硫酸盐还原菌和极化电位对海洋结构用钢在海泥中应力腐蚀开裂敏感性的影响

海洋设施长期处于恶劣的腐蚀环境中，如不加以防护，一旦发生应力腐蚀开裂（SCC），损失就会极为惨重。海底泥土区环境十分重要，因为管线和平台桩腿等都埋在海底泥中。海底泥中硫酸盐还原菌（SRB）十分活跃，而且为了防止腐蚀，海泥中的设施无一例外地采取了阴极保护，相当于设施处在长期稳定的充氢状态。因此非常有必要研究海泥中的活性SRB和极化电位对海洋结构用钢在海泥中的氢渗透行为和SCC敏感性造成的影响，弄清SCC发生和发展的过程以便采取相应的措施减缓或防止SCC。 本文通过慢应变速率拉伸实验（SSRT）、电化学阻抗谱（EIS）技术、动电位扫描极化曲线测定实验和氢渗透实验等研究了海泥中SRB和极化电位对16Mn钢和管线钢X56（API X56）的SCC敏感性造成的影响。 从渤海海泥中富集得到SRB菌种，并做出了SRB在海泥中的生长曲线；在荧光显微镜下观察SRB为弧状，可以归为脱硫弧菌属，为革兰氏阴性菌；海泥中活性SRB数量与硫电位等主要腐蚀环境因子具有一定的对应关系。 SSRT结果表明，施加阴极极化电位可以使试样断裂脆性特征明显，SCC敏感性增大；海泥中活性SRB浓度越高，断裂脆性特征越明显，SCC敏感性越大。在含SRB海泥中或阴极极化电位条件下，两种钢都容易发生SCC，氢脆（HIC）起主要作用。 随着浸泡天数的增加，试样在灭菌海泥中的Rp一直增大；在含SRB海泥中Rp先增大，又变小，并呈现出显著的Warburg阻抗特征；在灭菌海泥中，两种试样在阳极电位范围内无SCC敏感区，而在阴极电位范围内有明显的SCC敏感区；在含SRB海泥中，在阳极电位范围和阴极电位范围内均有SCC敏感区；SRB代谢产物既有阳极去极化作用，又有阴极去极化作用，能使腐蚀电流密度增加。 活性SRB的存在能够促进试样在海泥中的氢渗透；在实海工程应用中，两种钢在含SRB海泥中的氢渗透电流密度大约是在不含SRB海泥中的3~4倍。阴极极化电位能够促进试样在灭菌海泥中的氢渗透。在含SRB海泥中对试样施加阴极极化电位，氢渗透电流密度大于不加阴极极化电位时的氢渗透电流密度，也大于在不含SRB的海泥中的氢渗透电流密度。

硫酸盐还原菌对海洋用钢腐蚀行为的影响及其控制

本文研究了海水和海泥环境中硫酸盐还原菌（SRB）对海洋用钢腐蚀行为的影响及控制，探讨了SRB影响下的腐蚀机制，腐蚀产物的形成及转化过程，并研究了含有SRB的海泥环境中阴极保护对钢腐蚀的影响。 从我国青岛胶州湾海底泥中富集培养出SRB，进行分子生物学分析确定了研究菌种为肠状菌属，并以荧光显微镜和透射电镜（TEM）观察了SRB的形貌特征。 以失重法、电偶腐蚀、交流阻抗（EIS）、电子探针（EPMA）、TEM等手段研究了海洋用钢在含有活性SRB的海泥和海水环境中，从最初的细菌附着到代谢产物导致腐蚀产物从氧化物到硫化物的转化，腐蚀产物的形貌及成分确定，对腐蚀由抑制到加速的过程。此外从钢基体与腐蚀产物界面角度对SRB点蚀的形成和扩展，以及单晶氧化铁立方体在SRB菌液中的生物矿化进行了探讨。 对埋在含有SRB海泥中的低碳钢的阴极保护的可靠性进行评价，重点研究活性细菌存在下不同阴极保护电位下的交流阻抗行为，并结合失重法测试不同电位下的腐蚀速度、MPN法细菌计数以得出保护电位、腐蚀速度以及细菌活性之间的关系。为达到有效的保护，-950mV (CSE)甚至更低的保护电位是需要的。较高保护电位下，细菌的生长活性与稳定性低于低电位。

