Composition of Triterpene Glycosides of the Far Eastern Sea Cucumber Levin et Stepanov; Structure Elucidation of Five Minor Conicospermiumosides A-1, A-2, A-3, A-1, and A-2; Cytotoxicity of the Glycosides Against Human Breast Cancer Cell Lines; Structure-Activity Relationships.

Five new non-holostane di- and trisulfated triterpene pentaosides, conicospermiumosides A-1 (), A-2 (), A-3 (), A-1 (), and A-2 () were isolated from the Far Eastern sea cucumber Levin et Stepanov (Cucumariidae, Dendrochirotida). Twelve known glycosides found earlier in other species were also obtained and identified. The structures of new compounds were established on the basis of extensive analysis of the 1D and 2D NMR spectra, as well as by the HR-ESI-MS data.

New Zosteropenillines and Pallidopenillines from the Seagrass-Derived Fungus KMM 4679.

Ten new decalin polyketides, zosteropenilline M (), 11--8-hydroxyzosteropenilline M (), zosteropenilline N (), 8-hydroxyzosteropenilline G (), zosteropenilline O (), zosteropenilline P (), zosteropenilline Q (), 13-dehydroxypallidopenilline A (), zosteropenilline R () and zosteropenilline S (), together with known zosteropenillines G () and J (), pallidopenilline A () and 1-acetylpallidopenilline A (), were isolated from the ethyl acetate extract of the fungus KMM 4679 associated with the seagrass . The structures of isolated compounds were established based on spectroscopic methods. The absolute configurations of zosteropenilline Q () and zosteropenilline S () were determined using a combination of the modified Mosher's method and ROESY data.

Sulfated Polyhydroxysteroid Glycosides from the Sea of Okhotsk Starfish and Potential Mechanisms for Their Observed Anti-Cancer Activity against Several Types of Human Cancer Cells.

Three new monosulfated polyhydroxysteroid glycosides, spiculiferosides A (), B (), and C (), along with new related unsulfated monoglycoside, spiculiferoside D (), were isolated from an ethanolic extract of the starfish collected in the Sea of Okhotsk. Compounds - contain two carbohydrate moieties, one of which is attached to C-3 of the steroid tetracyclic core, whereas another is located at C-24 of the side chain of aglycon. Two glycosides (, ) are biosides, and one glycoside (), unlike them, includes three monosaccharide residues.

The Composition of Triterpene Glycosides in the Sea Cucumber : Anticancer Activity of the Glycosides against Three Human Breast Cancer Cell Lines and Quantitative Structure-Activity Relationships (QSAR).

Eight sulfated triterpene glycosides, peronioside A () and psolusosides A (), B (), G (), I (), L (), N () and P (), were isolated from the sea cucumber . Peronioside A () is a new glycoside, while compounds - were found previously in , indicating the phylogenetic and systematic closeness of these species of sea cucumbers. The activity of - against human erythrocytes and their cytotoxicity against the breast cancer cell lines MCF-7, T-47D and triple-negative MDA-MB-231 were tested.

New piperazine derivatives helvamides B-C from the marine-derived fungus Penicillium velutinum ZK-14 uncovered by OSMAC (One Strain Many Compounds) strategy.

Four extracts of the marine-derived fungus Penicillium velutinum J.F.H.

Rare Ophiuroid-Type Steroid 3β,21-, 3β,22-, and 3α,22-Disulfates from the Slime Sea Star and Their Colony-Inhibiting Effects against Human Breast Cancer Cells.

Two new steroid 3β,21-disulfates (, ) and two new steroid 3β,22- and 3α,22-disulfates (, ), along with the previously known monoamine alkaloid tryptamine () were found in the ethanolic extract of the Far Eastern slime sea star . Their structures were determined on the basis of detailed analysis of one-dimensional and two-dimensional NMR, HRESIMS, and HRESIMS/MS data. Compounds and have a Δ-21-sulfoxy-24-norcholestane side chain.

New Rare Triterpene Glycosides from Pacific Sun Star, , and Their Anticancer Activity.

