ELECTROCHEMICAL STUDY OF ISOPOLY AND HETEROPOLY OXOMETALLATE FILM MODIFIED MICROELECTRODES .5. PREPARATION AND ELECTROCHEMICAL-BEHAVIOR OF A 2/18-MOLYBDODIPHOSPHATE ANION MONOLAYER MODIFIED ELECTRODE

In this paper a carbon fibre (CF) microelectrode modified with the 2:18-molybdodiphosphate anion by simple adsorption is described and its electrochemical behaviour is reported. The 2:18-molybdodiphosphate anion (alpha-P2Mo18O626-), which is a Dawson structure, undergoes five successive multielectron reductions in acidic solution. The first three redox waves correspond to the two-electron process, and the last two waves are four-electron and six-electron processes respectively. On the basis of the experimental results it is shown that the electrode process of alpha-P2Mo18O626- on the CF electrode in acidic solution is simultaneously controlled by the diffusion and adsorption of alpha-P2Mo18O626- anions. When the concentration of the alpha-P2Mo18O626- in the solution is reduced, the electrode process mainly exhibits non-diffusion-controlled behaviour, and the diffusion-limited process takes over as the concentration of alpha-P2Mo18O626- becomes higher. The CF electrode modified with a thin film of alpha-P2Mo18O626- exhibits very good stability and redox behaviour in aqueous acidic solution. The alpha-P2Mo18O626- is reduced to heteropoly blue, with an accompanying protonation process. The addition of more than six electrons to the alpha-P2Mo18O626- anion in an aqueous solution does not result in its decomposition. The result obtained is not the same as that reported previously.

酞菁铜衍生物LB膜/N-si光伏电池的研究

报道了采用新型酞菁铜衍生物:三特戊基苯氧基对羧基苯氧基酞菁铜(ttc～CuPc)制备LB膜ttc-CuPc/硬脂酸(C_(18))/n-Si光伏电池的结果。测量了电池的光照I—V、暗I—V和光谱响应等特性。在辐照度为100mW/cm~2AMC混合光照射下电池的I_(sc)为240μA/cm~2,V_(oc)为0.33V,观察到反常二极管整流效应并进行了讨论。

聚合物载体-稀土金属络合物的研究——Ⅶ.聚合物载体-金属络合物的微观结构与络合物催化聚合丁二烯活性的关系

众所周知,在烯烃络合催化聚合中,过渡金属配位体的种类是影响催化剂活性的重要因素之一.用高分子代替小分子作为配位体,影响催化剂的活性因素则由原来单一的固定因素变成多重的可变因素.高分子金属络合物的结构因素,如金属含量、功能团含量,金属与功能团的含量比都将直接影响催化活性.本文从聚合物的微观结构角度,研究了作为载体的苯乙烯-丙烯酸共聚物中单体单元的序列分布及其与催化活性的关系.

二甲基乙烯基乙氧基硅烷等离子体聚合

在外部电极电容耦合式辉光放电装置中进行了二甲基乙烯基乙氧基硅烷(VDMES)的等离子体聚合,考察了压力、功率以及基片距离对聚合速率的影响。用红外光谱和X射线光电子能谱(XPS)等方法研究了聚合物的结构,并研究了聚合物的热稳定性及表面性能。

多晶富镉Hg_(1-x)Cd_xTe的电沉积及Hg_(0.09)Cd_(0.91)Te薄膜的光电化学行为

本文研究了在酸性CdSO_4+HTeO_2~+6HgCl_2 电解液中多晶富镉Hg_(1-x),Cd_(?),Te(x>0.5)的电沉积过程,实现了三种离子在同一电位下共沉积的技术。对在钛基底上沉积出的薄膜进行XRD,SEM和EDAX分析,结果表明薄膜为闪锌矿型的多晶结构,分布均匀连续。考察了(1—x)=0.09时多晶薄膜在多硫氧化还原电对液中的光电化学行为,光强为100mW/cm~2时,短路光电流I_(sc)=1.88mA/cm~2,开路光电压V_(oc)=0.25V,填充因子F·F=0.22。由光电化学光谱所确定出的禁带宽度E_g=1.26eV,Mott-schottky曲线给出了电极的平带电位φfb为—1.26V(vs.SCE),从而得到开路光电压V_(oc)可能达到的最大值为0.49V。因此,多晶富镉Hg_(1-x)Cd_xTe薄膜是一种很有潜力的光活性电极材料。

