonist ICI 182 780, indicating an ER-specific effect. Intracellular actions were also examined with the glycosylated ERr 731 constituents rhaponticin and desoxyrhaponticin. Treatment of U2OS cells with defined mixtures of both glycosides resulted in a reporter gene activity comparable to that of ERr 731, thereby providing evidence for the existence of cellular uptake mechanisms for glycosylated hydroxystilbenes. This report confirms the strong ERbeta-dependent activity of ERr 731 and provides evidence for a tissue selective ER agonistic activity by ERr 731 and its aglycones, as demonstrated by the activation of ERalpha in bone cells but not in endometrial cells.

Glycosidic juvenogens: Derivatives bearing α,β-unsaturated ester functionalities

A series of the protected alkyl glycosides 5a/ 5b– 12a/ 12b was synthesized from the parent isomeric alcohols (insect juvenile hormone bioanalogs; juvenoids), 4-[4′-(2″-hydroxycyclohexyl)methylphenoxy]-3-methyl-but-2-enoic acid ethyl ester ( 1a/ 1b– 4a/ 4b; racemic structures) and ( 1a– 4a; enantiopure structures). Cadmium carbonate was used as a promoter of this Koenigs–Knorr reaction, and the products were obtained in 82–92% yields. Deprotection of the carbohydrate functionality of 5a/ 5b– 12a/ 12b was carefully performed using ethanolysis in the presence of zinc acetate, due to the presence of another ester functionality in the aglycone part of the molecule of protected alkyl glycosides. Resulting alkyl glycosides 13a/ 13b– 20a/ 20b (diastereoisomeric mixtures) and 13a– 20a (enantiopure compounds), biochemically activated hormonogenic compounds (juvenogens), were obtained in 82–93% yields. Finally, chiral HPLC separation of the diastereoisomeric mixtures of alkyl glycosides was applied to get sufficient quantities of the respective enantiomers 13b– 20b of the alkyl glycosides for their structure elucidation and 13C chemical shift assignment by 1H and 13C NMR spectroscopy. Partial introductory entomological screening tests of the target alkyl glycosides 13a/ 13b– 20a/ 20b were performed on the red firebug ( Pyrrhocoris apterus). The results of this biological testing clearly demonstrated the time-extended effect of several juvenogens on P. apterus due to their biochemical activation, i.e., hydrolysis of the juvenogen molecule, which results in liberation of the biologically active juvenoid in the insect organism.

In vivo Anti-Inflammatory and Antinociceptive Activity Evaluation of Phenolic Compounds from Sideritis stricta

An acetone extract obtained from aerial parts of S. stricta Boiss. & Heldr. apud Bentham, its fractions and phenolic compounds were investigated for their in vivo anti-inflammatory and antinociceptive activities. For the anti-inflammatory activity and for the antinociceptive activity assessment, carrageenan-induced hind paw edema and p-benzoquinone-induced abdominal constriction tests were used, respectively. The acetone extract of the plant and its phenolic fraction exhibited potent inhibitory activity against both bioassay models in mice. From the active phenolic fraction a well-known phenylethanoid glycoside, verbascoside (acteoside) (1), and two flavonoid glycosides, isoscutellarein 7-O-[6"'-O-acetyl-beta-D-allopyranosyl-(1-->2)]-beta-D-glucopyranoside (2) and isoscutellarein 7-O-[6"'-O-acetyl-beta-D-allopyranosyl-(1-->2)]-6"-O-acetyl-beta-D-glucopyranoside (3), were isolated. During phytochemical studies we also isolated a methoxyflavone, xanthomicrol (4), from the non-polar fraction. The structures of the isolated compounds were established by spectroscopic evidence (UV, IR, 1D- and 2D-NMR, MS). Although antinociceptive and anti-inflammatory activities of the phenolic components were found not significant in the statistical analysis, compounds 1 to 3 showed a notable activity without inducing any apparent acute toxicity as well as gastric damage. Furthermore, a mixture of flavonoid glycosides (2 + 3) exhibited a significant inhibitory effect in both models at a higher dose.

Glycosylation and Pyranose—Furanose Isomerization of Carbohydrates Using HClO4—SiO2: Synthesis of Oligosaccharides Containing Galactofuranose.

