- A new 5α,8α-epidioxy sterol from the Okinawan marine sponge of the Axinyssa genus
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A new sterol (axinysterol) was isolated from the Okinawan marine sponge of the genus Axinyssa.The structure of axinysterol was assigned as 5α,8α-epidioxyergosta-6,22,25-trien-3β-ol based on spectroscopic analysis and chemical transformation. (Steroids 58: 410-413, 1993). Keywords: 5α,8α-epidioxyergosta-6,22,25-trien-3β-ol; axinysterol; marine sponge; Axinyssa genus; sterol; structure
- Iguchi, Kazuo,Shimura, Hiromi,Yang, Zhi,Yamada, Yasuji
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- Novel 26-oxygenated products in microbial degradation of ergosterol
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In order to investigate the effect of the different stereochemistry of C- 24 on the microbial C-26 oxidation of sterol side-chain the genetically modified Mycobacterium sp. BCS 396 strain was used to transform ergosterol. Ergosterol was converted to 3-oxo-4,22-ergostadien-26-oic acid methyl ester, 3-oxo-1,4,22-ergostatrien-26-oic acid methyl ester, and 3-oxol-1,4,22- erogstatrien-26-oic acid, the structures of which have been determined by 1R, 1H NMR, 13C NMR, and mass spectroscopy. The X-ray structure of 3-oxo- 4,22-ergostadien-26-oic acid methyl ester revealed that oxidation at C-26 of the ergostane side-chain generates a chiral center with S-configuration at C- 25 as a result of chiral induction of the C-24 center.
- Ambrus, Gabor
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- Synthesis and biological evaluation of novel steroidal 5α,8α-endoperoxide derivatives with aliphatic side-chain as potential anticancer agents
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By inspiration of significant anti-cancer activity of our previously screened natural ergosterol peroxide (EP), a series of novel steroidal 5α,8α-endoperoxide derivatives 5a–d and 14a–f were designed, synthesized, and biologically evaluated for their in vitro anti-proliferative inhibitory and cytotoxic activity. The results revealed that most of these compounds showed moderate-to-excellent anti-proliferative effects against the tested cancer cell lines (i.e. HepG2, SK-Hep1, MDA-MB-231 and MCF-7). Among them, compound 5b and 14d exhibited preferable inhibitory activities (IC50 of 5b and 14d are 8.07 and 9.50?μM against HepG2, respectively). The structure-activity relationships indicated that incorporation the peroxidic bridge to the steroid scaffolds at C-5 and C-8 positions together with the aliphatic side-chain at the C-17 position would provide synergistic effect for the bioactivity.
- Bu, Ming,Cao, Tingting,Li, Hongxia,Guo, Mingzhou,Yang, Burton B.,Zhou, Yue,Zhang, Na,Zeng, Chengchu,Hu, Liming
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- Antimycobacterial ergosterol-5,8-endoperoxide from Ajuga remota
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In a bioassay-guided search for antimycobacterial natural products from higher plants, we have chemically investigated the methanol extract of aerial parts of Ajuga remota Benth. (Labiatae) for its active constituent(s). Bioactive chromatographic fractions of the crude extract provided the known triterpene ergosterol-5,8-endoperoxide plus the diterpenes clerodin, ajugarin-I, and ajugarin-II, which had been previously isolated from A. remota. This is the first report on the isolation of ergosterol-5,8- endoperoxide from this plant. The above compounds were tested in a radiorespirometric bioassay for activity against Mycobacterium tuberculosis. Ergosterol-5,8-endoperoxide showed a minimum inhibitory concentration (MIC) of 1 μg/ml. while ergosterol-5,8-endoperoxide acetate, ergosterol, and ergosta-5,7,9(11),22-tetraen-3β-ol gave MICs of 8 μg/ml, > 128 μg/ml, and 128 μg/ml. respectively. Clerodin, ajugarin-I, and ajugarin-II were inactive with MICs of > 128 μg/ml.
- Cantrell, Charles L.,Rajab, Mohamed S.,Franzblau, Scott G.,Fronczek, Frank R.,Fischer, Nikolaus H.
