[Steroidal compounds from the Pacific starfish Mithrodia clavigera and their toxic properties against human melanoma cells].

The new sulfated polyhydroxysteroid has been isolated from the Pacific starfish Mithrodia clavigera, collected from Maldives Islands and named as mitrotriol (I, Na-salt of (20S)-3beta,6alpha,20-trihydroxy-5alpha-cholest-9(11)-ene 3-O-sulfate). In addition six previously known compounds, including glycosides: echinasteroside B, granulatoside A, linckoside K, forbeside L and thornasterol sulfate A and cholesterol sulfate were isolated and identified. The structure of mitrotriol was elucidated by spectroscopic methods (mainly 2D NMR: 1H, 13C, DEPT, COSY-45, NOESY, HSQC and HMBC) and mass-spectrometry. For selected compounds, concentrations that showed cytotoxic activity against melanoma cells SK-MEL-28, SK-MEL-5 and RPMI-7951 were determined.

[Polar steroids from Solaster endeca starfish and the physiological activity of polar steroids from three starfish species].

Four polyhydroxylated steroids, new (20R)-5alpha-cholestan-3beta,6alpha,8,15alpha,24,26-hexaol (I) and known (20R,25S)-5alpha-cholestan-3beta6alpha,8,15beta,16beta,26-hexaol, (20R,25S)-5alpha-cholestan-3beta,6alpha,15beta,16beta,26-pentaol, and marthasterone sulfate were isolated from the Solaster endeca starfish inhabiting the Sea of Okhotsk and characterized. Steroid (I) contains a 24,26-dihydroxylated side chain, which is uncommon for starfish polyols. The isolated steroids and related metabolites from two starfish species of the Evasterias genus (in total, 15 compounds) were weakly cytotoxic in a human HeLa cell culture and some of them were inhibitors of nonspecific esterase from mouse Ehrlich carcinoma. The effects of these compounds on the p53 protein activity were studied in a yeast two-hybrid test system and both inhibitors and stimulators of this activity were found among them.

[Steroid compounds from two pacific starfish of the genus Evasterias].

Three new steroid glycosides (evasteriosides C, D, and E), along with six known compounds, were isolated from two Pacific starfish of the genus Evasterias. Evasterioside C from E. retifera collected from the Sea of Japan was identified as (20R,22E)-3-O-(beta-D-xylopyranosyl)-24-nor-5alpha-cholest-22-ene-3beta,6beta,8,15alpha,26-pentaol 26-sulfate sodium salt. The structures of evasterioside D and E from E. echinosoma (collected from the Gulf of Shelichov, the Sea of Okhotsk) were established as (20R,24S)-24-O-(beta-D-glucopyranosyl)-5alpha-cholestane-3beta,6alpha,8,15beta,24-pentaol and (20R,24S)-3,24-di-O-(beta-D-xylopyranosyl)-cholest-4-ene-3beta,6beta,8,15alpha,24-pentaol, respectively. In addition, the known compounds pycnopodiosides A and C, luridoside A, 5alpha-cholestane-3beta,6alpha,8,15beta,16beta,26-hexaol, 5alpha-cholestane-3beta,6alpha,8,15beta,24-pentaol 24-sulfate sodium salt, and marthasterone sulfate sodium salt were identified in E. echinosoma. The structures of the isolated compounds were established on the basis of spectroscopic analyses using 1D and 2D NMR techniques, mass spectrometry, and some chemical transformations.

[Trofosides A and B and other cytostatic steroid-derived compounds from the Far East starfish Trofodiscus über].

Three new polar steroids identified as trofoside A, (20R,24S)-24-O-(3-O-methyl-beta-D-xylopyranosyl)-3beta,6alpha,8,15beta,24-pentahydroxy-5alpha-cholestane, its 22(23)-dehydro derivative (trofoside B), and 15-sulfoxy-(20R,24S)-5alpha-cholestane-3beta,6beta,8,15alpha,24-pentaol sodium salt, were isolated from Trofodiscus uber starfish extracts collected in the Sea of Okhotsk. Two known compounds, trofoside A aglycone, (20R,24S)-3beta,6alpha,8,15beta,24-pentahydroxy-5alpha-cholestane, and triseramide, (20R,24R,25S,22E)-24-methyl-3beta,6alpha,8,15beta-tetrahydroxy-5alpha-cholest-22-en-27-oic acid (2-sulfoethyl)amide sodium salt, were also found. The structures of the isolated polyoxysteroids were established from their spectra. Minimal concentrations causing degradation of unfertilized egg-cells of the sea-urchin Strongylocentrotus intermedius (C(min)) and terminating the cell division at the stage of the first division (C(min) embr.), as well as the concentrations causing 50% immobilization of sperm cells (ImC50) and inhibiting their ability to fertilize egg-cells by 50% (IC50) were determined for the isolated compounds. Of three compounds highly toxic in embryos and sea-urchin sperm cells, the polyol with a sulfo group in the steroid core was the most active; two glycosides with monosaccharide chains located at C3 and C24 atoms were less toxic. Note that all the compounds with the spermiotoxic activities differently affected the embryo development. The positions of monosaccharide residues in the core considerably influence the compound activity. For example, both mono- and double chained glycosides with the monosaccharide fragment at C3 and C24 atoms are active against sea-urchin sperm cells and embryos, whereas the C24 glycosylated trofoside A does not affect embryos and displays a poor spermiotoxicity.

