T-Muurolol Sesquiterpenes from the Marine Streptomyces sp M491 and Revision of the Configuration of Previously Reported Amorphanes

Two new sesquiterpenes, 15-hydroxy-T-muurolol (3d) and 11,15-dihydroxy-T-muurolol (3e), along with the plant cadinenes T-muurolol (3f) and 3 alpha-hydroxy-T-muurolol (3g), were isolated from the marine-derived Streptomyces sp. M491. Their absolute configuration was established via NMR spectroscopy and X-ray crystallography of 3-oxo-T-muurolol (3a), which was reisolated from this strain. In addition, the absolute configuration of further sesquiterpenes previously reported from this strain was revised. These products were tested for their cytotoxicity against 37 human tumor cell lines using the MTT method. Only 3d was cytotoxic against a range of human tumor cell lines with a mean IC50 of 6.7 mu g/mL.

Highly brominated mono- and bis-phenols from the marine red alga Symphyocladia latiuscula with radical-scavenging activity

Four new highly brominated and fully substituted mono- and bis-phenols, 1-(2,3,6-tribromo-4,5-dihydroxybenzyl)pyrrolidin-2-one (1), 1,2-bis(2,3,6-tribromo-4,5-dihydroxyphenyl)ethane (2), 6-(2,3,6-tribromo-4,5-dihydroxybenzyl)-2,5-dibromo-3,4-dihydroxybenzyl methyl ether (3), and 2,3,6-tribromo-4,5-dihydroxybenzyl methyl sulfone (4), were characterized from the marine red alga Symphyocladia latiuscula. In addition, five known bromophenols, bis(2,3,6-tribromo-4,5-dihydroxyphenyl)methane (5), bis(2,3,6-tribromo-4,5-dihydroxybenzyl) ether (6), 2,3,6-tribromo-4,5-dihydroxybenzyl methyl ether (7), 2,3,6-tribromo-4,5-dihydroxymethylbenzene (8), and 2,3,6-tribromo-4,5-dihydroxybenzaldehyde (9), were also isolated and identified. The structures of these compounds were elucidated by spectroscopic methods including 1D and 2D NMR as well as by low- and high-resolution mass spectrometric analysis. Structurally, all of these compounds are highly brominated and fully substituted, and contain one or two 2,3,6-tribromo-4,5-dihydroxyphenyl unit(s) in each of the molecules. In addition, compound 4 possesses a unique sulfone structural feature. Each of the isolated compounds was evaluated for alpha,alpha-diphenyl-beta-picrylhydrazyl (DPPH) radical-scavenging activity and all were found to be potent, with IC50 values ranging from 8.1 to 24.7 mu M, compared to the known positive control butylated hydroxytoluene (BHT), with an IC50 of 81.8 mu M.

Diterpenes, sesquiterpenes, and a C-15-acetogenin from the marine red alga Laurencia mariannensis

In addition to 10 known compounds (7-16), one new brominated diterpene, 10-hydroxykahukuene B (1), two new sesquiterpenes, 9-deoxyelatol (2) and isodactyloxene A (3), one new brominated C-15-acetogenin, laurenmariallene (4), and two new naturally occurring halogenated sesquiterpenes (5 and 6) that were previously obtained as intemediates in a biomimetic synthetic study of rhodolaureol and rhodolauradiol have been isolated and identified from the organic extract of the marine red alga Laurencia mariannensis. The structures of these compounds were established by spectroscopic methods. The antibacterial and antifungal activities of new compounds 1-4 were evaluated.

