Studies on the probing stimulants for the white-backed planthopper,Sogatella furcifera (Homoptera: Delphacidae) in rice plant (Oryza sativa L.)

To elucidate the probing stimulants in rice plants for the white-backed planthopper, Sogatella furcifera, bioassay-guided separations were conducted, which led to the isolation of four active compounds. Using NMR and LC-MS spectra, their structures were determined as isoorientin 2″-O-(6?-(E)-feruloyl)glucoside, isoorientin 2″-O-(6?-(E)-p-coumaroyl)glucoside, tricin 5-O-glucoside, and isoscoparin 2″-O-(6?-(E)-feruloyl)glucoside.     

Structure and Hypotensive Effect of Flavonoid Glycosides in Kinkan (Fortunella japonica) Peelings

An attempt was made to isolate the hypotensive substances from a hot water extract of kinkan. Eight flavonoid glycosides were isolated by repeated chromatography and by gel filtration after extracting with n-butanol and treating with lead subacetate. Their structures were established to be 6,8-di-C-glucosylapigenin (1), 3,6-di-C-glucosylacacetin (2), 2″-O-α-l-rhamnosyl-4′-O-methyl-vitexin (3), 2″-O-α-l-rhamnosyl-4′-O-methylisovitexin (4), 2″-O-α-l-rhamnosylvitexin (5), 2″-O-α-l-rhamnosylorientin (6), 2″-O-α-l-rhamnosyl-4′-O-methylorientin (7) and ponicilin (8) by UV. MS, ¹-NMR and ¹³C-NMR spectroscopy, and by sugar analysis. Each component was intravenously injected in SHR-SP (0.5 ~ 1.0 mg/100 g of body weight), 1, 2, 5 and 6 were found to lower the rat blood pressure.

Among these compounds, 2, 3, 4, 6 and 7 were new flavone glycosides.     

Studies Towards the Large Scale Chemical Synthesis of the Precursors of Ribonucleosides-3′,4′,5′,5″- 2H 4 and -2′,3′,4′,5′,5″- 2H 5

Abstract

A summary delineating the large scale synthetic studies to prepare labeled precursors of ribonucleosides-3′,4′,5′,5″- ²H ₄ and -2′,3′,4′,5′,5″- ²H ₅ from D-glucose is presented. The recycling of deuterium-labeled by-products has been devised to give a high overall yield of the intermediates and an expedient protocol has been elaborated for the conversion of 3-O-benzyl-α,β-D-allofuranose-3,4-d ₂ 6 to 1-O-methyl-3-O-benzyl-2-O-t-butyldimethylsilyl-α,β-D-ribofuranose-3,4,5,5′-d ₄ 16 (precursor of ribonucleosides-3′,4′,5′,5″- ²H ₄ ) or to 1-O-methyl-3,5-di-O-benzyl-α,β-D-ribofuranose-3,4,5,5′-d ₄ 18 (precursor of ribonucleosides-3′,4′,5′,5″- ²H ₄ ).     

18-Norspirostanol derivatives from Trillium tschonoskii

Three 18-norspironstanol oligoglycosides partly acylated in their sugar moieties were isolated from the underground parts of Trillium tschonoskii. Their structures were characterized, as 1-O-[2″,3″,4″-tri-O-acetyl-α-l-rhamnopyranosyl-(1 → 2)-α-l-arabinopyranosyl]-epitrillenogenin-24-O-acetate, 1-O-[2″,3″,4″-tri-O-acetyl-α-l-rhamno-pyranosyl-(1 → 2)-α-l-arabinopyranosyl]-epitrillenogenin and 1-O-[2″,4″-di-O-acetyl-α-l-rhamnopyranosyl-(1 → 2)-α-l-arabinopyranosyl]-epitrillenogenin-24-O-acetate.     

Regioselective acylation of several polyhydroxylated natural compounds by Candida antarctica lipase B

Regioselective acylation of four polyhydroxylated natural compounds, deacetyl asperulosidic acid (1), asperulosidic acid (2), puerarin (3) and resveratrol (4) by Candida antarctica Lipase B in the presence of various acyl donors (vinyl acetate, vinyl decanoate or vinyl cinnamoate) was studied. Compounds 1, 2 and 4 were regioselectively acetylated with vinyl acetate to afford products, 3′-O-acetyl-10-O-deacetylasperulosidic acid (1a), 3′,6′-O-diacetyl-10-O-deacetylasperulosidic acid (1b), 3′-O-acetylasperulosidic acid (2a), 3′,6′-O-diacetylasperulosidic acid (2b), 4′-O-acetylresveratrol (4a), respectively, with yields of 22 to 50%, while reactions with vinyl decanoate and vinyl cinnamoate were slow with lower yields. Compound 3 was readily acylated with all three acyl donors and quantitatively converted to products 6″-O-acetylpuerarin (3a), 6″-O-decanoylpuerarin (3b), 6″-O-cinnamoylpuerarin (3c), respectively. The structures of these acylated products were determined by spectroscopic methods (MS and NMR).     