立规聚甲基丙烯酸热表征研究

本文对不同立构的聚甲基丙烯酸(PMAA)进行了热表征。实验结果表明,在30℃～200℃内未出现玻璃化转变。间同PMAA分别在-245℃和-280℃发生脱水反应和脱羧,而全同PMAA只在-185℃观察到脱水反应。这种热稳定性的明显差别与不同立构PMAA链上相邻羧酸距离有关。实验数据证实PMAA脱水反应为无规反应,服从一级动力学反应方程。脱水温度和间同立构含量成正比,脱水反应活化能间同PMAA比全同PMAA高～7Kcal/mol。

Cultivation of the brown alga Hizikia fusiformis (Harvey) Okamura: enhanced seedling production in tumbled culture

The reuse of holdfasts for regeneration of young seedlings or using wild juvenile plants as the seedling source has played the major role in commercial cultivation of the brown alga Hizikia fusiformis in East Asia over the past 20 years. The possibility of employing zygote-derived germlings for producing seedlings has been discussed in the literature, but has not yet become a reality. Three main obstacles have limited the use of zygotes as a main source of seedlings, (1) the dioecious nature of the algal life cycle which may lead to asynchronous male and female receptacle development and thus different timing of egg and spermatozoa expulsion, (2) the low attachment rate when using zygote-derived germlings with developed rhizoids from wild parental plants for seeding production, and (3) the problem of culturing young germlings in regions where water temperature is high in summer. In this investigation, shifting the timing of receptacle formation earlier than in nature was performed by tumbling the algae in a long-day tank (16-h light per day). Synchronization of egg and spermatozoa expulsion and thereafter fertilization were conducted in indoor tanks. Receptacle formation in constant long days could be shifted by 20 days earlier than in plants cultured on long lines in the open sea, or I month earlier than in plants growing on intertidal rocks. Synchronized expulsion of eggs and spermatozoon led to a high rate of fertilization. This was achieved by tumbling the male and female receptacle-bearing branchlets in the same tank at low density in high irradiance. In two independent trials, a total of 1,400,000 zygote-derived germlings were obtained from 620 g (fresh weight) female sporophytes. The germlings shed from the receptacles were at an identical developmental stage indicating high synchronization of expulsion of eggs and spermatozoon followed by fertilization. Approximately 63% ( +/-9.6%) of the germlings were shed from the receptacle between 16 and 24 It after fertilization and 20% ( +/-11.9%) remained on the receptacle for 3 days after fertilization. Germlings were seeded on string collectors before rhizoids started to elongate and the attachment efficiency was enhanced. Young seedlings reached 800 ( +/-50) mum in length in 25 days at 25 degreesC before they were transferred to open sea cultivation. These results provide the basis of a practical way of seedling production by use of zygote-derived germlings in the commercial cultivation of Hizikia fusiformis. (C) 2004 Elsevier B.V All rights reserved.

Construction of AFLP-based genetic linkage map for Zhikong scallop, Chlamys farreri Jones et Preston and mapping of sex-linked markers

