Triterpene glycosides from <Emphasis Type="Italic">Lonicera</Emphasis>. Isolation and structural determination of seven glycosides from flower buds of <Emphasis Type="Italic">Lonicera macranthoides</Emphasis>

The structures of seven triterpene glycosides (1–7), of which the 23-O-acetyl, 28-O-β-D-glucopyranosyl-(1→6)-O-β-D-glucopyranosyl ester of hederagenin 3-O-β-D-glucopyranosyl-(1→3)-O-α-L-rhamnopyranosyl-(1→2)-O-α-L-arabinopyranoside (2) was new, from the flower buds of Lonicera macranthoides were established using chemical and NMR spectroscopic methods. Published in Khimiya Prirodnykh Soedinenii, No. 1, pp. 32–34, January–February, 2008.     

New glycosidic and other constituents from hulls of <Emphasis Type="Italic">Oryza sativa</Emphasis>

Three new compounds, 4-hydroxymethylene-7-(9,9,13-trimethylcyclohexyl)-heptanyl-3′,7′,7′-trimethylcyclohexa-2′,4′-dien-1′-oate (1), 1-(n-hexadec-7-enoxy)-6-(n-octadecanoxy)-β-D-glucopyranoside (2), and (Z)-12-hydroxy-9-octadecenoic acid-12-β-D-glucopyranoside (3), along with the known compound hexacosanoic acid (4), were isolated and identified from the rice hulls of Oryza sativa. Their structures were elucidated by 1D and 2D NMR spectroscopic techniques (¹H-¹H COSY, ¹H-¹³C HETCOR, DEPT) aided by EIMS, FABMS, HRFABMS, and IR spectra. Published in Khimiya Prirodnykh Soedinenii, No. 4, pp. 344–347, July–August, 2007.     

Novel <Emphasis Type="Italic">S</Emphasis>-containing lactones from monoterpene oxides

A new type of S-containing terpene lactones was produced by the reactions of limonene-1,2-oxide and β-pinene-α-oxide with mercaptoacetic acid. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 220–223, May–June, 2007.     

Cytotoxic metabolites of <Emphasis Type="Italic">Streptimonospora salina</Emphasis>

Streptimonospora salina gen. nov., sp. nov. was found to produce three phenoxazinone antibiotics, 2-amino-3H-phenoxazin-3-one (1), 2-methylamino-3H-phenoxazin-3-one (2), 2-acetylamino-3H-phenoxazin-3-one (3), and one phenazine antibiotic, phenazine-1-carboxylic acid (4). The chemical structures of the compounds were determined using 1D and 2D NMR spectrometry and electrospray mass spectrometry (ESMS). Compounds 1-4 exhibited modest cytotoxicity against a human renal carcinoma cell line ACHN with IC₅₀ values of 35.4, 12.4, 65.4, and 82.9 μM, respectively. Compound 2 was discovered for the first time from a biological origin. Published in Khimiya Prirodnykh Soedinenii, No. 4, pp. 405–406, July–August, 2008     

<Emphasis Type="Italic">Brønsted</Emphasis> Acids in Ionic Liquids: Fundamentals,Organic Reactions,and Comparisons

Summary. A background for studying acids in various solvents is developed, emphasizing the importance of knowing to what extent a solvent conducts electricity and is therefore ionized, the dissociation equilibria of common molecular solvents and the acidic and basic species generated by solvent leveling. Acidity measurements in the atypical solvent water are discussed and the common method of expressing acidity in other systems – by Hammett values – is introduced. Representative examples of reactions involving Br?nsted acids in ionic liquids are presented and attention paid to the questions of speciation and acidity values. It is found that the gas phase proton affinity of a base is often a better guide to the acidity of its conjugate acid in an ionic liquid than is the dissociation constant of the said acid in water.     

Sterol composition of the macromycete fungus <Emphasis Type="Italic">Laetiporus sulphureus</Emphasis>

The sterol composition of macromycete fungus Laetiporus sulphureus was analyzed by GC-MS. The fungus contained mainly C16 to C20 fatty acids, C16 to C24 fatty acid ethyl esters, and C28, C29, and C30, Δ⁵, Δ⁷, and Δ^5,7 conventional sterols, and in minor amounts Δ⁰ analogues with saturated and unsaturated side chains. Moreover, ergosterol peroxide and cerevisterol were identified. This sterol pattern was compared with those of other members of the family Polyporaceae reported in the literature. Published in Khimiya Prirodnykh Soedinenii, No. 2, pp. 170–172, March–April, 2009.     