硫酸盐还原菌对海洋腐蚀行为的影响

本文通过使用多参数水质分析仪、循环伏安法、电化学阻抗法等测试手段研究了硫酸盐还原菌生长过程中硫酸盐还原菌数量、环境参数和碳钢腐蚀行为三者之间的关系；建立了一种有效的快速检测硫酸盐还原菌数量的方法并研究了其检测的机制；研究了硫酸盐还原菌对阴极氧还原反应的影响。 研究发现，硫酸盐还原菌生长过程对介质化学状态影响主要为在硫酸盐还原菌的新陈代谢过程作用下，硫离子浓度在增殖期快速增加，并在衰亡期和残余期保持不变，体系的还原性也与硫离子浓度同步变化。该介质中碳钢腐蚀行为与活性硫酸盐还原菌并无直接关系，主要取决于体系氧化还原性能。即在硫酸盐还原菌增殖期增强了阳极过程与腐蚀速度，并在硫酸盐还原菌衰亡期和残余期保持不变。 采用测定银电极的电极电位的方法可以检测体系中硫酸盐还原菌的数量，检测范围为50~10000ml-1，检测时间为2~3分钟。硫酸盐还原菌的吸附及其代谢生成硫离子的过程是导致银电极电位负移的原因。 在氧气饱和的3.5% NaCl溶液中，玻碳电极的阴极氧还原反应包括氧气一电子还原为超氧离子、氧气二电子还原为过氧化氢以及过氧化氢二电子还原为水分子三个步骤。硫酸盐还原菌催化了第一步和第二步反应中间产物超氧离子和过氧化氢的分解，从而使得阴极氧还原反应电流加大。

氯离子和硫酸盐还原菌对Q235钢溶解氧还原反应的影响

在海水环境中，溶解氧阴极还原反应是钢铁材料腐蚀的主要因素之一，海水中的氯离子（Cl−）和硫酸盐还原菌（SRB）可能对溶解氧还原反应发生作用从而影响钢铁材料的腐蚀行为。本文以海洋工程材料Q235钢作为研究对象，通过循环伏安法、电化学阻抗谱、旋转圆盘电极和旋转圆盘-圆环电极线性扫描伏安法等电化学方法，研究了Cl−和硫酸盐还原菌对Q235钢电极表面溶解氧还原反应的影响，并对其影响机制进行了探讨。 研究表明：Q235钢在模拟混凝土孔隙液中电极表面氧化物的还原反应和溶解氧的还原反应同时进行；溶解氧还原反应在阴极反应电位范围内最初为混合过程控制的二电子反应，电位较负时为扩散过程控制的四电子反应。当在0.02 M Ca(OH)2溶液中加入Cl−时，随着Cl−浓度的增加，溶液电阻减小，溶解氧还原反应峰电位逐渐正移，即溶解氧还原反应的过电位减小；同时随着氯离子浓度的增加溶解氧还原反应速率逐渐减小。 由于硫酸盐还原菌在电极表面形成的生物膜阻碍了溶解氧到达电极表面，使得溶解氧还原反应与无菌时相比在一定程度上受到抑制，溶解氧还原反应速率降低；同时由于硫酸盐还原菌形成生物膜的作用，使得溶解氧还原机理也发生了改变，在没有硫酸盐还原菌时溶解氧还原以四电子还原为主，当硫酸盐还原菌数量较少时，溶解氧还原反应以二电子反应主，当硫酸盐还原菌数量较多时转为一电子反应为主。

Bromophenols coupled with methyl gamma-ureidobutyrate and bromophenol sulfates from the red alga Rhodomela confervoides

