Benzaldehyde derivatives from Eurotium rubrum, an endophytic fungus derived from the mangrove plant Hibiscus tiliaceus

Four new (1-4) and seven known (5-11) benzaldehyde derivatives were characterized from the liquid fermentation cultures of Eurotium rubrum, an endophytic fungus that was isolated from the inner tissue of stems of the mangrove plant Hibiscus tiliaceus. The structures of these compounds were determined by extensive analysis of their spectroscopic data. Among these metabolites, compound 1, which was named as eurotirumin, possesses a new carbon skeleton with a cyclopentabenzopyran ring system.

Flavanol derivatives from Rhizophora stylosa and their DPPH radical scavenging activity

A new acetylated flavanol, 3,7-O-diacetyl (-)-epicatechin (3), and seven known flavanol derivatives, (-)-epicatechin (1), 3-O-acetyl (-)-epicatechin (2), 3,3 ',4 ',5,7-O-pentaacetyl (-)-epicatechin (4), (+)-afzelechin (5), (+)-catechin (6), cinchonain Ib (7), and proanthocyanidin B2 (8), were isolated from the stems and twigs of the mangrove plant Rhizophora stylosa and identified. The crude extract, the different fractions and all of the purified compounds were evaluated for DPPH radical scavenging activity.

Natural Anthraquinone Derivatives from a Marine Mangrove Plant-Derived Endophytic Fungus Eurotium rubrum: Structural Elucidation and DPPH Radical Scavenging Activity

There is considerable interest in the isolation of potent radical scavenging compounds from natural resources to treat diseases involving oxidative stress. In this report, four new fungal metabolites including one new bisdihydroanthracenone derivative (1, eurorubrin), two new seco-anthraquinone derivatives [3, 2-O-methyl-9-dehydroxyeurotinone and 4, 2-O-methyl4-O-(alpha-D-ribofuranosyl)-9-dehydroxyeurotinone], and one new anthraquinone glycoside [6,3-O-(alpha-D-ribofuranosyl)questin], were isolated and identified from Eurotium rubrum, an endophytic fungal strain that was isolated from the inner tissue of the stem of the marine mangrove plant Hibiscus tiliaceus. In addition, three known compounds including asperflavin (2), 2-O-methyleurotinone (5), and questin (7) were also isolated and identified. Their structures were elucidated on the basis of spectroscopic analysis. All of the isolated compounds were evaluated for 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical scavenging activity.

Preparation of porous chitosan/agarose microsphere and its R-phycoerythrin release properties

The chitosan microspheres (CS-CL) were prepared by suspension crosslinking method and used as carriers of R-phycoerythrin (R-PE). In this study, R-PE was loaded in the microspheres and released in vitro. The effects of pH value, temperature, ionic strength, and R-PE concentration on loading efficiency and release behavior were discussed. A novel microsphere that contained agarose (CS-AR MP) was prepared and the basic loading and releasing behavior for R-PE of this kind of new micro-spheres were also investigated. The results showed that all these chitosan microspheres have the ability to control-release R-PE. The addition of agarose may somewhat accelerate the release rate of R-PE from microspheres and reduce the capacity of adsorption for R-PE. (c) 2006 Wiley Periodicals, Inc.

含硫、磷壳聚糖新衍生物的制备、结构与抑菌活性关系研究

由于化学农药和抗生素兽药残留问题严重影响着环境和人类健康，生物农药和兽药的开发迫在眉睫。壳聚糖无毒、无污染、可生物降解，已经成为这一方向研究热点。但是，目前对壳聚糖抑菌活性的研究大都集中于分子量和脱乙酰度对其活性的影响，而对壳聚糖衍生物的研究相对较少。本文制备了壳聚糖磺酰胺类、酰基异硫氰酸酯类和α-氨基烷基膦酸酯类共计40余种新型壳聚糖含硫、磷衍生物，研究了它们对6种真菌（棉花枯萎病菌、番茄早疫病菌、葡萄炭疽病菌、姜叶斑点病菌、黄瓜灰霉病菌、芦笋茎枯病）和4种细菌（大肠杆菌、绿脓杆菌、金黄色葡萄球菌、八叠球菌）的抑菌活性，结果发现，所有衍生物的抑菌活性均强于壳聚糖原料，其中4种新型衍生物对于真菌具有较强抑制活性，其抑制率大于或接近阳性对照武夷菌素；10余种衍生物对于细菌有较强的杀菌、抑菌活性，如4-HBSA(l)CMCS、4-HBSA(l)CSS等对四种细菌具有广谱性，效果接近甚至强于阳性对照诺氟沙星。 对影响因素、构效关系和机理进行了深入探讨。衍生物的分子量、浓度、溶解性、α-位C原子空间位阻、吸电子空间诱导效应、烷基链的增长、等因素变化均会对抑菌活性产生重大影响。

Preparation and in vitro antioxidant activity of kappa-carrageenan oligosaccharides and their oversulfated, acetylated, and phosphorylated derivatives