Synthesis of O-β-D-Ribofuranosyl-(1″-2′)-adenosine-5″-O-phosphate

Abstract

The first synthesis of O-β-D-ribofuranosyl-(1″-2′)-adenosine-5″-O-phosphate starting from protected 2′-O-β-D-ribofuranosyladenosine has been performed.     

Benzothiazolyl Guanidines as Antibacterials

Some new N-p-chlorophenyl-N′-2-(substituted) benzothiazolyl-N″-alkyl guanidines have been synthesized. Several of these including some N-p-chlorophenyl-N′-2-(substituted)benzothiazolyl guanidines and N-p-chlorophenyl-N′-2-(substituted) benzothiazolyl-N″-methyl guanidines^* have been tested for their antibacterial activities against B. subtilis, S. aureus, S. typhi., E. coli and A. tumefaciens, and also for their antitubercular activity against M. tuberculosis (H37Rv).     

Flavonoid glycosides in Malabar spinach Basella alba inhibit the growth of Spodoptera litura larvae

Basella alba is a perennial plant of the Basellaceae and is known by various common names including Malabar spinach. There are few insects that cause damage to B. alba. In this study, we examined the effect of B. alba leaves on the growth of Spodoptera litura larvae. B. alba leaves and a methanolic extract of the leaves inhibited the growth of S. litura larvae. Half of the larvae reared on the leaves died within 1 week. We found that two flavonoids, vitexin, and vitexin-2″-O-arabinofuranoside, were abundant in the methanol extract of leaves. When larvae were reared on purified vitexin or vitexin-2″-O-arabinofuranoside, their growth was significantly impaired compared with larvae reared on control spinach leaves. These results suggested that the flavonoid glycosides in B. alba leaves act as deterrents to S. litura larvae.     

Flavonolacyl glucosides from the aril of Schotia brachypetala Sond. and their antioxidant,antibacterial and antimalarial activities

Two new flavonolacyl glucosides, 3-O-methylquercetin 7-O-[β-D-6″-(E-p-coumaroyl) glucopyranoside] (1) and 3,4′-di-O-methylquercetin 7-O-[β-D-6″-(E-p-coumaroyl) glucopyranoside] (2), four known flavonol glycosides (3–5, 7) and one known dihydroflavonolglucoside (6) were isolated from the aril part of Schotia brachypetala with high-speed countercurrent chromatography (HSCCC) as the primary chromatographic technique. The structures of the isolated compounds were elucidated with spectroscopic and spectrometric methods and acid hydrolysis. The 1,1-diphenyl-2-picrylhydrazyl (DPPH) antioxidant, antibacterial and antimalarial activities of selected isolates were evaluated. Strong to moderate antioxidant activity (lowest IC₅₀ of 15.2 μM), moderate to weak antibacterial activity (lowest MIC of 0.13 mg/mL) and moderate antimalarial activity (lowest IC₅₀ of 5.18 μg/mL) compared to the positive controls were observed.     

Dihydrochalcone glucosides and antioxidant activity from the roots of Anneslea fragrans var. lanceolata

Bioassay-guided fractionation of the roots of Anneslea fragrans var. lanceolata led to the isolation of four dihydrochalcone glucosides, davidigenin-2′-O-(6″-O-4″′-hydroxybenzoyl)-β-glucoside (1), davidigenin-2′-O-(2″-O-4″′-hydroxybenzoyl)-β-glucoside (2), davidigenin-2′-O-(3″-O-4″′-hydroxybenzoyl)-β-glucoside (3), and davidigenin-2′-O-(6″-O-syringoyl)-β-glucoside (4), and 13 known compounds. The structures were identified by means of spectroscopic analysis. Davidigenin-2′-O-(6″-O-syringoyl)-β-glucoside (4), 1-O-3,4-dimethoxy-5-hydroxyphenyl-6-O-(3,5-di-O-methylgalloyl)-β-glucopyranoside (5), lyoniresinol (10), and syringic acid (13) showed ABTS [2,2′-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid)] cation radical scavenging activity, with SC₅₀ values of 52.6 ± 5.5, 26.0 ± 0.7, 6.0 ± 0.2, and 27.5 ± 0.6 μg/mL in 20 min, respectively. Lyoniresinol (10), isofraxidin (12), and syringic acid (13) also showed DPPH [1,1-diphenyl-2-picrylhydrazyl] radical scavenging activity, with SC₅₀ values of 8.4 ± 1.8, 51.6 ± 2.2, and 4.3 ± 0.7 μg/mL in 30 min, respectively.     