Six previously unknown triterpene glycosides, pacificusosides L-Q (-), and two previously known triterpene glycosides, cucumariosides B () and A (), were isolated from an alcoholic extract of Pacific sun star, . The structures of - were determined using 1D and 2D NMR, ESIMS, and chemical modifications. Compound is a rare type of triterpene glycoside with non-holostane aglycon, having a linear trisaccharide carbohydrate chain.

Sulfated Triterpene Glycosides from the Far Eastern Sea Cucumber : Djakonoviosides C, D, E, and F; Cytotoxicity against Human Breast Cancer Cell Lines; Quantitative Structure-Activity Relationships.

Four new mono- and trisulfated triterpene penta- and tetraosides, djakonoviosides C (), D (), E (), and F () were isolated from the Far Eastern sea cucumber (Cucumariidae, Dendrochirotida), along with six known glycosides found earlier in other species. The structures of unreported compounds were established on the basis of extensive analysis of 1D and 2D NMR spectra as well as by HR-ESI-MS data. The set of compounds contains six different types of carbohydrate chains including two new ones.

New Cyclopiane Diterpenes and Polyketide Derivatives from Marine Sediment-Derived Fungus KMM 4670 and Their Biological Activities.

Two new cyclopiane diterpenes and a new cladosporin precursor, together with four known related compounds, were isolated from the marine sediment-derived fungus KMM 4670, which was re-identified based on phylogenetic inference from ITS, , , and gene regions. The absolute stereostructures of the isolated cyclopianes were determined using modified Mosher's method and quantum chemical calculations of the ECD spectra. The isolation from the natural source of two biosynthetic precursors of cladosporin from a natural source has been reported for the first time.

Rhabdastrellosides A and B: Two New Isomalabaricane Glycosides from the Marine Sponge , and Their Cytotoxic and Cytoprotective Effects.

Investigation of the Vietnamese marine sponge led to the isolation of two new polar isomalabaricanes: rhabdastrellosides A () and B (). Their structures and stereochemistry were elucidated with the application of 1D and 2D NMR, HRESIMS, and HRESIMS/MS methods, as well as chemical modifications and GC-MS analysis. Metabolites and are the first isomalabaricanes with non-oxidized cyclopentane ring in the tricyclic core system.

Production of high- and low-molecular weight fucoidan fragments with defined sulfation patterns and heightened in vitro anticancer activity against TNBC cells using novel endo-fucanases of the GH107 family.

Fucoidans are complex fucose-containing sulfated polysaccharides with pronounced anticancer effects. Their structure-anticancer activity relationships are difficult to determine due to fucoidans' complex, often irregularities-including structures. Fucoidan-active enzymes can be used for this propose.

Djakonoviosides A, A, A, B-B - Triterpene Monosulfated Tetra- and Pentaosides from the Sea Cucumber : The First Finding of a Hemiketal Fragment in the Aglycones; Activity against Human Breast Cancer Cell Lines.

Seven new monosulfated triterpene glycosides, djakonoviosides A (), A (), A (), and B-B (-), along with three known glycosides found earlier in the other species, namely okhotoside A-1, cucumarioside A-1, and frondoside D, have been isolated from the far eastern sea cucumber (Cucumariidae, Dendrochirotida). The structures were established on the basis of extensive analysis of 1D and 2D NMR spectra and confirmed by HR-ESI-MS data. The compounds of groups A and B differ from each other in their carbohydrate chains, namely monosulfated tetrasaccharide chains are inherent to group A and pentasaccharide chains with one sulfate group, branched by C-2 Qui2, are characteristic of group B.

New Ceramides and Cerebrosides from the Deep-Sea Far Eastern Starfish .

Three new ceramides (1−3) and three new cerebrosides (4, 8, and 9), along with three previously known cerebrosides (ophidiocerebrosides C (5), D (6), and CE-3-2 (7)), were isolated from a deep-sea starfish species, the orange cookie starfish Ceramaster patagonicus. The structures of 1−4, 8, and 9 were determined by the NMR and ESIMS techniques and also through chemical transformations. Ceramides 1−3 contain iso-C21 or C23 Δ9-phytosphingosine as a long-chain base and have C16 or C17 (2R)-2-hydroxy-fatty acids of the normal type.

