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.     

A New Pregnane from Munronia delavayi Franc （Meliaceae）

To search for pharmacologically active constituents of folk medicine, a new pregnane, 2α,3α,15β-trihydroxy-20（S）-tigloyl-pregnane （compound 1）, and nine known compounds, geranylgeraniol （compound 2）, β-daucosterol （compound 3）, 6-hydroxystigmast-4oen-3-one （compound 4）, sitoindoside Ⅰ （compound 5）, sitoindoside Ⅱ （compound 6）, β-sitosterol （compound 7）, kaempferol （compound 8）, quercetin （compound 9）, and rutin （compound 10）, were isolated from the ethanol extract of whole plants of Munronia delavayi Franch using chromatographic methods. The structures of compounds 1-10 were elucidated on the basis of spectral data.     

Triterpenoids from the Roots of Craibiodendron henryi W. W. Smith

A new triterpenoid, 11a.O.trans-p-coumaroyltaraxerol （1）, along with 11 known triterpenoids, taraxerone （2）, taraxerol （3）, 2α,3β,23,24-tetrahydroxyolean-12-en-28-oic acid （4）, oleanolic acid （5）, β-amyrin （6）, 3β,23-dihydroxylursan-12-en- 28-oic acid （7）, 2α,3β-dihydroxyursan-12-en-28-oic acid （8）, 2α,3β,23-trihydroxyursan-12-en-28-oic acid （9）, 2α,3β,24- trihydroxyursan-12-en-28-oic acid （10）, u rsolic acid （11）, and 3-O-acetylursolic acid （12）, was isolated from Craibiodendron henryi W. W. Smith （Ericaceae）. The structures of these compounds were elucidated on the basis of spectral evidence. Antioxidant activity and vasodilator effect of compound 1 were assessed.     

Chemical Constituents of Siegesbeckia orientalis L.

The aerial parts of Siegesbeckia have been used as the traditional Chinese medicine in the treatment of rheumatic arthritis, hypertension, malaria, neurasthenia, and snakebite. In order to find new and bioactive compounds, the chemical constituents of the aerial parts of S. orientalis L. were investigated and two new compounds, namely β-D-glucopyranosyl-ent-2-oxo-15,16-dihydroxy-pimar-8（14）-en-19-oic-late （compound 1 ） and [1 （10） E,4Z]-8β-angeloyloxy-9α-methoxy-6α, 15-dihydroxy-14-oxogermacra-1 （10）,4,11 （13）-trien-12-oic acid 12,6-1actone （compound 2）, as well as five known ent-pimarane diterpenes （compounds 3-7） were isolated. The structures of the two new compounds were identified by their physicochemical properties and spectral analysis, particularly oneand two-dimensional nuclear magnetic resonance spectral methods.     

Novel Neolignan from Penthorum chinense

A new neolignan （7＇E）-2＇,4,8-trihydroxy-3-methoxy-2,4＇-epoxy-8,5＇-neolign-7＇-en-7-one （1） was isolated from the whole plants of Penthorum chinense Pursh, along with Iupeol （2）, betulinic acid （3）, glyceryl monopalmitate （4）, β-sitosterol （5）, palmitic acid （5）, ursolic acid （7）, 2β,3β,23-trihydroxy-urs-12-ene-28-oic acid （8）, glyceryl monolaurate （9）, scopoletin （10）, （-）syringaresinol （11）, 9,9＇-O-diferuIoyl-（-）-secoisolariciresionl （12）, pinocembrin （13）, apigenin （14）, kaempferol （15）, Iuteolin （16）, β-daucosterol （17）, quercetin （18）, 1-O-（β-D-glucopyranosyl）-（2S, 2＇R, 3R,4E,8E）-2-（2＇-hydroxyhexadecanoy- lamino）-4,8-octdecadiene-1,3-diol （19）, gallic acid （20）, pinocembrin-7-O-β-D-glucoside （21）, and quercetin-3-O-β-D- glucoside （22）. The structures of these compounds were elucidated on the basis of chemical and spectral evidence.     