Malonyl Isoflavone Glycosides in Soybean Seeds (Glycine max Merrill)

The isoflavone constituents in soybean seeds were investigated, and 9 kinds of isoflavone glycosides were isolated from the hypocotyls of soybean seeds. Three kinds were proved to be malonylated soybean isoflavones named 6″-O-malonyldaidzin, 6″-O-malonylglycitin and 6″-O-malonylgenistin by UV, MS, IR and NMR. The malonylated isoflavone glycosides as major isoflavone constituents in soybean seed were thermally unstable, and were converted into their corresponding isoflavone glycosides. All of the isoflavone components produced intensely undesirable taste effects such as bitter, astringent and dry mouth feeling.     

Purification and characterization of a novel O-methyltransferase from Flammulina velutipes

An enzyme catalyzing the methylation of phenolic hydroxyl groups in polyphenols was identified from mycelial cultures of edible mushrooms to synthesize O-methylated polyphenols. Enzyme activity was measured to assess whether methyl groups were introduced into (?)-epigallocatechin-3-O-gallate (EGCG) using SAM as a methyl donor, and (?)-epigallocatechin-3-O-(3-O-methyl)-gallate (EGCG3″Me), (?)-epigallocatechin-3-O-(4-O-methyl)-gallate (EGCG4″Me), and (?)-epigallocatechin-3-O-(3,5-O-dimethyl)-gallate (EGCG3″,5″diMe) peaks were detected using crude enzyme preparations from mycelial cultures of Flammulina velutipes. The enzyme was purified using chromatographic and two-dimensional electrophoresis. The purified enzyme was subsequently analyzed on the basis of the partial amino acid sequence using LC–MS/MS. Partial amino acid sequencing identified the 17 and 12 amino acid sequences, VLEVGTLGGYSTTWLAR and TGGIIIVDNVVR. In database searches, these sequences showed high identity with O-methyltransferases from other mushroom species and completely matched 11 of 17 and 9 of 12 amino acids from five other mushroom O-methyltransferases.     

Synthesis and Properties of Phosphorylated 3′-O-β-D-Ribofuranosyl-2′-deoxythymidine

Abstract

A strategy was developed for the synthesis of 3′-O-β-D-ribofuranosyl 2′-deoxythymidine derivatives using three different protecting groups, which allows the synthesis of a phosphoramidite building block for oligonucleotide synthesis. Likewise the 5′-O- and 5″-O-phosphorylated analogues were synthesized and their conformation was determined using NMR spectroscopy.     

Syntheses of procyanidin B2 and B3 gallate derivatives using equimolar condensation mediated by Yb(OTf)3 and their antitumor activities

Synthesis of procyanidin B2 and B3 gallate derivatives, 3-O-gallate, 3″-O-gallate, and 3,3″-di-O-gallate, were synthesized using equimolar condensation mediated by Yb(OTf)₃. Synthesized compounds showed significant antitumor effects against human prostate PC-3 cell lines. Their activities were weaker than well-known EGCG and prodelphinidin B3.     

Identification and characterization of a rhamnosyltransferase involved in rutin biosynthesis in Fagopyrum esculentum (common buckwheat)

Rutin, a 3-rutinosyl quercetin, is a representative flavonoid distributed in many plant species, and is highlighted for its therapeutic potential. In this study, we purified uridine diphosphate-rhamnose: quercetin 3-O-glucoside 6″-O-rhamnosyltransferase and isolated the corresponding cDNA (FeF3G6″RhaT) from seedlings of common buckwheat (Fagopyrum esculentum). The recombinant FeF3G6″RhaT enzyme expressed in Escherichia coli exhibited 6″-O-rhamnosylation activity against flavonol 3-O-glucoside and flavonol 3-O-galactoside as substrates, but showed only faint activity against flavonoid 7-O-glucosides. Tobacco cells expressing FeF3G6″RhaT converted the administered quercetin into rutin, suggesting that FeF3G6″RhaT can function as a rhamnosyltransferase in planta. Quantitative PCR analysis on several organs of common buckwheat revealed that accumulation of FeF3G6″RhaT began during the early developmental stages of rutin-accumulating organs, such as flowers, leaves, and cotyledons. These results suggest that FeF3G6″RhaT is involved in rutin biosynthesis in common buckwheat.     

Acylflavonoid C-glycosides from Eleusine coracana

Chromatographic fractionation of the methanolic extract of the shoots of Eleusine coracana led to the identification of three novel acylflavonoid glycosides, 6″-O-3-hydroxy-3-methylglutaroylorientin (1), 6″-O-malonylvitexin (2), and 4″-O-3-hydroxy-3-methylglutaroylvitexin (3) as well as five known flavonoid glycosides, orientin (4), isoorientin (5), vitexin (6), isovitexin (7), and 6″-O-3-hydroxy-3-methylglutaroylvitexin (8). The structures of these compounds were established on the basis of NMR and mass spectral data.     

