Garlicnin A from the fraction regulating macrophage activation of Allium sativum

Garlicnin A (1), a new stable, sulfur-containing compound isolated from a fraction of the acetone extracts of Allium sativum L. garlic bulbs, showed the potential to suppress tumor cell proliferation by inhibiting the polarization of M2 alternatively activated macrophages, and its structure was characterized as 3,4-dimethyl-5-(4,5-dithia-1E,7-octadiene)-tetrahydrothiophene-2-sulfoxide-S-oxide, on the basis of the results of spectroscopic analysis results.     

Bioactive constituents from Chinese natural medicines. XXXII. aminopeptidase N and aldose reductase inhibitors from Sinocrassula indica: structures of sinocrassosides B(4), B(5), C(1), and D(1)-D(3)

From the methanolic extract of the whole plant of Sinocrassula indica (Crassulaceae), six new flavonol glycosides, sinocrassosides B(4) (1), B(5) (2), C(1) (3), D(1) (4), D(2) (5), and D(3) (6), were isolated together with 30 compounds. The structures of 1-6 were elucidated on the basis of chemical and physicochemical evidence. In addition, several constituents were found to show inhibitory effects on aminopeptidase N and aldose reductase.     

New triterpene constituents, foliasalacins A(1)-A(4), B(1)-B(3), and C, from the leaves of Salacia chinensis

Four dammarane-type, three lupane-type, and an oleanane-type triterpenes named foliasalacins A(1) (1), A(2) (2), A(3) (3), A(4) (4), B(1) (5), B(2) (6), B(3) (7), and C (8) were isolated from the leaves of Salacia chinensis LINN. collected in Thailand. The structures of new triterpene constituents (1-8) were characterized on the basis of chemical and physiochemical evidence.     

Novel Trinor-eremophilanes (Dendryphiellin B,C, and D), Eremophilanes (Dendryphiellin E,F, and G), and Branched C9-Carboxylic Acids (Dendryphiellic Acid A and B) from the Marine Deuteromycete Dendryphiella salina (SUTHERLAND) PUGHet NICOT

Further investigation of global extracts from cultures of the marine deuteromycete Dendryphiella salina leads to the isolation of three novel trinor-eremophilanes esterified by branched C₉-carboxylic acids, dendryphiellin B (= (+)-(1R*,2S*,7R*,8aR*)-1,2,6,7,8,8a-hexahydro-7-hydroxy-1,8a-dimethyl-6-oxonaphthalen-2-yl (6R*, 2E, 4E)-6-hydroxy-6-methylocta-2,4-dienoate; (+)- 2 ), dendryphiellin C (=(+)-(1R*, 2S*, 7R*, 8aR*)-1,2,6,7,8,8a-hexa-hydro-7-hydroxy-1,8a-dimethyl-6-oxonaphthalen-2-yl (6S, 2E, 4E)-6-methylocta-2,4-dienoate; (+)- 3 )), and dendryphiellin D (=(+)-(1R*, 2S*, 7R*, 8aR*)-1,2,6,7(8,8a-hexahydro-7-hydroxy-1,8a-dimethyl-6-oxonaphthalen-2-yl (6R*,2E,4E)-6-(hydroxymethyl)octa-2,4-dienoate; (+)- 4 ). An intact eremophilane, dendryphiellin E ( 5 ), and its ethanolysis product dendryphiellin F whose absolute configuration is represented by structural formula (+)- 6 are also isolated from the above extracts. Dendryphiellin E exists as an open form 5a in equilibrium with a closed form 5b . A similar equilibrium exists between the open form 8a and the closed form 8b of a non-esterified eremophilane, dendryphiellin G ( 8 ), which is isolated too from the above extracts and proves structurally related to the cyclic portion of 5 . Finally, the free, branched C₉-carboxylic acids dendryphiellic acid A ((+)- 9 ) and B ((+)- 10 ) which correspond to side chains of the above esterified terpenes are also isolated from the above extracts.     

Total synthesis of maremycins A,B, C1/C2, D1, and D2

The total synthesis of maremycins A, B, C₁/C₂, D₁, and D₂ is achieved starting from the natural amino acids l-isoleucine and S-methyl-l-cysteine, in which the total synthesis of maremycins B, C₁/C₂, and D₂ is accomplished for the first time. The synthesis features a position-selective intramolecular bromination process for the synthesis of key chiral building block, a Pd-catalyzed indole synthesis for the preparation of (2S,3S)-β-methyltryptophan and hydroxylation of oxindoles by molecular oxygen. In addition, the protocol for conversion of maremycins A and B to maremycins C and D was improved.     

Solvent Mixture Optimization in the Extraction of Bioactive Compounds and Antioxidant Activities from Garlic (Allium sativum L.)