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Intrapilosins I−VII, Pentasaccharides from the Seeds of Ipomoea intrapilosa

Purification of a CHCl3-soluble extract from seeds of the Mexican medicinal arborescent morning glory, Ipomoea intrapilosa, by means of preparative-scale recycling HPLC, yielded seven new resin glycosides, intrapilosins I-VII (1-7). Their structures were established through the interpretation of their NMR spectroscopic and FABMS data. All pentasaccharides were found to be macrolactones of the known operculinic acid A with different fatty acids esterifying the same positions: C-2 on the second rhamnose unit and C-3 and C-4 on the third rhamnose moiety. The lactonization site of the aglycon could be placed at C-2 of the second saccharide. The fatty acid components of 1-7 were identified as (+)-(2S)-methylbutanoic, octanoic (caprylic), dodecanoic (lauric), and trans-cinnamic. The less common (-)-(2R)-methylbutanoic acid was also isolated as one of the saponification-liberated residues from intrapilosin IV (4). The presence of the (2R)- and (2S)-methylbutanoyl enantiomers bonded to the same oligosaccharide core in intrapilosins IV (4) and V (5) represents an example of diastereoisomerism due to a chiral esterifying moiety in the resin glycoside mixtures of a morning glory species.

Glycosylation and Pyranose-Furanose Isomerization of Carbohydrates Using HClO4-SiO2: Synthesis of Oligosaccharides Containing Galactofuranose

A series of di- and trisaccharides containing 6-O-linked galactofuranose were synthesized as an anomeric mixture of methyl glycosides using silica-supported perchloric acid.

Ontogenetic and Seasonal Variation in the Flavonoid Composition of Sophora japonica. Cultivated in Bulgaria

Quantitative changes in the accumulation of the flavonol glycosides rutin and kaempferol 3-rutinoside and the isoflavone glycosides genistin and sophorabioside have been investigated in flowers and fruits of cultivated in Bulgaria Sophora japonica. during ontogenetic and seasonal development. A method for extraction of flavonoids with good recovery was developed (98% for rutin and 97% for kaempferol 3-rutinoside). The subsequent high-performance liquid chromatography separation of flavonoid glycosides was achieved using Hypersil ODS C18 column and UV detection. The mobile phase comprised methanol and phosphate buffer, pH 3.23, and linear gradient elution mode within 25 min was applied. Accumulation of rutin started with initiation of the flower buds, having the maximal content up to 287 mg/g (dry weight) in mid-July during the earliest stages of flower development and tended to have high levels until mid-August. A further decrease in the amount of rutin up to 44 mg/g was found proportionally with the decline of flavonoids throughout and after the flowering period. Rutin was the predominant glycoside and can account for up to 90% of flavonoid glycoside mixture in young buds, whereas sophorabioside (64.7 mg/g, calculated as rutin equivalent) and kaempferol 3-rutinoside (46.8 mg/g) dominated at later development stages of the fruits. No significant differences in flavonoid quantity between the analysis periods of two successive years were observed. This indicated clearly the ontogenetic dependence of flavonoid formation.

Resin Glycosides from the Flowers of Ipomoea murucoides

The CHCl(3)-soluble extract from the flowers of the Mexican medicinal plant Ipomoea murucoides, through preparative-scale recycling HPLC, yielded murucoidins I-V (1-5), which are new pentasaccharides of jalapinolic acid, as well as the known stoloniferin I (6). Saponification of the crude resin glycoside mixture yielded two glycosidic acids, simonic acid B (9) and operculinic acid A (10), and their esterifying residues were composed of the two short-chain fatty acids, 2-methylpropanoic and (2S)-methylbutyric acids. All the isolated compounds (1-6) were characterized through high-field NMR spectroscopy. Compound 4 exhibited marginal cytotoxicity against Hep-2 cells (ED(50) 4 microg/mL).

Separation of O- and C-allyl glycoside anomeric mixtures by capillary electrophoresis and high-performance liquid chromatography

Rapid and reliable methods for the analysis of O- and C-allyl galactopyranosides and glucopyranosides are presented, based on capillary zone electrophoresis (CZE) and micellar electrokinetic capillary chromatography (MEKC). In MEKC, the formation of chromophoric and charged complexes between the saccharides and borate as well as the hydrophobic interactions with micelles jointly contributed to the selective separation and sensitive detection of all the investigated anomeric couples. Some non-purified synthesis mixtures of C-allyl glycosides were successfully characterised without pre-treatment. MEKC buffer conditions for which glycosides separation was successfully achieved were then exported and applied to reverse-phase liquid chromatography (RP-HPLC), for the quantitative isolation of each allyl glycoside anomer. Identification of the obtained anomeric products was performed by electrospray mass spectrometry and 13C NMR spectroscopy. Glycoside–solvent interactions driving the selective anomeric separation were shortly addressed and discussed on the basis of sugar derivatives structural differences.