Chemical Constituents of Daphne giraldii Nitsche

In a search for structurally interesting substances from traditional Chinese medicines, eight compounds were isolated from an ethanolic extract of the stem bark of Daphne giraldii Nitsche. On the basis of one- and two-dimensional nuclear magnetic resonance and mass spectrometry data, and chemical methods, their structures were determined to be 2H-1-benzopyran-2-one-8-hydroxy-7-O-β-D-glucopyranosyl-5-（2-oxo- 2H-1-benzopyran-7-hydroxy-8-yloxy） （compound 1）, 1-pentanone, 1-（4-hydroxyphenyl）-5-phenyl （compound 2）, octadecyl caffeate （compound 3）, （＋）syringaresinol-4,4＇-diglycoside （compound 4）, daphnetin-8-O-β-D- glucopyranoside （compound 5）, p-hydroxybenzoic acid （compound 6）, 7,7＇-dihydroxy-[6, 8＇-bi-2H-benzopyran]- 2, 2＇-dione （compound 7）, and daphnorin （compound 8）, respectively. Of the compounds isolated, compounds 1 and 2, which we named daphnolin and daphnolon, respectively, were new, and the others were obtained from this plant for the first time.     

Two New Triterpenoid Saponins from Akebia quinata （Thunb.） Decne.

Two new triterpenoid saponins, hederagenin 3-O-α-L-arabinopyranosyl-（1→〉2）-α-L-arabinopyranoside named akeboside La （compound 1）, oleanolic acid 3-O-α-L-arabinopyranosyl-（1→〉2）-β-D-glucopyranoside named akeboside Lb （compound 2）, along with five known saponins, oleanolic acid 3-O-α-L-rhamnopyranosyl-（1→〉2）-α-L- arabinopyranoside （compound 3）, hederagenin 3-O-α-L-rhamnopyranosyl-（1→〉2）-α-L-arabinopyranoside （compound 4）, oleanolic acid 3-O-β-D-xylopyranosyl-（1→〉3）-α-L-rhamnopyranosyl-（1→〉2）-α-L-arabinopyranoside （compound 5）, 3-O-α-L-rhamnopyranosyl-（1→〉2）-α-L-arabinopyranosyl oleanolic acid 28-O-α-L-rhamnopyranosyl-（1→〉4）-α-D- glucopyranosyl-（1→〉6）-β-D-glucopyranoside （compound 6）, 3-O-α-L-rhamnopyranosyl-（1→〉2）-α-L-arabinopyranosyl hederagenin 28-α-L-rhamnopyranosyl-（1→〉4）-β-D-glucopyranosyl-（1→〉6）-β-D-glucopyranoside （compound 7） were isolated from the n-butanol part of the 80% ethanol extracts of the dried stems of Akebia quinata （Thunb.） Decne. Compound 5 was isolated from plants of genus Akebia for the first time. The structures were elucidated on the basis of physicochemical properties and spectral data.     

Biotransformation of 4-Hydroxybenzen Derivatives by Hairy Root Cultures of Polygonum multiflorum Thunb.

The biotransformation of four 4-hydroxybenzen derivatives （1,4-benzenediol （compound 1）, 4-hydroxybenzaldehyde （compound 2）, 4-hydroxybenzyl alcohol （compound 3） and 4-hydroxybenzoic acid （compound 4）） by the hairy root cultures of Polygonum multiflorum Thunb. as a new biocatalyst was investigated. It was found that the substrates were transformed to their corresponding glucosides, 4-hydroxyphenyl β-D-glucopyranoside （arbutin, compound la）, 4-hydroxymethylphenyl β-D-glucopyranoside （gastrodin, compounds 2a, 3a） and 4-carboxyphenyl α-D- glucopyranoside （compound 4a）, respectively. In the meantime, the hairy roots of P. multiflorum were able to stereoselectively and regioselectively glucosylate phenolic hydroxyl groups of compounds 1-4, but the cultures could not glucosylate the aldehyde group of compound 2 or the benzyllc hydroxyl group of compound 3, and no glucosyl esterification of carboxyl groups of compound 4 was detected. On the other hand, the result also showed that the hairy roots of P. multiflorum were able to reduce the 4-hydroxybenzaldehyde to its corresponding alcohol. This is the first report that substrate 4 has been converted into its α-D-glucopyranoside by a plant biotransformα- tion system.     

Chemical Constituents of Phacellaria compressa Benth.