Garlic is a health promoter that has important bioactive compounds. The bioactive extraction is an important step in the analysis of constituents present in plant preparations. The purpose of this study is to optimize the extraction with the best proportion of solvents to obtain total phenolic compounds (TPC) and thiosulfinates (TS) from dried garlic powder, and evaluate the antioxidant activities of the optimized extracts. A statistical mixture simplex axial design was used to evaluate the effect of solvents (water, ethanol, and acetone), as well as mixtures of these solvents, after two ultrasound extraction cycles of 15 min. Results showed that solvent mixtures with a high portion of water and pure water were efficient for TPC and TS recovery through this extraction procedure. According to the regression model computed, the most significant solvent mixtures to obtain high TPC and TS recovery from dried garlic powder are, respectively, the binary mixture with 75% water and 25% acetone and pure water. These optimized extracts presented oxygen radical absorbance capacity. Pure water was better for total antioxidant capacity, and the binary mixture of water–acetone (75:25) was better for DPPH scavenging activity. These optimized extracts can be used for industrial and research applications.     

Purification and Characterization of a Cu,Zn-SOD from Garlic (Allium sativum L.). Antioxidant Effect on Tumoral Cell Lines

Crude garlic extract contains one Mn-superoxide dismutase designated as SOD1 and two Cu,Zn superoxide dismutases as SOD2 and SOD3. The major isoform SOD2 was purified to homogeneity by Sephacryl S200-HR gel filtration, DEAE Sepharose ion exchange chromatography, and chromatofocusing using PBE 94. SOD2 was purified 82-fold with a specific activity of 4,960 U/mg protein. This enzyme was stable in a broad pH range from 5.0 to 10.0 and at various temperatures from 25 to 60°C. The native molecular mass of SOD2 estimated by high performance liquid chromatography on TSK gel G2000SW column was 39 kDa. Sodium dodecyl sulfate–polyacrylamide gel electrophoresis analysis showed a single band near 18 kDa, suggesting that native enzyme was homodimeric. The isoelectric point as determined by chromatofocusing was 5. Analysis of its N terminal amino acid sequence revealed high sequence homology with several other cytosolic Cu,Zn-SODs from plants. Exposure of cancer cell lines to garlic Cu,Zn-SOD2 led to a significant decrease in superoxide content with a concomitant rise in intracellular peroxides, indicating that the enzyme is active in mammalian cells and could, therefore, be used in pharmacological applications.     

Comparative studies of bioactive organosulphur compounds and antioxidant activities in garlic (Allium sativum L.), elephant garlic (Allium ampeloprasum L.) and onion (Allium cepa L.)

We evaluated organosulphur compounds in Allium vegetables, including garlic, elephant garlic and onion, using high-performance liquid chromatography. Among organosulphur compounds, elephant garlic had considerable γ-glutamyl peptides, and garlic had the highest alliin content. Onion had low level of organosulphur compounds than did elephant garlic and garlic. In addition, antioxidant capacities were evaluated by oxygen radical absorbance capacity (ORAC) values and 2,2-diphenyl-1-picrylhydrazyl (DPPH) and 2,2′-azinobis(3-ethylbenzothiazoline-6-sulphonic acid) (ABTS) radical scavenging assay. The results showed that garlic had the highest antioxidant capacity, followed by elephant garlic and onion. Furthermore, a positive correlation was observed between antioxidant activities and organosulphur compounds (R > 0.77). Therefore, our results indicate that there was a close relationship between antioxidant capacity and organosulphur compounds in Allium vegetables.     

Steroids of the spirostan and furostan series from plants of the genus Allium. XXV. Structure of anzurogenin B from Allium suvorovii and Allium Stipitatum

A new genin of the spirostan series — anzurogenin B having the structure of 2,5-epoxy-(25R)-spirostan-3,6-diol — has been isolated form the collective fruit of the cocultivatedAllium suvorovii Rgl. andAllium stipitatum Rgl. (family Liliaceae).Institute of the Chemistry of Plant Substances, Uzbek SSR Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 218–221, March–April, 1988.     

Determination of vitamins A,B1, B2, D3 and C by densitometry of thin-layer chromatograms

Summary A method for densitometric determination of vitamins A, B₁, B₂, D₃, and C separated by t. l. c. is described. A silica gel layer is used with a solvent system of acetone-methanol-benzene (128). The spots are evaluated by direct densitometric light emission measurements. Preliminary separation of the vitamins one from another or from other pharmaceuticals is not necessary. The accuracy of the method is about 6%. The accuracy for vitamin A is up to 12%.