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- Development of ergosterol peroxide probes for cellular localisation studies
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Ergosterol peroxide selectively exhibits biological activity against a wide range of diseases; however, its mode of action remains unknown. Here, we present an efficient synthesis of ergosterol peroxide chemical probes for in vitro anticancer evaluation,
- Ling, Taotao,Lang, Walter H.,Martinez-Montemayor, Michelle M.,Rivas, Fatima
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- Synthesis of 5α,8α-Ergosterol Peroxide 3-Carbamate Derivatives and a Fluorescent Mitochondria-Targeting Conjugate for Enhanced Anticancer Activities
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Inspired by the significant anticancer activity of our previously screened natural ergosterol peroxide (1), we synthesized and characterized a series of novel ergosterol peroxide 3-carbamate derivatives. The antiproliferative activities of the synthesized
- Bu, Ming,Cao, Tingting,Li, Hongxia,Guo, Mingzhou,Yang, Burton B.,Zeng, Chengchu,Hu, Liming
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- New biologically active marine sesquiterpenoid and steroid from the okinawan sponge of the genus Axinyssa
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A new bisabolane-type sesquiterpenoid, (E)-3-isocyanobisabolane-7,10-diene (1), and a new epidioxyergostane-type steroid, 9(11)-dehydroaxinysterol (2), were isolated from the Okinawan sponge of the genus Axinyssa. Their structures were elucidated based on
- Iwashima, Makoto,Terada, Ikuo,Iguchi, Kazuo,Yamori, Takao
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- Synthesis of ergosterol peroxide conjugates as mitochondria targeting probes for enhanced anticancer activity
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Inspired by the significant bioactivity of ergosterol peroxide, we designed and synthesized four fluorescent coumarin and ergosterol peroxide conjugates 8a-d through the combination of ergosterol peroxide with 7-N,N-diethylamino coumarins fluorophore. The cytotoxicity of synthesized conjugates against three human cancer cells (HepG2, SK-Hep1, and MCF-7) was evaluated. The results of fluorescent imaging showed that the synthesized conjugates 8a-d localized and enriched mainly in mitochondria, leading to significantly enhanced cytotoxicity over ergosterol peroxide. Furthermore, the results of biological functions of 8d showed that it could suppress cell colony formation, invasion, and migration; induce G2/M phase arrest of HepG2 cells, and increase the intracellular ROS level.
- Bu, Ming,Li, Hongling,Wang, Haijun,Wang, Jing,Lin, Yu,Ma, Yukun
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- Minor and Trace Sterols in Marine Invertebrates. 26. Isolation and Structure Elucidation of Nine New 5α,8α-Epidioxy Sterols from Four Marine Organisms
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Sixteen 5α,8α-epidioxy Δ6 and Δ6,9(11) sterols, of which nine are new, have been isolated from the marine organisms Ascidia nigra, Dendrogyra cylindrus, Thalysias juniperina, and Aplysia dactylomela by reverse-phase high-performance liquid chromatography and characterized by high-resolution mass spectrometry and 360-MHz proton NMR spectroscopy.Attention is drawn to some unusual concentration-dependent NMR shifts of methyl signals.The probable biological significance of these epidioxy sterols is discussed with special reference to sterol biosynthesis.
- Gunatilaka, Leslie A. A.,Gopichand, Yalamanchili,Schmitz, Francis J.,Djerassi, Carl
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- New biologically active epidioxysterols from Stereum hirsutum
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From the fungus Stereum hirsutum have been isolated and identified two new epidioxysterols 1, 4, together with two known ones 2 and 3. Their structures were elucidated on the basis of spectroscopic analysis and chemical reactions. Epidioxysterols 1-4 have been shown to possess a significant activity against Mycobacterium tuberculosis.
- Cateni, Francesca,Doljak, Bojan,Zacchigna, Marina,Anderluh, Marko,Piltaver, Andrej,Scialino, Giuditta,Banfi, Elena
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- Biogenesis-Guided Synthesis and Structural Revision of Sarocladione Enabled by Ruthenium-Catalyzed Endoperoxide Fragmentation
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Sarocladione is the first 5,10:8,9-diseco-steroid with a 14-membered macrocyclic diketone framework to have been isolated from a natural source. Herein we report a biomimetic synthesis of sarocladione in only two or seven steps from inexpensive, commercially available ergosterol. The key feature of this synthesis was a novel ruthenium-catalyzed endoperoxide fragmentation, which transformed various saturated endoperoxides into olefinic diketones by cleavage of two C?C bonds. This synthesis allowed us to unambiguously determine the structure of sarocladione and provided experimental support for its revised biosynthetic origin. This work also vividly demonstrates that consideration of the biogenesis is a powerful tool for elucidating the structures of natural products.
- Ning, Yuhan,Tian, Hailong,Gui, Jinghan
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supporting information
p. 11222 - 11226
(2021/04/19)
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- Reactive oxygen species altering the metabolite profile of the marine-derived fungus Dichotomomyces cejpii F31-1
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To investigate the influence of reactive oxygen species (ROS) on the secondary metabolites of the marine-derived fungus Dichotomomyces cejpii F31-1, hydrogen peroxide (H2O2) was added to the GPY culture medium. The HPLC chromatogram of the EtOAc extract of the culture broth was distinct from that of the H2O2 free GPY medium. Further study of the metabolites in the GPY medium with H2O2 resulted in the discovery of eight known compounds. Among them, (22E)-5α, 8α-epidioxyergosta-6, 22-dien-3β-ol (2) and ergosta-4,6,8(14),22-tetraene-3-one (3) were present in the highest concentration, while ergosterol and diketopiperazines are abundant in the H2O2 free medium. Additionally, a new compound, dichocetide D (1) containing a chlorine element and a known ergosterol (10) were isolated from the H2O2 free medium. (22E)-5α, 8α-epidioxyergosta-6, 22-dien-3β-ol (2) exhibited moderate cytotoxic activity against human prostate cancer cell line LNCaP-C4-2B.