Two new compounds, 1-（3-methoxy-4-hydroxyphenyl）-3-（3,5-dimethoxy-4-hydroxyphenyl）-propane （1） and 5, 7, 3＇-trlmethyoxyflavan-4＇-O-β-D-glucopyranoslde （2） were Isolated from the ethanol extract of the dried aerial parts of Phacellarla compressa Benth., together with 2,3-bis[（4-hydroxy-3,5-dimethoxyphenyl）-methyl]-1,4- butanedlol （3）, ethyl 3,4,5-trlhydroxybenzoate （4）, methyl 3, 4, 5-trlhydroxybenzoete （5）, β-sltoeterol （6）, 5, 7, 3＇, 4＇- tetrahydroxyfiavan （7）, lupeol （8）, zhebelreslnol （9）, quercetln-3-O-α-L-rhamnopyranoslde （10）, （＋）-cetechin （11）, betulln （12）, β-daucosterol （13）, （＋）-sydngareslnol （14）, scopoletln （15）, and proxlmadlol （16）. The structures of these compounds were determined by spectral evidence or by comparing them with authentic samples. Compound 9 showed α-amylase Inhibitory activity of 57.55% at a concentration of 50 μg/mL.     

New Isoflavonoid Glycosides from the Rhizomes of Iris leptophylla Lingelsh.

Two new isoflavonoid glucosides, 5-hydroxy-6,7-methylenedioxy-isoflavone-4＇-O-D-glucopyranosyl （2→〉l）-L-rhamnoside （irilone-bioside） （compound 1） and 5,4＇-methoxy-6,7-methylenedioxyisoflavone-3＇-O-β-D-glucoside （irisleptophyllidin） （compound 2）, together with five known compounds, nigricanin- 4＇-O-β-D-glucoside （compound 3）, irifloside （compound 4）, irigenin （compound 5）, 5, 3＇, 4＇-trimethoxy-6,7-methylenedioxyisoflavone （compound 6）, and nigricanin （compound 7） were isolated from the alcoholic extract of rhizomes of Iris leptophylla Lingelsh. Their structures were elucidated by spectroscopic methods.     

Water-Soluble Constituents of Cudrania tricuspidata （Carr.） Bur.

In order to find new structural and biologically active compounds, the constituents of the bark of Cudrania tricuspidata （Carr.） Bur. were investigated and a new 6-p-hydroxybenzyltaxifolin glucoside, named tricusposide （compound 1）, together with 16 known compounds, was isolated by solvent partition, macroporous adsorption resin AB-8, silica gel, Sephadex LH-20 chromatography. Using spectroscopic methods, the structures of the compounds were elucidated as 6-p-hydroxybenzyl taxifolin-7-O-β-D-glucoside （compound 1）, dihydroquerctin-7-O-β-D-glucoside （compound 2）, dihydrokaempferol-3-O-β-D-glucoside （compound 3）, dihydroquercetin （compound 4）, peonoside （compound 5）, sphaerobioside （compound 6）, quercimeritrin （compound 7）, genistein （compound 8）, aromadendrin （compound 9）, kaempferol （compound 10）, genistin （compound 11）, 3,4-dihydroxystyryl alcohol （compound 12）, sucrose （compound 13）, 1,3,5,6-tetrahydroxyxanthone （compound 14）, gericudranin E （compound 15）, gericudranin C （compound 16）, and orobol （compound 17）. Compounds 2-6, 8, 9, 12-14, and 17 were isolated from this genus for the first time.     

Synthesis and binding potencies of cyclohexapeptide somatostatin analogs containing naphthylalanine and arylalkyl peptoid residues