In order to study the relationship between chemical structure and properties of modified carrageenans versus antioxidant activity in vitro, K-carrageenan oligosaccharides were prepared through mild hydrochloric acid hydrolysis of the polysaccharide, and these were used as starting materials for the partial synthesis of their oversulfated, acetylated, and phosphorylated derivatives. The structure and substitution pattern of the oligosaccharides and their derivatives were Studied using FTIR and C-13 NMR spectroscopy, and their in vitro antioxidant activities were investigated. Certain derivatives of the carrageenan oligosaccharides exhibited higher antioxidant activity than the polysaccharides and oligosaccharides in certain antioxidant systems. The oversulfated and acetylated derivatives, which scavenge superoxide radicals, the phosphorylated and low-DS acetylated derivatives, which scavenge hydroxyl radicals, and the phosphorylated derivatives, which scavenge DPPH radicals, all exhibited significant antioxidant activities it, the systems examined. The effect of the molecular weight of the carrageenan on antioxidant activities, however, is not obvious from these studies. (c) 2005 Elsevier Ltd. All rights reserved.

Study on cytocompatibility of carboxymethyl-chitosan membranes to skin fibroblasts

Chitosan and carboxymethl-chitosan (CM-chitosan) membranes with different molecular mass were prepared by a casting method. The cytocompatibility of two kinds of polysaccharide membranes to skin fibroblasts that cultured in vitro were studied. The methods were to culture the cells in soaking fluid of membranes and to culture the cells on the membranes directly. The results showed that the soaking fluid had no toxicity to fibroblasts and the biological security of lower molecular mass membranes were better than higher molecular mass membranes, and CM-chitosan membranes were better than chitosan membranes. In addition, the growth of fibroblasts on chitosan membranes was inhibited and the cells would fall off from chitosan membranes after a period of culture. However, the cells adhered and expanded well on CM-chitosan membranes. All these demonstrated that cytocompatibility of CM-chitosan membranes to skin fibroblasts was better than chitosan membranes.

Antioxidant activity and cytoprotective effect of kappa-carrageenan oligosaccharides and their different derivatives

Antioxidant activity of kappa-carrageenan oligosaccharides (OM) and their chemical modification derivatives was investigated employing various established in vitro systems, such as reducing power, iron ion chelation, and total antioxidant activity using beta-carotene-linoleic acid system. The oversulfated (SD), lowly (LAD), and highly acetylated derivatives (HAD) in reducing power assay, the phosphorylated derivative (PD) in metal chelating assay, and oversulfated and phosphorylated derivatives in total antioxidant activity assay exhibited antioxidant activity higher than that of carrageenan oligosaccharides. The results indicated that the chemical modification of carrageenan oligosaccharides can enhance their antioxidant activity in vitro. The protective effects of the carrageenan oligosaccharides and their chemically modified derivatives against H2O2 and UVA (long-wave ultraviolet radiation) induced oxidative damage on rat thymic lymphocyte were investigated by measuring cell viability via 3-(4,5-dimethylthiazol-2yl)-2,5-diphenyltetrazolium bromide (MTT). Thymic lymphocyte exposure to H2O2 and UVA, a marked reduction in cell survival was observed, which was significantly prevented by carrageenan oligosaccharides and their derivatives (preincubated for 2 h) at 66.7-2000 mu g/mL. But both the carrageenan oligosaccharides and their different derivatives showed the similar protective effects on intracellular level. Taken together, these results suggest that carrageenan oligosaccharides and their derivatives show relevant antioxidant activity both in vitro and in a cell system. (C) 2005 Elsevier Ltd. All rights reserved.

Bromophenol derivatives from the red alga Rhodomela confervoides

Eight new bromophenol derivatives, 2,3-dibromo-4,5-dihydroxybenzyl methyl sulfoxide (1), 4-(2,3-dibromo-4,5-dihydroxyphenyl)-3-butene-2-one (2), 2-(3-bromo-5-hydroxy-4-methoxyphenyl)-3-(2,3-dibromo-4,5-dihydroxyphenyl)propionic acid (3), 2-(3-bromo-5-hydroxy-4-methoxyphenyl)-3-(2,3-dibromo-4,5-dihydroxyphenyl)propionic acid methyl ester (4), 2-phenyl-3-(2,3-dibromo-4,5-dihydroxyphenyl)propionic acid (5), 4'-methoxy-2",3',3"-tribromo-4",5',5"-trihydroxydiphenylacetic acid (6), and 3-bromo-5-hydroxy-4-methoxyphenylacetic acid (7) and its methyl ester (8), together with a known bromophenol, 3-bromo-5-hydroxy4-methoxybenzoic acid (9), were isolated from the red alga Rhodomela confervoides. Their structures were elucidated by spectroscopic methods including IR, EIMS, FABMS, ESIMS, HRFABMS, HRESIMS, 1D and 2D NMR, and single-crystal X-ray structure analysis. Compounds 1-4, 8, and 9 were found inactive against several human cancer cell lines and microorganisms.