[Steroid compounds from the Far East starfish Pteraster obscurus and the ophiura Asteronyx loveni].

Seven sulfated polyhydroxysteroids were isolated from the Far East starfish Pteraster obscurus and the ophiura (snake star) Asteronyx loveni (collected in the Sea of Okhotsk) and characterized: disodium and sodium salts of (20R)-24-methyl-2beta-hydroxycholesta-5,24(28)-diene-3alpha,21-diyl disulfate, (20R)-5alpha-cholestane-3beta,21-diyl disulfate, (20R)-3beta-hydroxy-5alpha-cholestan-21-yl sulfate, (20R)-cholest-5-ene-3beta,21-diyl disulfate, (20R)-2beta-hydroxycholest-5-ene-3alpha,21-diyl disulfate, (20R)-cholest-5-en-3beta-yl sulfate, and (20R)-5alpha-cholestan-3beta-yl sulfate. The first four compounds turned out to be new, whereas the others were identical to the known compounds. Structures of the isolated steroids were identified by two-dimensional NMR spectroscopy and other physicochemical methods. The compounds isolated from starfish are structurally similar to typical ophiuroid metabolites, which support the opinion of some taxonomists that starfish and ophiuroids are phylogenetically related classes.

[New steroid glycosides from the starfish Fromia milleporella].

Two new steroid glycosides from the starfish Fromia milleporella collected in the Seychelles were isolated and characterized: milleporoside A, (20R, 24R)-29-O-[3-O-methyl-beta-D-xylopyranosyl-(1-->4)-3-O-methyl-beta-D-xylopyranosyl]-24-ethyl-5alpha-cholestane-3beta,4beta,6alpha,8,15beta,16beta,29-heptaol, and milleporoside B, (20R, 24R)-(22E)-28-O-[3-O-methyl-beta-D-xylopyranosyl-(1-->4)-3-O-methyl-beta-D-xylopyranosyl]-24-methyl-5alpha-cholest-22-ene-3beta,4beta,6alpha,8,15beta,16beta,28-heptaol. The structures of the glycosides were determined from their spectra and a comparison with spectral characteristics of known compounds. These compounds exhibit a moderate cytostatic activity toward the embryos of the sea urchin Strongylocentrotus intermedius.

[Steroid compounds from far Eastern starfishes Henricia aspera and H. tumida].

Six new natural compounds were isolated from two Far Eastern starfish species, Henricia aspera and H. tumida, collected in the Sea of Okhotsk. Two new glycosylated steroid polyols were obtained from H. aspera: asperoside A and asperoside B, which were shown to be (20R,24R,25S)-3-O-(2,3-di-O-methyl-beta-D-xylopyranosyl)-24-methyl-5alpha-cholest-4-ene-3beta,6beta,8,15a,16beta,26-hexaol and (20R,24R,25S,22E)-3-O-(2,4-di-O-methyl-beta-D-xylopyranosyl)-24-methyl-5alpha-cholest-22-ene-3beta,4beta,6beta,8,15alpha,26-hexaol, respectively. Two other glycosylated polyols, tumidoside A, with the structure elucidated as (20R,22E)-3-O-(2,4-di-O-methyl-beta-D-xylopyranosyl)-26,27-di-nor-24-methyl-5alpha-cholest-22-ene-3beta,4beta,6beta,8,15alpha,25-hexaol, and tumidoside B, whose structure was elucidated as (20R,24S)-3-O-(2,3-di-O-methyl-beta-D-xylopyranosyl)-5alpha-cholestan-3beta,4beta,6beta,8,15alpha,24-hexaol, were isolated from the two starfish species. (20R,24S)-Salpha-Cholestan-3beta,6beta,15alpha,24-tetraol and (20R,24S)-5alpha-cholestan-3beta,6beta,8,15alpha,24-pentaol were identified only in H. tumida. The known monoglycosides henricioside H1 and laeviuscolosides H and G were also identified in both species.

[Morphologic changes due to hyperthermia (experimental study)]. / Morfologicheskie izmeneniia pri peregrevanii (éksperimental'noe issledovanie).

Acute and chronic overheating appeared to induce similar shock reaction in all organs, with systemic disorders of microcirculation. The organs demonstrated irreversible hemodynamic disturbances with secondary hypoxic injury. Structural disorders in organs result in their functional deficiency and subsequent pathologic conditions.

[Steroidal polyols from Far Eastern starfish Henricia sanguinolenta and H. leviuscula leviuscula]. / Steroidnye polioly iz dal'nevostochnykh morskikh zvezd Henricia sanguinolenta i H. leviuscula leviuscula.