A bicyclo[3.2.1]octanoid neolignan and toxicity of the ethanol extract from the fruit of <Emphasis Type="Italic">Ocotea heterochroma</Emphasis>

A new bicyclo[3.2.1]octanoid neolignan rel-(7S,8R,1′S,2′R,3′S)-Δ8′-2′-hydroxy-5,1′,3′-trimethoxy-3,4methylenedioxy-7,3′,8,1′-neolignan (1) was isolated from ethanol extract from the fruit of Ocotea heterochroma Mez & Sodiro ex Mez as well as the known compounds β-friedelanol (2), meso-dehydroguaiaretic acid (3), and yangambin (4), whose structures were elucidated on the basis of their comprehensive spectroscopic analysis including 2D NMR data. Lethality bioassay using brine shrimp (Artemia salina Leach) was evaluated with the ethanol extract from the Ocotea heterochroma’s fruit. The toxicity of this extract was greater than the toxicity of those fractions obtained in a first solvent partition (benzene, ethyl acetate, and butanol subfractions) and that of a mixture of acetylated 2′-epimers from the new neolignan 1. Published in Khimiya Prirodnykh Soedinenii, No. 2, pp. 158–160, March–April, 2009.     

Composition of essential oils from <Emphasis Type="Italic">Salvia anatolica</Emphasis>, a new species endemic from Turkey

The component composition of essential oils produced by steam distillation from flower heads, leaves, and stems of Salvia anatolica (Lamiaceae), a recently described new species endemic from Turkey, was studied by GC/FID and GC/MS. A total of 127 volatile components representing 96% of the oil was identified in essential oil from flower heads and leaves. It was found that the principal oil components of flower heads and leaves were α-pinene (10.9%), β-pinene (6.7%), α-copaene (6.3%), heptacosane (6.2%), and hexadecanoic acid (5.0%). A total of 109 volatile compounds representing 87.9% of the oil was characterized in essential oil isolated from stems. The principal oil components of stems were identified as hexadecanoic acid (27.2%), tetradecanoic acid (15.2%), dodecanoic acid (5.5%), and α-copaene (5.0%). __________ Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 552–555, November–December, 2007.     

Essential Oil Composition of Four <Emphasis Type="Italic">Achillea</Emphasis> Species from the Balkans and Its Chemotaxonomic Significance

The chemical composition of the essential oils of Achillea clavennae L., Achillea holosericea Sibth. & Sm., Achillea lingulata W. & K., and Achillea millefolium L. from the Balkans was determined by GC and GC/MS analyses. The main components were 1,8-cineole in A. holosericea, camphor in A. clavennae, β-pinene in A. millefolium, and τ-cadinol in A. lingulata. A detailed chemotaxonomic discussion is presented. __________ Published in Khimiya Prirodnykh Soedinenii, No. 6, pp. 555–558, November–December, 2005.     

Chemical Constituents of Brown Rice Grain (<Emphasis Type="Italic">Oryza sativa</Emphasis>)

One new compound 3,7,11,15,19-pentamethyl-9α,10α,11α,17α,18α-pentahydroxy-n-tetracosan-1-oxy-p-hydroxycaffeoate (oryzaterpenyl caffeoate) (1), together with three known fatty acids linoleic acid, stearic acid and myristic acid were isolated and identified from the rice grain of Oryza sativa. The structure of the new compound was elucidated by 1D and 2D NMR spectroscopic techniques (¹H-¹HCOSY, ¹H-¹³C HETCOR) aided by EI-MS, and IR spectra. __________ Published in Khimiya Prirodnykh Soedinenii, No. 6, pp. 535–537, November–December, 2005.     

Synthesis of 4<Emphasis Type="Italic">E</Emphasis>,7<Emphasis Type="Italic">Z</Emphasis>-tridecadien-1-ylacetate,a component of the <Emphasis Type="Italic">Phthorimaea opercucella</Emphasis> sex pheromone

A new synthetic approach to 4E,7Z-tridecadien-1-ylacetate, a component of the Phthorimaea opercucella (Zeller) potato moth sex pheromone, was developed using a highly stereoselective Claisen rearrangement and Wittig reaction. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 235–236, May–June, 2007.     