Structures and Biologic Activity of Chitonoidosides I, J, K, K and L-Triterpene Di-, Tri- and Tetrasulfated Hexaosides from the Sea Cucumber .

Five new triterpene di-, tri- and tetrasulfated hexaosides (chitonoidosides I (), J (), K (), K () and L ()) were isolated from the Far-Eastern sea cucumber , collected near Bering Island (Commander Islands) from a depth of 100-150 m. The structural variability of the glycosides concerned both the aglycones (with 7(8)- or 9(11)-double bonds) and carbohydrate chains differing from each other by the third sugar residue (Xyl or sulfated by C-6 Glc) and/or by the fourth-terminal in the bottom semi-chain-residue (Glc or sulfated by C-6 MeGlc) as well as by the positions of a sulfate group at C-4 or C-6 in the sixth-terminal in the upper semi-chain-residue (MeGlc). Hemolytic activities of these compounds - against human erythrocytes as well as cytotoxicity against human cancer cell lines, HeLa, DLD-1 and HL-60, were studied.

In Vitro Anticancer and Cancer-Preventive Activity of New Triterpene Glycosides from the Far Eastern Starfish .

Sea stars or starfish (class Asteroidea) and holothurians or sea cucumbers (class Holothuroidea), belonging to the phylum Echinodermata (echinoderms), are characterized by different sets of glycosidic metabolites: the steroid type in starfish and the triterpene type in holothurians. However, herein we report the isolation of eight new triterpene glycosides, pacificusosides D−K (1−3, 5−9) along with the known cucumarioside D (4), from the alcoholic extract of the Far Eastern starfish Solaster pacificus. The isolated new compounds are closely related to the metabolites of sea cucumbers, and their structures of 1−3 and 5−9 were determined by extensive NMR and ESIMS techniques.

Disulfated Ophiuroid Type Steroids from the Far Eastern Starfish and Their Cytotoxic Activity on the Models of 2D and 3D Cultures.

New steroidal 3β,21-disulfates (-), steroidal 3β,22-disulfate (), and the previously known related steroidal 3β,21-disulfate () were isolated from the ethanolic extract of the Far Eastern starfish , collected off Urup Island in the Sea of Okhotsk. The structures of these compounds were determined by intensive NMR and HRESIMS techniques as well as by chemical transformations. Steroids and have an oxo-group in the tetracyclic nucleus at position C-7 and differ from each other by the presence of the 5(6)-double bond.

Triterpene Glycosides from the Far Eastern Sea Cucumber : Chemical Structures and Cytotoxicities of Chitonoidosides E, F, G, and H.

Four new triterpene disulfated glycosides, chitonoidosides E (), F (), G (), and H (), were isolated from the Far-Eastern sea cucumber and collected near Bering Island (Commander Islands) at depths of 100-150 m. Among them there are two hexaosides ( and ), differing from each other by the terminal (sixth) sugar residue, one pentaoside () and one tetraoside (), characterized by a glycoside architecture of oligosaccharide chains with shortened bottom semi-chains, which is uncommon for sea cucumbers. Some additional distinctive structural features inherent in - were also found: the aglycone of a recently discovered new type, with 18(20)-ether bond and lacking a lactone in chitonoidoside G (), glycoside 3--methylxylose residue in chitonoidoside E (), which is rarely detected in sea cucumbers, and sulfated by uncommon position 4 terminal 3--methylglucose in chitonoidosides F () and H ().

Unusual Structures and Cytotoxicities of Chitonoidosides A, A, B, C, D, and E, Six Triterpene Glycosides from the Far Eastern Sea Cucumber .

Six new triterpene tetra-, penta- and hexaosides, chitonoidosides A (), A (), B (), C (), D (), and E (), containing one or two sulfate groups, have been isolated from the Far-Eastern sea cucumber , collected near Bering Island (Commander Islands) from the depth of 100-150 m. Three of the isolated compounds (, and ) are characterized by the unusual aglycone of new type having 18(20)-ether bond and lacking a lactone in contrast with wide spread holostane derivatives. Another unexpected finding is 3--methylxylose residue as a terminal unit in the carbohydrate chains of chitonoidosides B (), C (), and E (), which has never been found before in the glycosides from holothurians belonging to the family.