- Shaker, Sharpkate,Sun, Ting-Ting,Wang, Liang-Yue,Ma, Wen-Zhe,Wu, Dong-Lan,Guo, Yong-Wei,Dong, Jun,Chen, Yan-Xiu,Zhu, Long-Ping,Yang, De-Po,Li, Hou-Jin,Lan, Wen-Jian
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- Antagonistic activity of hydroxycoumarin-based antioxidants as possible singlet oxygen precursor photosensitizers
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Coumarins are phenolic-type compounds with efficient antioxidant activity due to their ability to scavenge reactive oxygen species. Nevertheless, their ability to behave as photosensitizers capable of generating reactive oxygen species, such as singlet oxygen, has been less studied. In this work, the photosensitizing ability of seven hydroxycoumarins was evaluated through the photooxidation of ergosterol by quantifying the conversion of ergosterol into ergosterol peroxide. In our experimental conditions, we found that almost every tested antioxidant coumarin promotes the peroxidation of ergosterol. The results suggest that the hydroxycoumarins exhibit potential photosensitizing activity by promoting singlet oxygen generation by a Type II photochemical mechanism. Density functional theory (DFT) calculations were also performed to obtain further insight into the chemical reactivity of tested compounds; the observed tendency in the group of antioxidant coumarins to promote the reaction was their hardness due to the principle of maximum hardness. To evaluate our conclusion, we performed the reaction using a highly polarizable coumarin as a photosensitizer, which resulted in an increased photosensitizing capacity supported with DFT calculations, which reinforces our analysis. Finally, we found that hydroxycoumarins can be potentially pro-oxidants since some of them can act as photosensitizers and generate singlet oxygen in the presence of UV–Vis light, a characteristic that must be considered when these compounds are used as antioxidants.
- Guerrero, Tomás,Vázquez-Ortega, Fernanda,Lagunes, Irene,Ortiz-Blanco, Erik,Sosa-Ortiz, Gabriela,Tovar-Miranda, Ricardo,Medina, Manuel E.,Trigos, ángel
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- BIOLOGICALLY ACTIVE GANODERMA LUCIDUM COMPOUNDS AND SYNTHESIS OF ANTICANCER DERIVATIVES; ERGOSTEROL PEROXIDE PROBES FOR CELLULAR LOCALIZATION
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The bioactive compounds of Ganoderma lucidum extract (GLE) responsible for anticancer activity were elucidated using NMR, X-ray crystallography and analogue derivatization, as well as anti-cancer activity studies. Structures of the seven most abundant GLE
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Paragraph 000106; 000149
(2020/08/22)
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- 5β,8β-EPIDIOXYERGOSTA-6,22-DIEN-3β-OL FROM Typha latifolia
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5β,8β-epidioxyergosta-6,22-dien-3β-ol has been isolated from Typha latifolia beside the 5α,8α isomer and 5α,8α-epidioxyergosta-6,9(11),22-trien-3β-ol.A short discussion on the origin of ergosterol epidioxides is reported.
- Greca, Marina Della,Mangoni, Lorenzo,Molinaro, Antonio,Monaco, Pietro,Previtera, Lucio
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p. 391 - 392
(2007/10/02)
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- Oxidative Breaking of Long-Chain Acetylenic Enol Ethers of Glycerol of the Marine Sponges Raspailia pumila and R. ramosa and of Model Compounds with Aerial Oxygen
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The raspailynes (novel long-chain enol ethers of glycerol having the enol ether double bond conjugated, in sequence, to an acetylenic and an olefinic bond, isolated from the North-East-Atlantic sponges Raspailia pumila and R. ramosa) are stable under normal hydrolytic conditions for enol ethers.In contrast, when their solutions are evaporated, these lipids such as raspailyne B1 (=(-)-3--1,2-propanediol; (-)-2) rapidly react with aerial O2 under normal laboratory-daylight conditions, with rupture of the C=C enol ether bond to give 1-O-formylglycerol (3) and an aldehyde (such as tridec-4-en-3-ynal(4) from (-)-2).This reaction must be caused by triplet O2, since thermally generated singlet O2 has no effect on (-)-2 in solution.That the mere presence of an enol-ether moiety conjugated to an acetylenic group is responsible for such a behaviour is demonstrated with the model compounds 1-methoxypentadec-1-en-3-yn-5-ol (6a) and its 5-O-acetyl or 5-O-tetrahydropyranyl derivatives 6b and 6c, respectively.Resistance to both hydrolytic conditions and singlet O2 of these compounds is thought to arise from electron depletion at the enol-ether C(β) atom by the acetylenic group.Plausible reaction pathways for enol-ether bond rupture in these compounds by aerial O2 are outlined.
- Guella, Graziano,Mancini, Ines,Pietra, Francesco
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p. 1400 - 1411
(2007/10/02)
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