Grayanoside C,a new diterpene glucoside from Leucothoe grayana

A new diterpene glucoside has been isolated from Leucothoe grayana. Its structure was elucidated by X-ray diffraction analysis of a dehydrated product of the aglycone and conversion of the same to leucothol A.     

Computational prediction and experimental validation of the activator function of C2-β-D-glucopyranosyl-1,3,6,7-tetrahydroxyxanthone on pancreatic and hepatic hexokinase

Abstract

This study identifies and validates hexokinase type 4 (HK4), an isozyme of hexokinase in the liver and pancreas, as an important target of C2-β-D-glucopyranosyl-1,3,6,7-tetrahydroxyxanthone (βdGT), a xanthone glucoside suggested to have antidiabetic property. In the study, we applied the computational pipeline of molecular docking followed by the molecular dynamics simulations to shortlist potential βdGT protein targets. The analysis of protein dynamics and the binding free energy (ΔG) led us to the identification of HK4 as a key βdGT target, whereby the binding mode and domain dynamics suggested the activator function of βdGT. βdGT bound to the allosteric site of the isozyme ～13?Å away from the substrate (glucose)-binding site. The binding free energy of the ligand-protein complex was energetically feasible (ΔG, –41.61?kcal/mol) and the cleft angle deviation between the two (small and large) domains of HK4 revealed differential HK4 dynamics in response to βdGT binding. 3D structure analysis of the isozyme-ligand complex highlighted the role of Arg63, Glu67 and Lys458 in ligand stabilization and hydrophobic interactions mediated by Tyr214 and Met235. Experimental validation of the results of computational analysis confirmed the activator function of βdGT on HK4. The study has implication in diabetes as βdGT may be used to lower the blood glucose level by activating hepatic and pancreatic hexokinase without the risk of hypoglycemia.

Communicated by Ramaswamy H. Sarma     

Male-to-female transfer of 5-hydroxytryptophan glucoside during mating in Zygaena filipendulae (Lepidoptera)

Zygaena filipendulae accumulates the cyanogenic glucosides linamarin and lotaustralin by larval sequestration from the food plant or de novo biosynthesis. We have previously demonstrated that the Z. filipendulae male transfers linamarin and lotaustralin to the female in the course of mating. In this study we report the additional transfer of 5-hydroxytryptophan glucoside (5-(β-d-glucopyranosyloxy)-l-Tryptophan) from the Z. filipendulae male internal genitalia to the female spermatophore around 5 h into the mating process. 5-Hydroxytryptophan glucoside is present in the virgin male internal genitalia, and production continues during the early phase of mating. Following initiation of 5-hydroxytryptophan glucoside transfer to the female, the amount in male internal genitalia is drastically reduced until after mating where it is slowly replenished. For unambiguous structural identification, 5-hydroxytryptophan glucoside was chemically synthesized and used as an authentic standard. The biological function of 5-hydroxytryptophan glucoside remains to be established, although we have indications that it may be involved in inducing the female to stay in copula and delay egg-laying to prevent re-mating of the female. To our knowledge 5-hydroxytryptophan glucoside has not previously been reported present in animal tissues.     

Isolation of a Novel Carotenoid,OH-chlorobactene Glucoside Hexadecanoate,and Related Rare Carotenoids from Rhodococcus sp. CIP and Their Antioxidative Activities

In the course of screening for antioxidative carotenoids from bacteria, we isolated and identified a novel carotenoid, OH-chlorobactene glucoside hexadecanoate (4), and rare carotenoids, OH-chlorobactene glucoside (1), OH-γ-carotene glucoside (2) and OH-4-keto-γ-carotene glucoside hexadecanoate (3) from Rhodococcus sp. CIP. The singlet oxygen (¹O₂) quenching model of these carotenoids showed potent antioxidative activities IC₅₀ 14.6 μM for OH-chlorobactene glucoside hexadecanoate (4), 6.5 μM for OH-chlorobactene glucoside (1), 9.9 μM for OH-γ-carotene glucoside (2) and 7.3 μM for OH-4-keto-γ-carotene glucoside hexadecanoate (3).     

Study on the interaction between pelargonidin‐3‐O‐glucoside and bovine serum albumin using spectroscopic,transmission electron microscopy and molecular modeling techniques

The aim of this study is to evaluate the binding behavior between pelargonidin‐3‐O‐glucoside (P3G) and bovine serum albumin (BSA) using multi‐spectroscopic, transmission electron microscopy (TEM) and molecular docking methods under physiological conditions. Fluorescence spectroscopy and time‐resolved fluorescence showed that the fluorescence of BSA could be quenched remarkably by P3G via a static quenching mechanism, and there is a single class of binding site on BSA. In addition, the thermodynamic functions ΔH and ΔS were –21.69 kJ/mol and 24.46 J/mol/K, indicating that an electrostatic interaction was a main acting force. The distance between BSA and P3G was 2.74 nm according to Förster's theory, illustrating that energy transfer occurred. In addition, the secondary structure of BSA changed with a decrease in the α‐helix content from 66.2% to 64.0% as seen using synchronous fluorescence, UV/vis, circular dichroism and Fourier transform infrared spectroscopies, whereas TEM images showed that P3G led to BSA aggregation and fibrillation. Furthermore, site marker competitive experiments and molecular docking indicated that P3G could bind with subdomain IIA of BSA. The calculated results of the equilibrium fraction showed that the concentration of free P3G in plasma was high enough to be stored and transported from the circulatory system to its target sites to provide therapeutic effects. Copyright © 2015 John Wiley & Sons, Ltd.     