Zhikong scallop (Chlamys farreri) is an economically important aquaculture species in China; however, frequent mass mortality seriously affects the development of its industry. Genetic linkage map is useful for genetic improvement and selective breeding of C. farreri. Linkage maps were constructed using an intraspecific F-1 cross and amplified fragment length polymorphism (AFLP) markers. Thirty-two selected AFLP primer combinations produced 545 AFLP markers that were polymorphic in either of the parents and segregated in the progeny. Of these segregating markers, 166 were mapped to 19 linkage groups of the female framework map, covering a total of 1503.9 cM, with an average marker spacing of 10.2 cM; and 197 markers were assigned to 20 linkage groups of the male map, covering a total of 1630.7 cM, with 9.2 cM per marker. A sex-linked marker was mapped on the female map with zero recombination and a LOD of 27.3. The genetic length of C farreri genome was estimated as 1889.0 cM for the female and 1995.9 cM for the male. The coverage of the framework map was calculated as 79.6% for the female and 81.7% for the male. When the triplets and doublets were considered, the observed length of the map was calculated as 1610.2 cM with coverage of 85.2% for the female, and 1880.5 cM with coverage of 94.2% for the male. The genetic maps presented here will serve as a basis for the construction of a high-resolution genetic map and mapping of economically important genes. (C) 2004 Published by Elsevier B.V.

Chemical species of iodine in some seaweeds II. Iodine-bound biological macromolecules

The distribution of iodine in various biological macromolecules in Sargassum kjellmanianum was studied using neutron activation analysis combined with chemical and biochemical separation techniques. The results indicate that iodine is mainly bound with protein, part of iodine with pigment and polyphenol, and little with polysaccharides, such as algin, fucoidan and cellulose. This result is significant for the mechanism of enriching iodine of algae and utilization of alga iodine.

Impact of difference accuracy on computational properties of vertical grids for a nonhydrostatic model

Starting from nonhydrostatic Boussinesq approximation equations, a general method is introduced to deduce the dispersion relationships. A comparative investigation is performed on inertia-gravity wave with horizontal lengths of 100, 10 and 1 km. These are examined using the second-order central difference scheme and the fourth-order compact difference scheme on vertical grids that are currently available from the perspectives of frequency, horizontal and vertical component of group velocity. These findings are compared to analytical solutions. The obtained results suggest that whether for the second-order central difference scheme or for the fourth-order compact difference scheme, Charny-Phillips and Lorenz ( L) grids are suitable for studying waves at the above-mentioned horizontal scales; the Lorenz time-staggered and Charny-Phillips time staggered (CPTS) grids are applicable only to the horizontal scales of less than 10 km, and N grid ( unstaggered grid) is unsuitable for simulating waves at any horizontal scale. Furthermore, by using fourth-order compact difference scheme with higher difference precision, the errors of frequency and group velocity in horizontal and vertical directions produced on all vertical grids in describing the waves with horizontal lengths of 1, 10 and 100 km cannot inevitably be decreased. So in developing a numerical model, the higher-order finite difference scheme, like fourth-order compact difference scheme, should be avoided as much as possible, typically on L and CPTS grids, since it will not only take many efforts to design program but also make the calculated group velocity in horizontal and vertical directions even worse in accuracy.

Generation of internal and surface waves by seafloor movement in a two layer fluid system

Internal and surface waves generated by the deformations of the solid bed in a two layer fluid system of infinite lateral extent and uniform depth are investigated. An integral solution is developed for an arbitrary bed displacement on the basis of a linear approximation of the complete description of wave motion using a transform method (Laplace in time and Fourier in space) analogous to that used to study the generation of tsunamis by many researchers. The theoretical solutions are presented for three interesting specific deformations of the seafloor; the spatial variation of each seafloor displacement consists of a block section of the seafloor moving vertically either up or down while the time-displacement history of the block section is varied. The generation process and the profiles of the internal and surface waves for the case of the exponential bed movement are numerically illustrated, and the effects of the deformation parameters, densities and depths of the two layers on the solutions are discussed. As expected, the solutions derived from the present work include as special cases that obtained by Kervella et al. [Theor Comput Fluid Dyn 21:245-269, 2007] for tsunamis cased by an instantaneous seabed deformation and those presented by Hammack [J Fluid Mech 60:769-799, 1973] for the exponential and the half-sine bed displacements when the density of the upper fluid is taken as zero.