Four new bromophenols C-N coupled with methyl gamma-ureidobutyrate (1-4), a phenylethanol bromophenol (5), and three phenylethanol sulfate bromophenols (6-8) have been isolated from polar fractions of an ethanolic extract of the red alga Rhodomela confervoides. On the basis of spectroscopic evidence including HRMS and 2D NMR data, the structures of the new compounds were determined as methyl N'-(2,3-dibromo-4,5-dihydroxybenzyl)-gamma-ureidobutyrate (1), methyl N,N'-bis(2,3-dibromo-4,5-dihydroxybenzyl)-gamma-ureidobutyrate (2), methyl N'-[3-bromo-2-(2,3-dibromo-4,5-dihydroxybenzyl)-4,5-dihydroxybenzyl]-gamma-ureidobutyrate (3), methyl N'-(2,3-dibromo-4,5-dihydroxybenzyl)-A7-[3-bromo2-(2,3-dibromo-4,5-dihydroxybenzyl)-4,5-dihydroxybenzyl]-gamma-ureidobutyrate (4), 2,3-dibromo-4,5-dihydroxyphenylethanol (5), 2,3-dibromo-4,5-dihydroxyphenylethanol Sulfate (6), 3-bromo-4,5-dihydroxyphenylethanol sulfate (7), and 3-bromo2-(2,3-dibromo-4,5-dihydroxybenzyl)-4,5-dihydroxyphenylethanol sulfate (8). The cytotoxicity of all compounds was evaluated against several human cancer cell lines including human colon cancer (HCT-8), hepatoma (Bel7402), stomach cancer (BGC-823), lung adenocarcinoma (A549), and human ovarian cancer (A2780). Among them, the phenylethanol and the phenylethanol sulfate bromophenols (5-8) showed moderate cytotoxicity against all tested cell lines.

Antimicrobial activity of hydroxylbenzenesulfonailides derivatives of chitosan, chitosan sulfates and carboxymethyl chitosan

Chitosan, carboxymethyl chitosan (CIVICS) and chitosan sulfates (CSS) with different molecular weight were modified by reacting with 4-hydroxyl-5-chloride-1,3-benzene-disulfo-chloride or 2-hydroxyl-5-chloride-1,3 -benzene-disulfo-chloride to give 12 kinds of new hydroxylbenzenesulfonailides derivatives of them. The preparation conditions of the derivatives were discussed in this paper, and their structures were characterized by FT-IR and C-13 NMR spectroscopy. The solubility of the derivatives was measured in the experiment. In addition, their antimicrobial activities against four bacteria and five crop-threatening pathogenic fungi were tested in the experiment. Besides, the rule and mechanism of their antibacterial activities were discussed in this paper. (C) 2009 Published by Elsevier B.V.

Relevance of molecular weight of chitosan and its derivatives and their antioxidant activities in vitro

The antioxidant potency of different molecular weight (DMW) chitosan and sulfated chitosan derivatives was investigated employing various established in vitro systems, such as superoxide (O-2(.-))/hydroxyl ((OH)-O-.) radicals scavenging, reducing power, iron ion chelating. As expected, we obtained several satisfying results, as follows: Firstly, low molecular weight chitosan had stronger scavenging effect on O-2(.-) and (OH)-O-. than high molecular weight chitosan. For example the O-2(.-) scavenging activity of low molecular weight chitosan (9 kDa) and high molecular weight chitosan (760 kDa) were 85.86 % and 35.50 % at 1.6 mg/mL, respectively. Secondly, comparing with DMW chitosan, DMW sulfated chitosans had the stronger inhibition effect on 0(2)(.-). At 0.05 mg/mL, the scavenging activity on O-2(.-) reached 86.26 %, for low molecular weight chitosan sulfate (9 kDa), but that of low molecular weight chitosan (9 kDa) was 85.86 % at 1.6 mg/mL. As concerning chitosan and sulfated chitosan of the same molecular weight, scavenging activities of sulfated chitosan on superoxide and hydroxyl radicals were more pronounced than that of chitosan. Thirdly, low molecular weight chitosan sulfate had more effective scavenging activity on 02 and (OH)-O-. than that of high molecular weight chitosan sulfate. Fourthly, DMW chitosans and sulfated chitosans were efficient in the reducing power, especially LCTS. Their orders were found to be LCTS > CTS4 > HCTS > CTS3 > CTS2 > CTS1 > CTS. Fifthly, CTS4 showed more considerable ferrous ion-chelating potency than others. Finally, the scavenging rate and reducing power of DMW chitosan and sulfated derivatives increased with their increasing concentration. Moreover, change of DMW sulfated chitosans was the most pronounced within the experimental concentration. However, chelating effect of DMW chitosans were not concentration dependent except for CTS4 and CTS1. (C) 2004 Elsevier Ltd. All rights reserved.