Isolation of Ceramides from Tagetes patula L. Yellow Flowers and Nematicidal Activity of the Fractions and Pure Compounds against Cyst Nematode,Heterodera zeae

Investigation of yellow flower extract of Tagetes patula L. led to the identification of an aggregate of five phytoceramides. Among them, (2R)‐2‐hydroxy‐N‐[(2S,3S,4R,8E)‐1,3,4‐trihydroxyicos‐8‐en‐2‐yl]icosanamide, (2R)‐2‐hydroxy‐N‐[(2S,3S,4R,8E)‐1,3,4‐trihydroxyicos‐8‐en‐2‐yl]heneicosanamide, (2R)‐2‐hydroxy‐N‐[(2S,3S,4R,8E)‐1,3,4‐trihydroxyicos‐8‐en‐2‐yl]docosanamide, and (2R)‐2‐hydroxy‐N‐[(2S,3S,4R,8E)‐1,3,4‐trihydroxyicos‐8‐en‐2‐yl]tricosanamide were identified as new compounds and termed as tagetceramides, whereas (2R)‐2‐hydroxy‐N‐[(2S,3S,4R,8E)‐1,3,4‐trihydroxyicos‐8‐en‐2‐yl]tetracosanamide was a known ceramide. A steroid (β‐sitosterol glucoside) was also isolated from the subsequent fraction. The structures of these compounds were determined on the basis of spectroscopic analyses, as well as chemical method. Several other compounds were also identified by GC/MS analysis. The fractions and some commercial products, a ceramide HFA, β‐sitosterol, and stigmasterol were evaluated against an economically important cyst nematode, Heterodera zeae. Ceramide HFA showed 100 % mortality, whereas, β‐sitosterol and stigmasterol were 40–50 % active, at 1 % concentration after 24 h of exposure time, while β‐sitosterol glucoside revealed no activity against the nematode.     

Two New Sesquiterpenoid Glucosides from the Aerial Parts of Saussurea involucrate

Two new sesqulterpenoid glucosides, namely α-hydroxycostic acid 6-β-D-glucopyranoside （compound 1） and 11 βH-11,13-dlhydrodehydrocostuslactone 8α-O-（6＇-acetyl）-β-D-glucopyranoside （compound 2）, along with 11 known sesqulterpenoids （compounds 3-13） were isolated from the aerial parts of Saussurea involucrate （Kar. et Kir.） Sch.- BIp. The structures of the new sesquiterpenoid glucosides were established by one- and two-dimensional nuclear magnetic resonance and mass spectrometry analysis.     

Cytotoxic naphthoquinones and plumbagic acid glucosides from Plumbago zeylanica

Two plumbagic acid glucosides, 3'-O-beta-glucopyranosyl plumbagic acid and 3'-O-beta-glucopyranosyl plumbagic acid methylester along with five naphthoquinones (plumbagin, chitranone, maritinone, elliptinone and isoshinanolone), and five coumarins (seselin, 5-methoxyseselin, suberosin, xanthyletin and xanthoxyletin) were isolated from the roots of Plumbago zeylanica. All coumarins were not previously found in this plant. Cytotoxicity of these compounds to various tumor cells lines was evaluated, and plumbagin significantly suppressed growth of Raji, Calu-1, HeLa, and Wish tumor cell lines.     

Plastoquinones are effectively reduced by ferredoxin:NADP+ oxidoreductase in the presence of sodium cholate micelles. Significance for cyclic electron transport and chlororespiration

The effect of sodium cholate and other detergents (Triton X-100, sodium dodecyl sulphate, octyl glucoside, myristyltrimethylammonium bromide) on the reduction of plastoquinones (PQ) with a different length of the side-chain by spinach ferredoxin:NADP(+) oxidoreductase (FNR) in the presence of NADPH has been studied. Both NADPH oxidation and oxygen uptake due to plastosemiquinone autoxidation were highly stimulated only in the presence of sodium cholate among the used detergents. Sodium cholate at the concentration of 20 mM was found to be the most effective on both PQ-4 and PQ-9-mediated oxygen uptake. The FNR-dependent reduction of plastoquinones incorporated into sodium cholate micelles was stimulated by spinach ferredoxin but inhibited by Mg(2+) ions. It was concluded that the structure of sodium cholate micelles facilitates contact of plastoquinone molecules with the enzyme and creates favourable conditions for the reaction similar to those found in thylakoid membranes for PQ-9 reduction. The obtained results were discussed in terms of the function of FNR as a ferredoxin:plastoquinone reductase both in cyclic electron transport and chlororespiration.     

Sesquiterpene lactone glucosides and alkyl glycosides from the fruit of cumin

From the polar portion of the methanolic extract of cumin (fruit of Cuminum cyminum L.), two sesquiterpenoid glucosides, cuminoside A and B, and two alkyl glycosides were isolated together with five known compounds. Their structures were established as (1S,5S,6S,10S)-10-hydroxyguaia-3,7(11)-dien-12,6-olide beta-D-glucopyranoside, (1R,5R,6S,7S,9S,10R,11R)-1,9-dihydroxyeudesm-3-en-12,6-olide 9-O-beta-D-glucopyranoside, methyl beta-D-apiofuranosyl-(1-->6)-beta-D-glucopyranoside and ethane-1,2-diol 1-O-beta-D-apiofuranosyl-(1-->6)-beta-D-glucopyranoside, respectively.