Bromophenols coupled with derivatives of amino acids and nucleosides from the red alga Rhodomela confervoides

Three new bromophenols coupled with pyroglutamic acid derivatives and one bromophenol coupled with deoxyguanosine were obtained from the red alga Rhodomela confervoides. By spectroscopic methods including 2D NMR and single-crystal X-ray structure analysis their structures were elucidated as N-(2,3-dibromo-4,5-dihydroxybenzyl)methyl pyroglutamate (1), N-(2,3-dibromo-4,5-dihydroxybenzyl)pyroglutamic acid (2), N-[3-bromo-2-(2,3-dibromo-4,5-dihydroxybenzyl)-4,5-dihydroxybenzyllmethyl pyroglutamate (3), and 2-N-(2,3-dibromo-4,5-dihydroxybenzylamino)deoxyguanosine (4), respectively. Compounds 1-4 were evaluated against several microorganisms and human cancer cell lines, but found inactive. To our knowledge this is the first report of bromophenols coupled with amino acid or nucleoside derivatives through the C-N bond.

The antitumor effect of bromophenol derivatives in vitro and Leathesia nana extract in vivo

To investigate the antitumor effect of bromophenol derivatives in vitro and Leathesia nana extract in vivo, six bromophenol derivatives 6-(2,3-dibromo-4,5-dihydroxybenzyl)-2,3-dibromo-4,5-dihydroxy benzyl methyl ether (1), (+)-3-(2,3-dibromo-4,5-dihydroxyphenyl)-4-bromo-5,6-dihydroxy-1,3-dihydroisobenzofuran (2), 3-bromo-4-(2,3-dibromo-4,5-dihydroxybenzyl)-5-methoxymethyl-pyrocatechol (3), 2,2',3,3'-tetrabromo-4,4',5,5'-tetrahydroxy-diphenylmethane (4), bis(2,3-dibromo-4,5-dihydroxybenzyl) ether (5), 2,2',3-tribromo-3',4,4',5-tetrahydroxy-6'-ethyloxymethyldiphenylmethane (6) were isolated from brown alga Leathesia nana, and their cytotoxicity were tested by MTT assays in human cancer cell lines A549, BGC-823, MCF-7, B16-BL6, HT-1080, A2780, Bel7402 and HCT-8. Their inhibitory activity against protein tyrosine kinase (PTK) with over-expression of c-kit was analyzed also by ELISA. The antitumor activity of ethanolic extraction of Leathesia nana (EELN) was evaluated on S-180-bearing mice. All compounds showed very potent cytotoxicity against all of the eight cancer cell lines with IC50 below 10 mu g/mL. In PTK inhibition study, all bromophenol derivatives showed moderate inhibitory activity and compounds 2, 5 and 6 showed significant bioactivity with the inhibition ratio of 77.5%, 80.1% and 71.4%, respectively. Pharmacological studies reveal that EELN could inhibit the growth of Sarcoma 180 tumor and increase the indices of thymus and spleen to improve the immune system remarkably in vivo. Results indicated that the bromophenol derivatives and EELN can be used as potent antitumor agents for PTK over-expression of c-kit and considered in a new therapeutic strategy for treatment of cancer.

Synthesized different derivatives of low molecular fucoidan extracted from Laminaria japonica and their potential antioxidant activity in vitro

Six low molecular fucoidan (DFPS) derivatives were synthesized successfully, and their potential antioxidant activities were investigated employing various established in vitro systems. All DFPS derivatives possessed considerable antioxidant activity, and had stronger antioxidant ability than DFPS in certain tests. The benzoylated DFPS (PHDF) showed strongest scavenging activity on superoxide, hydroxyl and 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical, however, DFPS exhibited greatest reducing power. Available data suggested that substituted groups of DFPS played an important role on antioxidant activity, and the mechanism on influence the antioxidant activity of samples of substituted group was indicated. (C) 2009 Elsevier B.V. All rights reserved.

Synthesized oversulphated, acetylated and benzoylated derivatives of fucoidan extracted from Laminaria japonica and their potential antioxidant activity in vitro

Three sulphated polysaccharide derivatives (oversulphated, acetylated and benzoylated fucoidan) were successfully synthesized, and their antioxidant activities were investigated employing various established in vitro systems. A novel catalyst N-bromosuccinimide (NBS) was used in acetylation and benzoylation reaction, and the degree of acetylation was evaluated using IR and NMR spectra. Both fucoidan derivatives possessed considerable antioxidant activity, and had stronger antioxidant ability than fucoidan in certain tests. The benzoylated fucoidan showed strongest superoxide and hydroxyl radical scavenging activity, however, the acetylated fucoidan exhibited strongest activity on scavenging DPPH radical and reducing power. Available data obtained with in vitro models suggested that substituted groups of fucoidan played an important role on antioxidant activity. The mechanism on the antioxidant activity of sulphonyl, acetyl and benzoyl group is different. (C) 2008 Elsevier Ltd. All rights reserved.