Chemical characteristics of a polysaccharide from Porphyra capensis (Rhodophyta)

The structure of a polysaccharide from the red seaweed, Porphyra capensis, growing along the coast of Namibia and South Africa was investigated. Algae growing at different sites and collected at different times gave a polysaccharide extract with similar chemical components. FTIR and NMR spectral analysis showed that the polysaccharide from P. capensis had a typical porphyran structure. It has the linear backbone of alternating 3-linked beta-D-galactose and 4-linked alpha-L-galactose-6-sulfate or 3,6-anhydro-alpha- L-galactose units. The ratio of alpha-L-galactose-6-sulfate and the 3,6-anhydrogalactose is 121, as reflected by a H-1 NMR spectrum. A high degree of methylation occurred at the C-6 position of the D-galactose units. The degree of methylation was 0.64 for the D-galactose residues. (C) 2005 Elsevier Ltd. All rights reserved.

The structure of a sulfated galactan from Porphyra haitanensis and its in vivo antioxidant activity

The sulfated galactan fraction F1 isolated from the red seaweed, Porphyra haitanensis, showed typical porphyran structure. It has a linear backbone of alternating 3-linked beta-D-galactosyl units and 4-linked alpha-L-galactosyl 6-sulfate and 3,6-anhydro-alpha-L-galactosyl units. The L-residues are mainly composed of alpha-L-galactosyl 6-sulfate units, and the 3,6-anhydrogalactosyl units are minor. Partial methylation occurred at the C-6 position of the D-galactosyl units and at the C-2 position of the 3,6-anhydro-alpha-L-galactosyl units. Intraperitoneal administration of F1 significantly decreased the lipid peroxidation in aging mice. F1 treatment increased the total antioxidant capacity and the activity of superoxide dismutase (SOD) and glutathione peroxidase (GSH-Px) in aging mice. The results indicated that F1 had significant in vivo antioxidant activity. (C) 2003 Elsevier Ltd. All rights reserved.

Polysaccharides from Ulva pertusa (Chlorophyta) and preliminary studies on their antihyperlipidemia activity

Polysaccharides from Ulva pertusa were isolated and prepared by extraction in hot water and precipitation by ethanol. The water-soluble polysaccharides were chemically well defined, containing 47.0% total carbohydrate, 23.2% uronic acids, 17.1% sulfate groups, 1.0% N and 29.9% ash. Gas chromatography analysis demonstrated that the neutral sugars were mainly composed of rhamnose, xylose and glucose and smaller amounts of mannose, galactose and arabinose. The FTIR and C-13-NMR spectra indicated that basic repeating units of the polysaccharides were (beta-D-GlcpA-(1->4)-alpha-L-Rhap 3S) and (alpha-L-IdopA-(1->4)-alpha-L-Rhap 3S). Fifty ICR mice were used to study the effect of water-soluble polysaccharides from Ulva pertusa on the level of plasma lipids, with inositol niacinate as positive control. The results indicated that the polysaccharides significantly lowered the contents of plasma total cholesterol, low-density lipoprotein cholesterol, triglyceride and markedly increased the contents of serum high-density lipoprotein cholesterol, compared with the hyperlipidemia control group (p<0.01). Moreover, administration of polysaccharides significantly decreased the atherogenic index. The present results suggest that the polysaccharides from Ulva pertusa have great potential for preventing ischemic cardiovascular and cerebrovascular diseases.