Laurendecumallenes A-B and laurendecumenynes A-B, halogenated nonterpenoid C-15-Acetogenins from the marine red alga Laurencia decumbens

Four new halogenated nonterpenoid C-15-acetogenins, 4:7,6:13-bisepoxy-9,10-diol-1,12-dibromopentadeca-1,2-diene (1, laurendecumallene A), 4:7,6:12-bisepoxy-9,10-diol-1,13-dibromopentadeca-1,2-diene (2, laurendecumallene 13), (3Z)-6:10,7:13-bisepoxy-12-bromo-9-hydroperoxylpentadeca-3-en-1-yne (3, laurendecumenyne A), and (3Z)-6:10,9:13-bisepoxy-12-bromo-7-chloropentadeca-3-en-1-yne (4, laurendecumenyne 13), together with one known halogenated C-15-acetogenin elatenyne (5) were isolated and identified from the organic extract of the marine red alga Laurencia decumbens. Their structures and relative stereochemistry were established by means of spectroscopic analysis including UV, IR, high-resolution electrospray ionization mass spectrometry (HRESIMS), and ID and 2D NMR techniques. All these metabolites were submitted for the cytotoxic assay against tumor cell line A549 (human lung adenocarcinoma), but all of them were found inactive (IC50 > 10 mu g/mL).

Brominated Selinane Sesquiterpenes from the Marine Brown Alga Dictyopteris divaricata

Two new brominated selinane sesquiterpenes, 1-bromoselin-4(14), 11-diene (1) and 9-bromoselin-4(14), 11-diene (2), one known cadinane sesquiterpene, cadalene (3), and four known selinane sesquiterpenes, alpha-selinene (4), beta-selinene (5), beta-dictyopterol (6), and cyperusol C (7), were isolated from a sample of marine brown alga Dictyopteris divaricata collected off the coast of Yantai (China). Their structures were established by detailed MS and NMR spectroscopic analysis, as well as comparison with literature data.

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.

Chinikomycins A and B: Isolation, structure elucidation, and biological activity of novel antibiotics from a marine Streptomyces sp isolate M045

In our screening of marine Streptomycetes for bioactive principles, two novel antitumor antibiotics designated as chinikomycins A (2a) and B (2b) were isolated together with manumycin A (1), and their structures were elucidated by a detailed interpretation of their spectra. Chinikomycins A (2a) and B (2b) are chlorine-containing aromatized manumycin derivatives of the type 64-pABA-2 with an unusual para orientation of the side chains. They exhibited antitumor activity against different human cancer cell lines, but were inactive in antiviral, antimicrobial, and phytotoxicity tests.

Bromophenols from the marine red alga Polysiphonia urceolata with DPPH radical scavenging activity

Three new (1-3) and three known (4-6) bromophenols were isolated and identified from the marine red alga Polysiphonia urceolata. On the basis of extensive analysis of spectroscopic data, the structures of these compounds were determined to be 7-bromo-9,10-dihydrophenanthrene-2,3,5,6-tetraol (1), 4,7-dibromo-9,10-dihydrophenanthrene-2,3,5,6-tetraol (2), 1,8-dibromo-5,7-dihydrodibenzo[c,e]oxepine-2,3,9,10-tetraol (3), urceolatol (4), 3-,bromo-4,5-dihydroxybenzaidehyde (5), and 3,5-dibromo-4-hydroxybenzaldehyde (6). Each of the isolated compounds was evaluated for alpha,alpha-dipheny1-beta-picrylhydrazyl (DPPH) radical scavenging activity, and all were found to be potent, with IC50 values ranging from 6.1 to 35.8 mu M, compared to the positive control, butylated hydroxytoluene (BHT), with an IC50 of 83.8 mu M.

Aglacins I-K, three highly methoxylated lignans from Aglaia cordata

Further chemical investigation of the stem bark of Aglaia cordata has led to the isolation and identification of three new lignans, namely, aglacins I-K (1-3), all of which contain two contiguous trimethoxylated phenyl systems. Among them, aglacins I and J (1 and 2) are new members of the aryltetralin cyclic lactol class, while aglacin K (3) is a new example of tetralrydrofuran lignan. The structures of these compounds were established on the basis of spectroscopic data interpretation.

