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.

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.

Combined Radiomodifying Effect of Fucoidan from the Brown Alga and Pacificusoside D from the Starfish in the Model of 3D Melanoma Cells.

Cancer is one of the main causes of human mortality worldwide. Despite the advances in the diagnostics, surgery, radiotherapy, and chemotherapy, the search for more effective treatment regimens and drug combinations are relevant. This work aimed to assess the radiomodifying effect and molecular mechanism of action of fucoidan from the brown alga (ScF) and product of its autohydrolysis (ScF_AH) in combination with pacificusoside D from the starfish (SpD) on the model of viability and invasion of three-dimension (3D) human melanoma cells SK-MEL-2.

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.

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.

Combined Anticancer Effect of Sulfated Laminaran from the Brown Alga and Polyhydroxysteroid Glycosides from the Starfish on 3D Colorectal Carcinoma HCT 116 Cell Line.

Colorectal cancer is one of the most frequent types of malignancy in the world. The search for new approaches of increasing the efficacy of cancer therapy is relevant. This work was aimed to study individual, combined anticancer effects, and molecular mechanism of action of sulfated laminaran AaLs of the brown alga and protolinckiosides A (PL1), B (PL2), and linckoside L1 (L1) of the starfish   using a 3D cell culture model.

Sphingolipids of Asteroidea and Holothuroidea: Structures and Biological Activities.

Sphingolipids are complex lipids widespread in nature as structural components of biomembranes. Commonly, the sphingolipids of marine organisms differ from those of terrestrial animals and plants. The gangliosides are the most complex sphingolipids characteristic of vertebrates that have been found in only the Echinodermata (echinoderms) phylum of invertebrates.

Fucoidan from brown algae Fucus evanescens potentiates the anti-proliferative efficacy of asterosaponins from starfish Asteropsis carinifera in 2D and 3D models of melanoma cells.

This study was aimed to determine the efficacy of combination of fucoidan from the brown algae Fucus evanescens (FeF) or its derivatives with thornasteroside A (ThA) or asteropsiside A (AsA) from the starfish Asteropsis carinifera in combating human melanoma cells. In vitro MTS and soft agar methods were performed to determine effect of FeF, its derivatives, ThA, AsA or their combination on proliferation and colony formation of SK-MEL-28 cells in 2D and 3D culture. Desulfation of FeF, but not deacetylation, led decreasing of its Mw and anti-proliferative activity.

Asterosaponins: Structures, Taxonomic Distribution, Biogenesis and Biological Activities.

Asterosaponins are a class of steroid oligoglycosides isolated from starfish with characteristic structures and diverse biological activities. In this review, we have attempted to combine the most important data concerning asterosaponins and give a list of these secondary metabolites with their structural peculiarities. The purpose of this review is to provide a brief but as complete as possible principal information about their chemical structures, taxonomic distribution in the marine environment, distribution in different geographical areas and depths, some properties, biological activities, and functions.

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.

New Conjugates of Polyhydroxysteroids with Long-Chain Fatty Acids from the Deep-Water Far Eastern Starfish and Their Anticancer Activity.

Four new conjugates, esters of polyhydroxysteroids with long-chain fatty acids (-), were isolated from the deep-water Far Eastern starfish Ceramaster patagonicus The structures of - were established by NMR and ESIMS techniques as well as chemical transformations. Unusual compounds - contain the same 5α-cholestane-3β,6β,15α,16β,26-pentahydroxysteroidal moiety and differ from each other in the fatty acid units: 5'Z,11'Z-octadecadienoic (), 11'Z-octadecenoic (), 5'Z,11'Z-eicosadienoic (), and 7'Z-eicosenoic () acids. Previously, only one such steroid conjugate with a fatty acid was known from starfish.

The Distribution of Asterosaponins, Polyhydroxysteroids and Related Glycosides in Different Body Components of the Far Eastern Starfish .

Glycoconjugated and other polar steroids of starfish have unique chemical structures and show a broad spectrum of biological activities. However, their biological functions remain not well established. Possible biological roles of these metabolites might be indicated by the studies on their distribution in the organism-producer.

Effects of Polar Steroids from the Starfish in Combination with X-Ray Radiation on Colony Formation and Apoptosis Induction of Human Colorectal Carcinoma Cells.