Antioxidant activities of sulfated polysaccharide fractions from Porphyra haitanesis

Three sulfated polysaccharide fractions (F1, F2, and F3) were isolated from Porphyra haitanesis, an important economic alga in China, through anion-exchange column chromatography and their in vitro antioxidant activities were investigated in this study. Galactose was the main sugar unit of the three fractions. The analytical results indicated that polysaccharide fractions from P. haitanesis had similar chemical components to porphyran from other species, but differed in their high sulfate content. The sulfate content of F1, F2 and F3 was 17.4%, 20.5% and 33.5% respectively. All three polysaccharide fractions showed antioxidant activities. They had strong scavenging effect on superoxide radical, and much weaker effect on hydroxyl free radical. Lipid peroxide in rat liver microsome was significantly inhibited, and H2O2 induced hemolysis of rat erythrocyte was partly inhibited by F1, F2 and F3. Among them, F3 showed strongest scavenging effect on superoxide radical; F2 had strongest effect on hydroxyl radical and lipid peroxide.

Biosorption of copper(II) from aqueous solutions by green alga Cladophora fascicularis

Biosorption is an effective means of removal of heavy metals from wastewater. In this work the biosorption behavior of Cladophora fascicularis was investigated as a function of pH, amount of biosorbent, initial Cu2+ concentration, temperature, and co-existing ions. Adsorption equilibria were well described by Langmuir isotherm models. The enthalpy change for the biosorption process was found to be 6.86 kJ mol(-1) by use of the Langmuir constant b. The biosorption process was found to be rapid in the first 30 min. The presence of co-existing cations such as Na+, K+, Mg2+, and Ca2+ and anions such as chloride, nitrate, sulfate, and acetate did not significantly affect uptake of Cu2+ whereas EDTA substantially affected adsorption of the metal. When experiments were performed with different desorbents the results indicated that EDTA was an efficient desorbent for the recovery of Cu2+ from biomass. IR spectral analysis suggested amido or hydroxy, C=O, and C-O could combine strongly with Cu2+.

Study on extraction of agaropectin from Gelidium amansii and its anticoagulant activity

Gelidium amansii agar was fractionated on DEAE-cellulose and four fractions were obtained sequentially. The yields of 1.0 mol/L NaCl fraction and 2.5 mol/L NaCl fraction were 2.80% and 2.03%. They are highly sulfated agar, and named as agaropectin with sulfate content being 22.8% and 32.5%, respectively. The anticoagulant experiment results show that agaropectin could effectively prolong the coagulation time in a dose-dependent manner in vitro. Agaropection could be absorbed and effectively prolong the plasma coagulation time in vivo. After intragastric administration at the doses of 100, 200, and 400 mg/kg.d in rats for 15 days, TT (thrombin time), CT (coagulation time), PT (prothrombin time), and APTT (activated partial thromboplastin time) could be effectively prolonged and the plasma Fib level could be significantly lowered.

Antioxidant activity of sulfated polysaccharide fractions extracted from Laminaria japonica

Fucoidan, a group of sulfated heteropolysaccharide, was extracted from Laminaria japonica, an important economic alga species in China. Three sulfated polysaccharide fractions (F1, F2, and F3) were successfully isolated through anion-exchange column chromatography and had their antioxidant activities investigated employing various established in vitro systems, including superoxide and hydroxyl radical scavenging activity, chelating ability, and reducing power. Chemical analysis suggested that F1 and F3 were heteropolysaccharide in which galactose was the major component, while F2 was a typical fucoidan. All fractions possessed considerable antioxidant activity, and F1, F2 and F3 had stronger antioxidant ability than fucoidan in certain tests. The correlation between the sulfate content and scavenging superoxide radical ability was positive. Available data obtained with in vitro models suggested that the ratio of sulfate content/fucose was an effective indicator to antioxidant activity of the samples. (C) 2007 Elsevier B.V. All rights reserved.

Prediction of marine sediment corrosion by fuzzy clustering analysis

Along with the development of marine industries, especially marine petroleum exploitation, more and more pipelines are buried in the marine sediment. It is necessary and useful to know the corrosion environment and corrosiveness of marine sediment. In this paper, field corrosion environmental factors were investigated in Liaodong Bay marine sediment containing sulfate-reducing bacteria (SRB) and corrosion rate of steel in the partly sediment specimens were determined by the transplanting burying method. Based on the data, the fuzzy clustering analysis (FCA) was applied to evaluate and predict the corrosiveness of marine sediment. On that basis, the influence factors of corrosion damage were discussed.