Cloning and Comparative Studies of Seaweed Trehalose-6-Phosphate Synthase Genes

The full-length cDNA sequence (3219 base pairs) of the trehalose-6-phosphate synthase gene of Porphyra yezoensis (PyTPS) was isolated by RACE-PCR and deposited in GenBank (NCBI) with the accession number AY729671. PyTPS encodes a protein of 908 amino acids before a stop codon, and has a calculated molecular mass of 101,591 Daltons. The PyTPS protein consists of a TPS domain in the N-terminus and a putative TPP domain at the C-terminus. Homology alignment for PyTPS and the TPS proteins from bacteria, yeast and higher plants indicated that the most closely related sequences to PyTPS were those from higher plants (OsTPS and AtTPS5), whereas the most distant sequence to PyTPS was from bacteria (EcOtsAB). Based on the identified sequence of the PyTPS gene, PCR primers were designed and used to amplify the TPS genes from nine other seaweed species. Sequences of the nine obtained TPS genes were deposited in GenBank (NCBI). All 10 TPS genes encoded peptides of 908 amino acids and the sequences were highly conserved both in nucleotide composition (>94%) and in amino acid composition (>96%). Unlike the TPS genes from some other plants, there was no intron in any of the 10 isolated seaweed TPS genes.

Chaetopyranin, a benzaldehyde derivative, and other related metabolites from Chaetomium globosum, an endophytic fungus derived from the marine red alga Polysiphonia urceolata

Cultivation of the endophytic fungus Chaetomium globosum, which was isolated from the inner tissue of the marine red alga Polysiphonia urceolata, resulted in the isolation of chaetopyranin (1), a new benzaldehyde secondary metabolite. Ten known compounds were also isolated, including two benzaldehyde congeners, 2-(2 ',3-epoxy-1 ',3 '-heptadienyl)-6-hydroxy- 5-(3-methyl-2-butenyl) benzaldehyde (2) and isotetrahydroauroglaucin (3), two anthraquinone derivatives, erythroglaucin (4) and parietin (5), five asperentin derivatives including asperentin ( 6, also known as cladosporin), 5 '-hydroxy-asperentin-8-methylether (7), asperentin-8-methyl ether (8), 4 '-hydroxyasperentin (9), and 5 '-hydroxyasperentin (10), and the prenylated diketopiperazine congener neoechinulin A (11). The structures of these compounds were determined on the basis of their spectroscopic data analysis (H-1, C-13, H-1-H-1 COSY, HMQC, and HMBC NMR, as well as low- and high-resolution mass experiments). To our knowledge, compound 1 represents the first example of a 2H-benzopyran derivative of marine algal-derived fungi as well as of the fungal genus Chaetomium. Each isolate was tested for its DPPH (1,1-diphenyl-2-picrylhydrazyl) radical-scavenging property. Compounds 1-4 were found to have moderate activity. Chaetopyranin (1) also exhibited moderate to weak cytotoxic activity toward several tumor cell lines.

Amorphane sesquiterpenes from a marine Streptomyces sp.

The chemical investigation of the crude extract of the marine-derived Streptomyces sp. M491 yielded three new sesquiterpenes, namely, 10 alpha,11-dihydroxyamorph-4-ene (4), 10 alpha,15-dihydroxyamorph-4-en-3-one (6), and 5 alpha,10 alpha,11-trihydroxyamorphan-3-one (7). In addition, the known compounds 10 alpha-hydroxyamorph-4-en-3-one (2), o-hydroxyacetanilide, genistein, prunetin, and indole-3-carbaldehyde and the macrolide antibiotic chalcomycin A were identified. The structures were determined on the basis of spectroscopic analysis, especially 1D and 2D NMR data. This is the first report of these sesquiterpenes from bacteria.