Despite significant advances in the understanding, prevention, and treatment of cancer, the disease continues to affect millions of people worldwide. Chemoradiation therapy is a rational approach that has already proven beneficial for several malignancies. However, the existence of toxicity to normal tissue is a serious limitation of this treatment modality.

Six new polyhydroxylated steroids conjugated with taurine, microdiscusols A-F, from the Arctic starfish Asterias microdiscus.

Six new polyhydroxylated steroids conjugated with taurine, microdiscusols A-F, were isolated from the alcoholic extract of the Arctic starfish Asterias microdiscus. Three of them have been found to have additional sulfate groups in tetracyclic cores. The structures of new compounds were established by 1D and 2D NMR and HRESIMS techniques.

Asterosaponins from the tropical starfish and their cytotoxic and anticancer activities .

New asterosaponin, acanthaglycoside G (), along with three previously known steroidal oligoglycosides (), were isolated from the ethanolic extract of the starfish , collected off the coast of Vietnam. The structure of was mainly elucidated by extensive NMR and ESIMS techniques as sodium 6--{-D-fucopyranosyl-(1→2)--D-quinovopyranosyl-(1→4)-[-D-quinovopyranosyl-(1→2)]--D-quinovopyranosyl-(1→3)--D-quinovopyranosyl}-6-hydroxy-5-pregn-9(11)-en-20-one-3-yl sulfate. Compounds and showed slight cytotoxic activities against cancer RPMI-7951, HT-29, and MDA-MB-231 cell lines, but effectively inhibited in non-toxic concentrations colony formation of HT-29 and MDA-MB-231 cells and cell migration of MDA-MB-231 cells.

Structural Characterization of Polar Steroid Compounds of the Far Eastern Starfish Lethasterias fusca by Nanoflow Liquid Chromatography Coupled to Quadrupole Time-of-Flight Tandem Mass Spectrometry.

Nanoflow liquid chromatography coupled with a captive spray ionization time-of-flight tandem mass spectrometer (nLC/CSI-QTOF-MS/MS) was used in the structural determination of polar steroid compounds of starfish Lethasterias fusca. A total of 207 compounds including 106 asterosaponins, 81 glycosides of polyhydroxysteroids, and 14 polyhydroxylated steroids were detected and characterized by MS and MS/MS. Twenty compounds among them were unambiguously identified using authentic standard compounds, isolated earlier from this and other starfish species.

Triterpene glycosides from the Vietnamese sea cucumber .

From the MeOH extract of the Vietnamese sea cucumber , eight triterpene glycosides (-), including one new compound namely holothurin A (), were isolated by using various chromatographic separations. Their structures were established by spectroscopic experiments including 1D, 2D NMR and HR-ESI-MS. Holothurin A () has a hydroperoxy group at C-25.

In Vitro Anticancer and Proapoptotic Activities of Steroidal Glycosides from the Starfish .

New marine glycoconjugates-the steroidal glycosides designated as anthenosides V⁻X (⁻)-and the seven previously known anthenosides E (), G (), J (), K (), S1 (), S4 (), and S6 () were isolated from the extract of the tropical starfish . The structures of ⁻ were elucidated by extensive NMR and ESIMS techniques. Glycoside contains a rare 5α-cholest-8(14)-ene-3α,7β,16α-hydroxysteroidal nucleus.

Two New Steroidal Monoglycosides, Anthenosides A₁ and A₂, and Revision of the Structure of Known Anthenoside A with Unusual Monosaccharide Residue from the Starfish .

Two new polyhydroxysteroidal glycosides, anthenosides A₁ () and A₂ (), and one previously known steroidal glycoside anthenoside A () were isolated from extract of the tropical starfish . Structures of ⁻ were determined by analysis of the spectroscopic data as well as chemical transformations. As a result, the structure of anthenoside A has been revised and the structures of and were established.

Granulatosides D, E and other polar steroid compounds from the starfish . Their immunomodulatory activity and cytotoxicity.

Two new steroid glycosides, granulatosides D () and E (), belonging to the group of bi- and monoglycosides of polyhydroxysteroids, respectively, were isolated from the ethanolic extract of the starfish along with thirteen previously known glycosides of polyhydroxysteroids (-) and one steroid heptaol (). The structures of the new compounds were elucidated by extensive NMR and ESIMS techniques. Cytotoxic and immunomodulatory activities of compounds , -, and - using murine splenocytes and peritoneal macrophages were studied.