Triterpene Glycosides from the Far Eastern Sea Cucumber (Levin): The Structures, Cytotoxicities, and Biogenesis of Kurilosides A, D, G, H, I, I, J, K, and K.

Nine new mono-, di-, and trisulfated triterpene penta- and hexaosides, kurilosides A (), D (), G (), H (), I (), I (), J (), K (), and K () and two desulfated derivatives, DS-kuriloside L (), having a trisaccharide branched chain, and DS-kuriloside M (), having hexa--lanostane aglycone with a 7(8)-double bond, have been isolated from the Far-Eastern deep-water sea cucumber (Levin) and their structures were elucidated based on 2D NMR spectroscopy and HR-ESI mass-spectrometry. Five earlier unknown carbohydrate chains and two aglycones (having a 16,(20S)-dihydroxy-fragment and a 16-acetoxy,(20S)-hydroxy fragment) were found in these glycosides. All the glycosides - have a sulfate group at C-6 Glc, attached to C-4 Xyl1, while the positions of the other sulfate groups vary in different groups of kurilosides.

New Isomalabaricane-Derived Metabolites from a sp. Marine Sponge.

In continuation of our studies on a Vietnamese collection of a sp., sponge we have isolated two new isomalabaricane triterpenoids, stellettins Q and R ( and ), and four new isomalabaricane-derived -terpenoids, stellettins S-V -, along with previously known globostelletin N. Among them, compound contains an acetylenic fragment, unprecedented in the isomalabaricane family and extremely rare in other marine sponge terpenoids.

Kurilosides A, A, C, D, E and F-Triterpene Glycosides from the Far Eastern Sea Cucumber (Levin): Structures with Unusual Non-Holostane Aglycones and Cytotoxicities.

Six new monosulfated triterpene tetra-, penta- and hexaosides, namely, the kurilosides A (), A (), C (), D (), E () and F (), as well as the known earlier kuriloside A (), having unusual non-holostane aglycones without lactone, have been isolated from the sea cucumber (Levin) (Cucumariidae, Dendrochirotida) collected in the Sea of Okhotsk near Onekotan Island from a depth of 100 m. Structures of the glycosides were established by 2D NMR spectroscopy and HR-ESI mass spectrometry. Kurilosides of the groups A and E contain carbohydrate moieties with a rare architecture (a pentasaccharide branched by C(4) Xyl1), differing from each other in the second monosaccharide residue (quinovose or glucose, correspondingly); kurilosides of the group C are characterized by a unique tetrasaccharide branched by a C(4) Xyl1 sugar chain; and kurilosides of the groups D and F are hexaosides differing from each other in the presence of an -methyl group in the fourth (terminal) sugar unit.

Polar steroid compounds from the Arctic starfish and their cytotoxic properties against normal and tumor cells .

Two new natural compounds, sulfated polyhydroxysteroid, microdiscusol G (), and polyhydroxysteroid bioside, microdiscusoside A (), along with eight previously known polar steroid substances , were isolated from the Arctic starfish . The structures of and have been elucidated by extensive 1D and 2D NMR spectroscopy and HRESIMS techniques. The 28-sulfooxy-24-methylcholestane side chain in has been found among starfish steroid metabolites for the first time.

Enzymatic transformation and anti-tumor activity of Sargassum horneri fucoidan.

Structure of the fucoidan from Sargassum horneri and products of its enzymatic transformation with molecular weight over 20 kDa were investigated. Fucoidan was hydrolyzed by recombinant fucoidanase FFA1 and its fraction of higher molecular weight was fractionated using anion-exchange chromatography, resulting in three sulphated polysaccharides of various molecular weight (63-138 kDa). Their structures were analyzed using NMR spectroscopy, showing the fucoidan (ShF) to be a branched polysaccharide with the backbone consisting of the repeating →3-α-l-Fucp(2SO)-1→4-α-l-Fucp(2,3SO)-1→ fragment and side chains including the α-l-Fucp-1→2-α-l-Fucp-1→ or α-l-Fucp-1→3-α-l-Fucp(4SO)-1→ fragments attached to the main chain at C4.