We report the synthesis, binding affinities to the recombinant human somatostatin receptors, and structure‐activity relationship studies of compounds related to the cyclic hexapeptide, c‐[Pro⁶‐Phe⁷‐D‐Trp⁸‐Lys⁹‐Thr¹⁰‐Phe¹¹], L‐363,301 (the numbering in the sequence refers to the position of the residues in native somatostatin). The Pro residue in this compound is replaced with the arylalkyl peptoid residues Nphe (N‐benzylglycine), (S)βMeNphe [(S)‐N‐[(α‐methyl)benzyl]glycine] or (R)βMeNphe [(R)‐N‐[(α‐methyl)benzyl]glycine] and l ‐1‐naphthylalanine is incorporated into either position 7 or 11 of the parent compound. The synthesis and binding data of the Nnal⁶ ([N‐naphthylmethyl]glycine) analog of L‐363,301 is also reported. The incorporation of the Nnal residue into position 6 of L‐363,301 resulted in an analog with weaker binding affinities to all hsst receptors but enhanced selectivity towards the hsst2 receptor compared with the parent compound. The other compounds bind effectively to the hsst2 receptor but show some variations in the binding to the hsst3 and hsst5 receptors resulting in different ratios of binding affinities to the hsst5 and hsst2 or hsst3 and hsst2, respectively. The incorporation of the Nphe residue into position 6 and the Nal residue into position 7 of L‐363,301 led to a compound which binds potently to the hsst2 and has increased selectivity towards this receptor (weaker binding to hsst3 and hsst5 receptors) compared with the parent compound. The analogs with β‐methyl chiral substitutions in the aromatic peptoid side chain and Nal in position 7 or 11 bind effectively to the hsst2 and hsst5 receptors. They exhibit similar ratios of binding affinities to the hsst5 and hsst2 receptors as observed for L‐363,301. There are however minor differences in binding to the hsst3 receptor among these analogs. These studies allow us to investigate the influence of additional hydrophobic groups on the binding activity to the isolated human somatostatin receptors and the results are important for the design of other somatostatin analogs. Copyright © 1999 European Peptide Society and John Wiley & Sons, Ltd.     

Structural characterization of the mitomycin 7-O-methyltransferase

Mitomycins are quinone‐containing antibiotics, widely used as antitumor drugs in chemotherapy. Mitomycin‐7‐O‐methyltransferase (MmcR), a key tailoring enzyme involved in the biosynthesis of mitomycin in Streptomyces lavendulae, catalyzes the 7‐O‐methylation of both C9β‐ and C9α‐configured 7‐hydroxymitomycins. We have determined the crystal structures of the MmcR–S‐adenosylhomocysteine (SAH) binary complex and MmcR–SAH–mitomycin A (MMA) ternary complex at resolutions of 1.9and 2.3 Å, respectively. The study revealed MmcR to adopt a common S‐adenosyl‐L ‐methionine‐dependent O‐methyltransferase fold and the presence of a structurally conserved active site general acid–base pair is consistent with a proton‐assisted methyltransfer common to most methyltransferases. Given the importance of C7 alkylation to modulate mitomycin redox potential, this study may also present a template toward the future engineering of catalysts to generate uniquely bioactive mitomycins. Proteins 2011. © 2011 Wiley‐Liss, Inc.     

A new ferulic acid ester, a new ellagic acid derivative, and other constituents from pachycentria formosana: effects on neutrophil pro-inflammatory responses

A new ferulic acid ester derivative, tetracosane‐1,24‐diyl di[(Z)‐ferulate] ( 1 ), and a new ellagic acid derivative, 3,4 : 3′,4′‐bis(O,O‐methylene)ellagic acid ( 2 ), have been isolated from leaves and twigs of Pachycentria formosana, together with eight known compounds. Their structures were determined by in‐depth spectroscopic and mass‐spectrometric analyses. Among the isolated compounds, oleanolic acid ( 6 ), ursolic acid acetate ( 7 ), and 3‐epibetulinic acid ( 9 ) exhibited potent inhibition (IC₅₀ values ≤21.8 μM ) of O₂^⋅− generation by human neutrophils in response to N‐formyl‐L ‐methionyl‐L ‐leucyl‐L ‐phenylalanine/cytochalasin B (fMLP/CB). In addition, oleanolic acid ( 6 ), 3‐O‐[(E)‐feruloyl]ursolic acid ( 8 ), 3‐epibetulinic acid ( 9 ), and lawsonic acid ( 10 ) also inhibited fMLP/CB‐induced elastase release with IC₅₀ values ≤18.6 μM .     