Natural bromophenols from the marine red alga Polysiphonia urceolata (Rhodomelaceae): Structural elucidation and DPPH radical-scavenging activity

Three new natural occurring bromophenols, 3-(3-bromo-4,5-dihydroxyphenyl)-2-(3,5-dibromo-4-hydroxyphenyl)propionic acid (1), (E)-4-(3-bromo-4,5-dihydroxyphenyl)-but-3-en-2-one (2), and (3,5-dibromo-4-hydroxyphenyl) acetic acid butyl ester (3), together with one known bromophenol, 1,2-bis(3-bromo-4,5-dihydroxyphenyl)ethane (4), were isolated and identified from the marine red alga Polysiphonia urceolata. The structures of these compounds were elucidated by extensive analysis of ID and 2D NMR and IR spectra and MS data. Each of the isolated compounds was evaluated for scavenging alpha,alpha-diphenyl-beta-picrylhydrazyl (DPPH) radical activity and all of them exhibited significant activity with IC50 values ranging from 9.67 to 21.90 mu M, compared to the positive control, a well-known antioxidant butylated hydroxytoluene (BHT), with IC50 83.84 mu M. (C) 2007 Elsevier Ltd. All rights reserved.

5,7-Dihydroxy-5,6,7,8-tetrahydro-1H-azocin-2-one from a marine-derived Streptomyces sp.

In the course of a screening program, we have isolated the new natural product, 5,7-dihydroxy-5,6,7,8-tetrahydroazocin-2(IH)-one (1), from the staurosporine producing marine-derived Streptomyces sp. strain QD518. Here we report the isolation and structure elucidation of 1 and the artifacts 3 and 4 resulting from I by acid catalyzed intra- and inter-molecular reactions.