Chemotypical Variability of Leaf Oils in <Emphasis Type="Italic">Elephantopus scaber</Emphasis> from 12 Locations in China

The chemical constituents of leaf oils of Elephantopus scaber L. from 12 locations in Southern China, including three provinces and Hong Kong, were investigated using GC/MS. A total of 24 compounds were detected, of which 20 were identified by their mass spectra fragmentation patterns. The major compounds include hexadecanoic acid (8.19–39.22%), octadecadienoic acid (trace - 29.22%), five alkane homologues, i.e., n-tetradecane (1.19–5.26%), n-pentadecane (3.22–12.05%), n-hexadecane (2.38–16.26%), n-heptadecane (2.48–15.32%), and n-octadecane (1.39–9.59%), as well as tetramethylhexadecenol (2.06–4.31%). Hierarchical cluster analysis classified the leaf oils into two groups. Two main chemotypes of leaf oils in E. scaber were thus identified, one rich in hexadecanoic acid and octadecadienoic acid, and the other rich in the five alkane homologues. __________ Published in Kimiya Prirodnikh Soedinenii No. 5, pp. 403–404, September–October, 2005.     

A new triterpene glycoside from <Emphasis Type="Italic">Premna microphylla</Emphasis>

A new triterpene glycoside, namely 28-O-α-L-rhamnopyranosyl (1→2)-β-D-glucopyranoside tormentic acid ester, was isolated from the leaves of Premna microphylla, together with two known triterpenes, i.e., arjunolic acid (2) and hyptatic acid A (3). Its structure was established by mass-spectrometric and spectroscopic methods, especially 2D NMR techniques. This is the first report of the isolation of triterpenes from this plant. Published in Khimiya Prirodnykh Soedinenii, No. 2, pp. 173–174, March–April, 2009.     

Triterpene glycosides from <Emphasis Type="Italic">Astragalus</Emphasis> and their genins. LXXX. Cyclomacroside D,a new bisdesmoside

The structure of the new cycloartane glycoside cyclomacroside D, which was isolated from Astragalus macropus Bunge (Leguminosae) and is 24R-cycloartan-1α,3β,7β,24,25-pentaol 3-O-α-L-rhamnopyranoside–24-O-β-D-xylopyranoside, was proved. Presented at the 7th International Symposium on the Chemistry of Natural Compounds (SCNC, Tashkent, Uzbekistan, October 16–18, 2007). Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 48–50, January–February, 2009.     

Fatty acid profile of <Emphasis Type="Italic">Trichosanthes kirilowii</Emphasis> Maxim. seed oil

Fatty acid profile data for refined cold-pressed Trichosanthes kirilowii Maxim. seed oil, in comparison to other commercially available oils — olive, rapeseed and camellia, are presented. Trichosanthes kirilowii Maxim. seed oil has high oleic and linoleic acid content and high polyunsaturated acid content. Squalene elutes as a distinct peak in the GC chromatograph. For a positive identification, MS detection was used. In the samples analyzed, squalene occurred in the range of 57.4–68.2 mg g⁻¹.     

Separation, purification and structure elucidation of a polysaccharide from root of Cudrania tricuspidata

A water-soluble polysaccharide (CPS-0) was obtained from the root of Cudrania tricuspidata (Carr.) Bur., by hot water extraction (70°C), deproteination using enzymolysis and Sevag method, precipitation with ethanol, and fractionation through DEAE-Sephadex A-50 chromatography. The purity of CPS-0 was determined by HPLC and the structure was elucidated by monosaccharide composition analysis, methylation analysis, GC, GC-MS, NMR spectral (¹H-NMR, ¹³C-NMR, HMQC), UV, IR, and elemental analysis. The CPS-0 was found to contain glucose residues only. The average repeating unit is a decasaccharide having a backbone consisting of 1,4-linked α-D-glucopyranosyl residues to which the side chain consisting of terminal and 1,4-linked α-D-glucopyranosyl residues was attached at position 6 of the branching residues. __________ Translated from Chemical Journal of Chinese Universities, 2007, 28(6): 1088–1091 [译自: 高等学校化学学报]     

Alpinine,A New Norditerpene Alkaloid from <Emphasis Type="Italic">Delphinium alpinum</Emphasis>

The known alkaloids deltaline, methyllycaconitine, elasine, and the new norditerpene alkaloid alpinine were isolated from the aerial part of Delphinium alpinum. The structure of the last was proposed as 1α,6β, 16β-trimethoxy-7-hydroxy-8-ethoxy-14α-propionyloxy-4β-(2″-methyl)succinylanthranoyloxymethyl-N-ethylaconitane on the basis of PMR, ¹³C NMR, IR, and mass spectra. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 469–471, September–October, 2005.     