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Zusammenfassung Ein Verfahren zur Bestimmung der dünnschichtchromatographisch getrennten Vitamine A, B₁, B₂, D₃ und C wurde beschrieben. Dazu dient eine Kieselgelschichte mit Aceton Methanol Benzol (128) als Lösungsmittel. Die Flecken werden densitometrisch gemessen. Eine vorhergehende Trennung der einzelnen Vitamine voneinander bzw. von anderen pharmazeutischen Begleitstoffen ist nicht nötig. Die Methode ist auf etwa 6% genau, für Vitamin A auf 12%.

     

Ilwensisaponins A,B, C,and D: Triterpene Saponins from Scrophularia ilwensis

From the aerial parts of Scrophularia ilwensis, four new triterpene saponins, ilwensisaponins A–D ( 1 – 4 ) were isolated. The structures of the compounds were elucidated using chemical and spectral data as 13β, 28-epoxy-3-β-{{[β-D -glucopyranosyl-(1→2)]-[α-L -rhamnopyranosyl-(1→4)-β-D -glucopyranosyl-(1→3)]-β-D -fucopyranosyl}-oxy} olean-11-en-23-ol ( 1 ), 3-β-{{[β-D -glucopyranosyl-(1→2)]-[α-L -rhamnopyranosyl-(1→4)-β-D -glucopyranosyl-(1→3)]-β-D -fucopyranosyl}oxy}olena-11, 13(18)-diene-23, 28-diol ( 2 ), 3-β-{{[β-D -glucopyranosyl-(1→2)]-[α-L -rhamnopyranosyl-(1→4)-β-D glucopyranosyl-(1→3)]-β-D fucopyranosyl}oxy}-11α-methoxyolean- 12-ene-23, 28-diol (3) , and 3-β-{{[β-D -glucopyransoyl-(1→2)]-[α-L -rhamnopyranosyl-(1→4)-β-D -glucopyranosyl-(1→3)]-β-D -fucopyranosyl}oxy}olean-12-ene-11α,23,28-triol (4) .     

Chaxines B, C, D, and E from the edible mushroom Agrocybe chaxingu

Four novel compounds, chaxines B (1), C (2), D (3), and E (4), were isolated from an edible mushroom Agrocybe chaxingu. The structures of 1-4 were determined by the interpretation of spectroscopic data. Compounds 1 and 2 suppressed the formation of osteoclast.     

Steroids of the spirostan and furostan series of plants of the Allium genus. XXIII. Structure of cepagenin and of alliospirosides C and D from Allium cepa

Two new steroid glycosides of the spirostan series have been isolated from the fruit ofAllium cepa L. (family Liliaceae): alliospirosides C and D. On the basis of chemical transformations and spectral characteristics it has been established that the aglycon of both glycosides is a new steroid sapogenin — cepagenin — having the structure of (24S,25R)-spirost-5-ene-1,3,24-triol. Alliospirosides C and D are cepagenin 1-O-[O--L-rhamnopyranosyl-(12)-L-arabinopyranoside] and 1-O-[O--L-rhamnopyranosyl-(12)-O--D-galactopyranoside], respectively.Institute of the Chemistry of Plant Substances, Uzbek SSR Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 843–849, November–December, 1987.     

Computational study of the conformational space of methyl 2,4-diacetyl-beta-D-xylopyranoside: 4C1 and 1C4 chairs, skew-boats (2SO, 1S3), and B3,O boat forms

Ring and substituent rotamer conformations of methyl 2,4-diacetyl-beta-D-xylopyranoside, for which experimental results are controversial, were studied in the gas phase and in solvents of different polarity (CCl4, CHCl3, DMSO, and H2O) by B3LYP density functional theory. The 1C4 chair is the most stable ring form in the gas phase, followed by 4C1 and 2S0. Solvents of increasing polarity shift the equilibrium toward the 4C1 chair. Homodesmotic reaction energies show that the 1C4 and 2SO forms are stabilized by hydrogen bonding and anomeric effects and that steric repulsion is smallest in the 4C1 chair and largest in skew-boats.     

Steroids of the spirostan and furostan series of plants of the Allium genus. XXIII. Structure of cepagenin and of alliospirosides C and D from Allium cepa

Two new steroid glycosides of the spirostan series have been isolated from the fruit ofAllium cepa L. (family Liliaceae): alliospirosides C and D. On the basis of chemical transformations and spectral characteristics it has been established that the aglycon of both glycosides is a new steroid sapogenin — cepagenin — having the structure of (24S,25R)-spirost-5-ene-1β,3β,24-triol. Alliospirosides C and D are cepagenin 1-O-[O-α-L-rhamnopyranosyl-(1→2)α-L-arabinopyranoside] and 1-O-[O-α-L-rhamnopyranosyl-(1→2)-O-β-D-galactopyranoside], respectively.