Effect of Neuroprotective Flavonoids of Agrimonia eupatoria on Glutamate-Induced Oxidative Injury to HT22 Hippocampal Cells

A methanolic extract of Agrimonia eupatoria (Rosaceae) significantly attenuated glutamate-induced oxidative stress in HT22 hippocampal cells. A new flavonoid, characterized as kaempferol 3-O-β-D-(2″-O-acetyl-6″-(E)-p-coumaroyl)-glucopyranoside (2″-acetyl-tiliroside (1), was isolated from the methanolic extract of A. eupatoria stems together with nine known flavonoids. Compounds 4, 7, 8 and 9 all showed a neuroprotective effect on glutamate-induced toxicity in HT22 cells.     

Anti-inflammatory activity of flavonoids from Chrozophora tinctoria

Chemical investigation of Chrozophora tinctoria (L.) A. Juss. growing in Saudi Arabia revealed the isolation of two new acylated flavonoids identified as acacetin-7-O-β-d-[α-l-rhamnosyl(1 → 6)]3″-E-p-coumaroyl glucopyranoside (4) and apigenin-7-O-(6″-Z-p-coumaroyl)-β-d-glucopyranoside (5), in addition to amentoflavone (1), apigenin-7-O-β-d-glucopyranoside (2), apigenin-7-O-6″-E-p-coumaroyl-β-d-glucopyranoside (3) and rutin (6). The structures of isolated compounds were established by 1D, 2D NMR and HRESIMS spectral data, in addition to comparison with literature data. The anti-inflammatory activities of isolated compounds were assessed by measuring the levels of IL-1β, IL-6, TNF-α and PGE₂ in the supernatant media of human peripheral blood mononuclear cells (PBMCs) stimulated by phytohaemagglutinin (PHA). At a concentration of 100 μM, compounds 1, 2, 4 and 6 significantly decreased Il-1β, Il-6 and PGE₂ to nearly normal values. All tested compounds caused a dose-dependent decrease in TNF-α level but failed to reach that of the control values.     

Coumarins from the roots of Prangos uloptera

Three new coumarins, 6-O-[β-d-apiofuranosyl-(1 → 6)-β-d-glucopyranosyl]-prenyletin, 3″-O-[β-d-apiofuranosyl-(1 → 6)-β-d-glucopyranosyl]-oxypeucedanin hydrate and 2″-O-[β-d-apiofuranosyl-(1 → 6)-β-d-glucopyranosyl]-oxypeucedanin hydrate, together with six known coumarins, 3″-O-[β-d-apiofuranosyl-(1 → 6)-β-d-glucopyranosyl]-heraclenol, 3″-O-(β-d-glucopyranosyl)-heraclenol, tortuoside, 3″-O-(β-d-glucopyranosyl)-oxypeucedanin hydrate, heraclenol and oxypeucedanin hydrate, have been isolated from the roots of Prangos uloptera, and the structures of these coumarins were unequivocally determined by spectroscopic means, notably UV, HRESIMS, and 1D and 2D NMR spectroscopy.     

Biosynthesis of a water solubility-enhanced succinyl glucoside derivative of luteolin and its neuroprotective effect

The natural flavonoids luteolin and luteoloside have anti-bacterial, anti-inflammatory, anti-oxidant, anti-tumour, hypolipidemic, cholesterol lowering and neuroprotective effects, but their poor water solubility limits their application in industrial production and the pharmaceutical industry. In this study, luteolin-7-O-β-(6″-O-succinyl)-d -glucoside, a new compound that was prepared by succinyl glycosylation of luteolin by the organic solvent tolerant bacterium Bacillus amyloliquefaciens FJ18 in an 8.0% DMSO (v/v) system, was obtained and identified. Its greater water solubility (2293 times that of luteolin and 12 232 times that of luteoloside) provides the solution to the application problems of luteolin and luteoloside. The conversion rate of luteolin (1.0 g l⁻¹) was almost 100% at 24 h, while the yield of luteolin-7-O-β-(6″-O-succinyl)-d -glucoside reached 76.2%. In experiments involving the oxygen glucose deprivation/reoxygenation injury model of mouse hippocampal neuron cells, the cell viability was significantly improved with luteolin-7-O-β-(6″-O-succinyl)-d -glucoside dosing, and the expressions of the anti-oxidant enzyme HO-1 in the nucleus increased, providing a neuroprotective effect for ischemic cerebral cells. The availability of biosynthetic luteolin-7-O-β-(6″-O-succinyl)-d -glucoside, which is expected to replace luteolin and luteoloside, would effectively expand the clinical application value of luteolin derivatives.