Two new asterosaponins, (20R)-3-O-beta-D-(2-O-methylxylopyranosyl)-24-propylcholest-4-ene-3 beta,6 beta, 8, 15 alpha, 16 beta, 29-hexaol (sanguinoside A) and (20R,24S)-3-O-beta-D-(2,3,4-tri-O-methylxylopyranosyl)-5 alpha-cholestane-3 beta, 4 beta, 6 beta, 8, 15 alpha, 24-hexaol (sanguinoside B), were isolated from two species of Pacific Far Eastern Starfish Henricia sanguinolenta and H. leviuscula leviuscula, collected in the Sea of Okhotsk. Both glycosides contain aglycones with pentahy-droxysteroid nuclei of similar structures, which are substituted at the 3-hydroxy group with differently methylated beta-D-xylosyl residues. Sanguinoside A has an unusual structure of its aglycone side chain, whereas sanguinoside B has a unique permethylated carbohydrate chain. In addition, laevisculoside G, a known glycoside, was identified in the H. leviuscula starfish. The structures of the isolated glycosides were established by interpreting their spectral data and by comparing their spectral characteristics with those of known compounds. The English version of the paper. Russian Journal of Bioorganic Chemistry, 2004, vol. 30, no. 2; see also http://www.maik.ru.

[Steroid compounds from the Far Eastern starfish Diplopteraster multipes]. / Steroidnye soedineniia iz dal'nevostochnoi morskoi zvezdy Diplopteraster multipes.

Sodium salt of (20R)-3 alpha,4 beta-dihydroxycholest-5-ene-21-yl sulfate and disodium salts of (20R)-4 beta-hydoxycholest-5-ene-3 alpha,21-diyl disulfate, (20R)-24-methylcholest-5,24(28)-diene-3 alpha,21-diyl disulfate, (20R)-24-methyl-5 alpha-cholest-24(28)-ene-3 alpha,21-diyl disulfate, (20R)-cholest-5-ene-3 alpha, 21-diyl disulfate, (20R)-5 alpha-cholestane-3 alpha,21-diyl disulfate, and (20R)-3 alpha-hydroxycholest-5-ene-2 beta,21-diyl disulfate were isolated from the far eastern starfish Diplopteraster multipes and characterized. These compounds differ structurally from sulfated polyhydroxysteroids in other starfish species. At the same time, they are typical secondary metabolites of Ophiuroidea and have some structural features characteristic of the ophiuroid-isolated steroids, namely the 3 alpha-hydroxy (or 3 alpha-sulfoxy) and 21-sulfoxy groups. These data support the opinion of some taxonomists that starfishes and ophiuroids are phylogeneteically related classes and are closer to each other than to other classes of the Echinodermata phylum.

Immediate feedback of HbA1c levels improves glycemic control in type 1 and insulin-treated type 2 diabetic patients.

OBJECTIVE: Accurate and reliable HbA1c results can be obtained at the time of the office visit by using benchtop analyzers. We tested the hypothesis that immediately available HbA1c results could improve glycemic control by changing physician or patient behavior or both. RESEARCH DESIGN AND METHODS: A randomized controlled trial was conducted in 201 type 1 and insulin-treated type 2 diabetic patients attending an academic diabetes center. HbA1c levels, changes in insulin therapy, and use of health care resources were assessed during a 12-month follow-up period. RESULTS: HbA1c levels decreased significantly at 6 and 12 months in the immediate assay group (-0.57 +/- 1.44 and -0.40 +/- 1.65%, respectively; P < 0.01) but did not change in the control group (-0.11 +/- 0.79 and -0.19 +/- 1.16%, respectively; NS). The changes were similar for both type 1 and type 2 diabetic patients. There were no differences in the rates of hypoglycemic events or use of health care resources. CONCLUSIONS: In the setting of a controlled randomized trial, the immediate feedback of HbA1c results at the time of patient encounters resulted in a significant improvement of glycemic control at 6-month follow-up and persisted for the 12-month study. The introduction of this assay was positively received by both patients and physicians.

[Temporary work incapacity in the workers of the heat-treatment shops of the metallurgical industry due to diseases of the digestive system]. / Vremennaia netrudosposobnost' rabochikh goriachikh tsekhov metallurgicheskoi promyshlennosti, obuslovlennaia bolezniami pishchevaritel'noi sistemy.

Transitory disablement in 5886 workers engaged for the whole year into heat treating metallurgy was compared during 5 years (1981-1985) with that in 291 workers engaged into repairing mechanical occupations so as to reveal metallurgical occupational factors influencing on gastrointestinal morbidity. Metallurgical occupational hazards harm the health status in workers engaged into heat-treating metallurgy, induce the gastrointestinal disorders, which are demonstrated by the elevated transitory disablement. The workers engaged into heat treating metallurgy showed higher gastrointestinal morbidity rate than those engaged into repairing mechanical work.