Intensification of Biocatalytical Processes by Synergistic Substrate Conversion. Fungal Peroxidase Catalyzed <Emphasis Type="Italic">N</Emphasis>-Hydroxy Derivative Oxidation in Presence of 10-Propyl Sulfonic Acid Phenoxazine

Many industrial pollutants, xenobiotics, and industry-important compounds are known to be oxidized by peroxidases. It has been shown that highly efficient peroxidase substrates are able to enhance the oxidation of low reactive substrate by acting as mediators. To explore this effect, the oxidation of two N-hydroxy derivatives, i.e., N-hydroxy-N-phenyl-acetamide (HPA) and N-hydroxy-N-phenyl-carbamic acid methyl ester (HPCM) catalyzed by recombinant Coprinus cinereus (rCiP) peroxidase has been studied in presence of efficient substrate 3-(4a,10a-dihydro- phenoxazin-10-yl)-propane-1-sulfonic acid (PPSA) at pH 8.5. The bimolecular constant of PPSA cation radical reaction with HPA was estimated to be (2.5 ± 0.2)·10⁷ M⁻¹ s⁻¹ and for HPCM was even higher. The kinetic measurements show that rCiP-catalyzed oxidation of HPA and HPCM can increase up to 33,000 times and 5,500 times in the presence of equivalent concentration of high reactive substrate PPSA. The mathematical model of synergistic rCiP-catalyzed HPA–PPSA and HPCM–PPSA oxidation was proposed. Experimentally obtained rate constants were in good agreement with those calculated from the model confirming the synergistic scheme of the substrate oxidation. In order to explain the different reactivity of substrates, the docking of substrates in the active site of the enzyme was calculated. Molecular dynamic calculations show that the enzyme–substrate complexes are structurally stable. The high reactive PPSA exhibited higher affinity to enzyme active site than HPA and HPCM. Furthermore, the orientation of HPA and HPCM was not favorable for proton transfer to the distal histidine, and different substrate reactivity was explained by these diversities.     

Functionalization of <Emphasis Type="Italic">N-tert</Emphasis>-butoxycarbonyl-7-and <Emphasis Type="Italic">N-tert</Emphasis>-butoxycarbonyl-8-bromo-10-azabicyclo[4.3.1]deca-3,7-dienes. A route to a ferruginine homolog

N-tert-Butoxycarbonyl-7-and N-tert-butoxycarbonyl-8-bromo-10-azabicyclo[4.3.1]deca-3,7-dienes are convenient substrates for further modification using replacement of the Br atom by a cyano group or a Li atom. Treatment of lithium derivatives with dimethylformamide and N-methoxy-N-methylacetamide gave the corresponding α,β-unsaturated aldehydes (67–84%) and ketones (∼70%). Ketone 4b is a direct precursor of a homolog of the alkaloid ferruginine. Dedicated to Academician G. A. Abakumov on the occasion of his 70th birthday. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1794–1796, September, 2007.     

Influence of inhibitory compounds and minor sugars on xylitol production by <Emphasis Type="Italic">Debaryomyces hansenii</Emphasis>

To obtain in-depth information on the overall metabolic behavior of the new good xylitol producer Debaryomyces hansenii UFV-170, batch bioconversions were carried out using semisynthetic media with compositions simulating those of typical acidic hemicellulose hydrolysates of sugarcane bagasse. For this purpose, we used media containing glucose (4.3–6.5 g/L), xylose (60.1–92.1 g/L), or arabinose (5.9–9.2 g/L), or binary or ternary mixtures of them in either the presence or absence of typical inhibitors of acidic hydrolysates, such as furfural (1.0–5.0 g/L), hydroxymethylfurfural (0.01–0.30 g/L), acetic acid (0.5–3.0 g/L), and vanillin (0.5–3.0 g/L). D. hansenii exhibited a good tolerance to high sugar concentrations as well as to the presence of inhibiting compounds in the fermentation media. It was able to produce xylitol only from xylose, arabitol from arabinose, and no glucitol from glucose. Arabinose metabolization was incomplete, while ethanol was mainly produced from glucose and, to a lesser less extent, from xylose and arabinose. The results suggest potential application of this strain in xyloseto-xylitol bioconversion from complex xylose media from lignocellulosic materials.