Cytotoxic Triterpenoids from the Barks of Betula platyphylla var. japonica

Phytochemical investigation on the barks of Betula platyphylla var. japonica (Betulaceae) was carried out, resulting in the isolation and identification of three new triterpenoids, 27‐O‐cis‐caffeoylcylicodiscic acid ( 1 ), 27‐O‐cis‐feruloylcylicodiscic acid ( 2 ), and 27‐O‐cis‐caffeoylmyricerol ( 3 ), along with six known triterpenoids, obtusilinin ( 4 ), winchic acid ( 5 ), 27‐O‐trans‐caffeoylcylicodiscic acid ( 6 ), uncarinic acid E ( 7 ), myriceric acid B ( 8 ), and 3‐O‐trans‐caffeoyloleanolic acid ( 9 ). The structures of the new compounds were elucidated by extensive spectroscopic methods, including 1D‐ and 2D‐NMR, and HR‐ESI‐MS. All of the isolated compounds were evaluated for cytotoxicity against four human tumor cell lines (A549, SK‐OV‐3, SK‐MEL‐2, and Bt549). Compounds 2 , 6 , 8 , and 9 exhibited potent cytotoxicity against all of the tumor cells tested (IC₅₀ < 10.0 μm ), while compounds 3 , 4 , 5 , and 7 showed moderate cytotoxicity against all of the tumor cells tested (IC₅₀ < 20.0 μm ).     

Piptadenin,a Novel 3,4‐Secooleanane Triterpene and Piptadenamide,a New Ceramide from the Stem Bark of Piptadeniastrum africanum (Hook.f.) Brenan

Piptadenin ( 1 ), a new triterpene along with piptadenamide ( 10 ), a new ceramide, have been isolated from the AcOEt‐soluble fraction of the MeOH extract of the stem bark of Piptadeniastrum africanum along with nine known compounds, 1‐O‐[(3β,22β)‐3,22‐dihydroxy‐28‐oxoolean‐12‐en‐28‐yl]‐β‐d ‐glucopyranose ( 2 ), 22β‐hydroxyoleanic acid ( 3 ), oleanic acid ( 4 ), lupeol ( 5 ), betulinic acid ( 6 ), 5α‐stigmasta‐7,22‐dien‐3β‐ol ( 7 ), 5α‐stigmasta‐7,22‐dien‐3‐one ( 8 ), (3β)‐stigmast‐5‐en‐3‐yl β‐d ‐glucopyranoside ( 9 ) and 2,3‐dihydroxypropyl hexacosanoate ( 11 ). Except for compound 11 , all the isolated compounds are reported for the first time from this plant. The structures of the isolated compounds were elucidated by spectroscopic data including 1D and 2D NMR. The pure compounds 1 – 11 were subjected to the pharmacological screening and compounds 2 , 5 – 7 and 9 exhibited potent urease inhibitory activity with IC₅₀ value of 25.8, 28.9, 30.1, 31.8 and 32.7 μm , respectively, whereas compound 1 showed moderate activity (IC₅₀ = 98.7 μm ). The potent urease inhibitory activity supplemented the previous literature reports and medicinal uses of this plant.     

Chemical Constituents from the Flowers of Wild Gardenia jasminoides J.Ellis

Four new iridoids, 2′‐O‐(E)‐coumaroylshanzhiside ( 1 ), 6′‐O‐(E)‐coumaroylshanzhiside ( 2 ), 8α‐butylgardenoside B ( 3 ), 6α‐methoxygenipin ( 4 ), and one new phenylpropanoid glucoside, 5‐(3‐hydroxypropyl)‐2‐methoxyphenyl β‐d ‐glucopyranoside ( 5 ), together with sixteen known compounds, were isolated from the edible flowers of wild Gardenia jasminoides J.Ellis . Their chemical structures were characterized by extensive spectroscopic techniques, including 1D‐ and 2D‐NMR, HR‐ESI‐MS, and CD experiments. The absolute configurations of the new isolates’ sugar moiety were assigned by HPLC analysis of the acid hydrolysates. Furthermore, the antioxidant activities of those isolates were preliminarily evaluated by DPPH scavenging experiment. And comparison of ¹H‐NMR spectra for the EtOH extract of G. jasminoides J.Ellis , gardenoside B and geniposide revealed that the flowers of this plant have a considerable content of gardenoside B instead of geniposide in the fruits, indicating different activities and applications in people's daily life.