台风海面风场的动力分析、四维同化及数值试验

台风是最具破坏性的海洋大气系统。台风及其引起的沿海强风暴潮和海上巨浪不仅给沿海地区人民的生命财产造成严重的损失，而且对海上交通运输、军事活动、海洋工程和渔业都带来严重影响。准确的台风海面风场是获得比较真实的海浪、风暴潮等海洋现象的关键所在。由于不准确的海面初始场和台风海面风场数值模式中物理过程不完善等问题，模拟预报台风海面风场的精度达不到要求，极大的影响了海浪、风暴潮等海洋过程的模拟预报精度。因此获得准确真实的台风海面风场不仅对国民经济的顺利健康发展起到至关重要的作用，而且会很好地促进海浪、风暴湖等过程的研究。中尺度大气数值模式MM5在灾害性天气的预报研究方面具有重要的地位，并在暴雨研究方面取得了成功。在本论文中，我们结合气象工作者和海洋学者在台风研究中的不同侧重点，耦合自由大气和边界层过程，考察海气相互作用对台风海面风场的作用，首次将MM5应用于台风海面风场的研究之中，这对台风海面风场的研究来说是一个新的起点。本论文在MM5中，将中国国家气象中心中期预报谱模式T63／T106分析和预报场与常规地面和探空观测资料相结合，合理调整模式参数(海面粗糙度等参数)，建立了一套适用于中国区域的台风海面风场的模拟、预报系统。本论文利用改造过的中尺度大气数值模式MM5对两个台风个例：9608号台风(HERB)和9711号台风(WINNIE)进行数值试验。对海面风场而言，海气热通量交换对海面风场发挥着重要作用。因此本论文研究海面热量通量交换对9608号台风的强度和中心位置的影响，这也是以前国内台风数值模式中疏于考虑的方面。最后将模式模拟风场用于波浪的模拟研究之中，考察模拟海面风场在海洋环境研究中应用的有效性；并与目前国内较先进的LAGFD-WIN海面动力风场模式对比，检验MM5在台风海面风场研究中的性能。研究结果表明，MM5较好的反映出台风特性，并且优于LAGFD-WIN海面动力风场模式结果。在考察台风不稳定扰动特征时，我们区别于以往的本征值方法，利用中尺度二维扰动模式，由MM5提供9711号台风数值试验结果作为扰动模式的初始场，从动力学角度研究台风过程的扰动特征。初始资料问题对台风模式的预报模拟精度来说是一个最大、最重要的问题。因此改善、弥补模式初始场所造成的不足是本研究论文的重点工作之一。目前，在国内关于MM5中的四维资料同化(FDDA)方案试验刚刚起步。在本论文中，我们成功的启动MM5的四维资料同化方案：分析逼近和观测逼近。我们改造模式，同时启动这两种逼近方法，充分发挥探空资料和地面观测资料各自的优越性，I探索不同尺度、不同类型的资料在台风海面风场的应用。尝试卫星高度计风场资料溶于MM5中的同化方案中，这是本研究论文的另一个创新之处。本文的主要结论是(1)对两个台风个例：9608号台风(HERB)和9711号台风(WINNIE)进行了控制试验(CNTL)研究，分析台风模拟过程的温度距平、海平面气压及海面风场分布特点。研究表明，两个台风过程分别在不同高度上具有暖中心结构；模拟出的两个台风环流都呈现出台风的非对称及涡旋型态，模拟出的台风强度令人满意。对移动路径来说，对9608号台风过程，12h模拟台风路径误差为1.3个纬度，0.7个经度，而24h的模拟误差则为0.4个纬度，0.2个纬度；而对于9711号台风过程，其12h模拟台风路径误差为1.2个纬度，1.6个经度；24h路径误差为1.9个纬度，1．5个经度；36h模拟路径误差为3.2个纬度，2.8个经度。我们认为，由于9711号台风过程不准确的初始场，9711号台风模拟路径精度逊色于9608号台风过程的结果。(2)9608号台风过程中感热通量和潜热通量交换，在台风中心附近，热通量较小，但在台风周围，存在热通量的高值压，随着台风强度的减弱，热量通量交换也随之减小。在海面上始终是海水给大气提供热量。海面潜热通量总为正通量，并且都大于相应时刻的感热通量，表明水汽通量对台风系统比感热通量更重要。在分析热通量在不同下垫面演变特征时发现，在下午2h左右，在水陆交界处的次之，上最大，陆地上最小。感热通量在陆地下垫面上最大，其峰值出现而在水域上的最小，对于潜热通量则是水域(3)应用9608号台风的模拟海面风场到海浪的数值模拟研究中，发现由于台风海面风场分布的不对称性(在台风前进方向的右侧风速最大)，也因此造成了海浪有效波高分布的不对称性，同时在台风影响的右前方也传播得较远。随着台风海面风场减弱，风浪能量也逐渐消耗，有效波高也逐渐降低。(4)在台风发展的动力学特征研究方面，首先从不稳定扰动理论角度出发，讨论了台风发展的条件，得到了和天气学分析的台风形成发展条件一致的判据；在台风不稳定扰动的数值试验方面，针对9711号台风过程进行了数值试验，数值试验结果表明：扰动环流型以倾斜的扰动特征出现，并略向西倾斜，这是发展型的扰动型态；促使中尺度扰动发展和维持的能源主要来自于基本流场的有效位能和扰动场的有效位能。(5)利用标准探空资料和卫星高度计风场资料，在MM5中对9608号台风进行了七个试验：一个控制试验，三个分析逼近试验(AW，AWTQ，ATQ)，两个观测逼近试验(IWT，IW)和一个同时进行分析和观测逼近的试验(AWTQ+IWT)。七个试验中海平面气压场都形成了闭合低压中心，海面风场具有台风的气旋型态，再次证明MM5对台风的模拟能力；在定量的描述上，AWTQ+IWT试验较好地模拟出台风的中心位置和强度。因此联合有相对好的垂直分辨率的探空资料以及相对于探空资料有好的时间和水平分辨率的地面资料，能有效地提高台风海面风场的模拟预报精度。由于没有同化SLP的观测资料到模式中，SLP成为确定FDDA有效程度的有力手段。我们发现同时同化风场和质量场(温度场和湿度场)的试验AWTQ对风场和质量场均有一致的正面影响；对由强烈动力作用和大尺度强迫的台风过程，风场优于质量场。试验AWTQ，AW和ATQ的结果表明在风场中只有非常少的质量场诱导信息。试验ATQ，IWT对风场，海平面气压场具有负面影响。而利用包含常规气象观测资料无法拥有的海面风场信息的高度计风场资料，仅进行风场同化的IW试验，对海面气压场有非常好的效果。结果表明而AW，AWTQ，IW，AWTQ+IWT在24h模拟期间，则对SLP的平均RMS有明显的减小，分别约为3％，9％，12％和8％。