藻类有机物在富含粘土海洋沉积物中的氧化还原降解研究

研究海洋沉积有机物的早期成岩过程是海洋地球化学的重要内容，也是研究全球碳循环不可缺少的核心课题。本文通过模拟有机物在沉积物－海水界面的降解实验，研究了海洋藻类有机物在富含粘土沉积物中不同氧化还原条件下的降解过程及有机物稳定碳同位素比值的变化。通过为期245天的培养实验，我们分析测定了总有机碳（TOC）、脂肪酸、长链烷烃的含量随时间的变化以及总有机碳和单一脂肪酸化合物同位素组成的变化。结果表明粘土、沉积物氧化还原环境、微生物活动，化合物分子结构、有机物来源等是影响有机物降解的重要因素。藻类有机物在富含粘土沉积物中的降解是一个快速过程，其降解速率可以用简单的早期成岩公式（-dGt / dt = ∑kiGi）很好的描述。应用该模型计算了脂肪酸和长链烷烃的降解速率常数。其中脂肪酸的降解速率常数为0.011-0.119 d-1，低于已报道的用未添加粘土的海洋沉积物培养实验得到的速率常数值。该研究实验显示，粘土对沉积有机物有一定的吸附作用，从而对有机物的降解过程起到不同程度的保护作用。长链烷烃的降解速率常数比脂肪酸稍高，为0.013-0.158 d-1，该值与已报道的经水体降解后沉降到海洋沉积物中残余长链烷烃的降解速率常数相当。TOC，脂肪酸和长链烷烃的降解在氧化环境下比在还原环境下快。脂肪酸和长链烷烃的降解不仅受到环境因素的影响，其自身分子结构特征也是很重要的控制因素。脂肪酸化合物双键数目越多，降解的越快；长链烷烃的碳链越短，降解越快。沉积有机物的早期成岩过程对总有机碳及不同化合物的稳定碳同位素比值具有不同的影响。在245天的培养实验过程中，总有机碳稳定同位素比值（δ13C）有所降低，但变化范围不大且受环境影响较小。而几种主要脂肪酸的δ13C值有不同程度的变化趋势。14：0和16：1的δ13C值降低，18：1的δ13C值升高，而16：0和20：5的δ13C值基本保持不变。因此，在利用沉积物中的生物标志化合物碳稳定同位素研究有机物来源及古海洋生物地球化学过程时，应考虑到早期成岩作用对其同位素比值的影响。

扇贝丝氨酸蛋白酶抑制剂基因CfKZSPI及Aikunitz的克隆与重组表达

扇贝养殖是我国重要的海水养殖产业，然而自1997 年以来，养殖扇贝陆续爆发的大规模死亡，不但造成了巨大的经济损失，而且严重影响了该产业的健康发展。丝氨酸蛋白酶抑制因子及丝氨酸蛋白酶在无脊椎动物的免疫应答中起着核心作用，它们的协同作用直接导致外界病源入侵的信号转导和级联放大，并进一步激活一系列防御体系，如黑化反应、血液凝结和抗菌肽的合成等。因此，克隆扇贝参与免疫防御的丝氨酸蛋白酶抑制剂基因并对其功能进行研究，将有助于进一步研究扇贝的免疫防御机制，丰富和发展无脊椎动物免疫学的内容。 运用大规模EST技术和RACE技术从栉孔扇贝中克隆出一个Kazal型丝氨酸蛋白酶抑制剂基因，定名为CfKZSPI。该基因cDNA序列全长1788bp，其中5' 非编码区（Untranslated Region, UTR）为97 bp，3' UTR161 bp，有一个典型的多聚腺苷酸信号序列（AATAAA）和一个ploy A 尾巴，开放阅读框（Open Reading Frame, ORF）含有1530 bp，编码509 个氨基酸残基。对其推测氨基酸序列进行分析，发现其中包括22个氨基酸残基组成的信号肽序列和12个Kazal型丝氨酸蛋白酶抑制剂结构域。采用QRT-PCR（quantitative real time PCR）对鳗弧菌浸泡刺激后栉孔扇贝血淋巴中CfKZSPI 的 mRNA表达量进行了检测，发现其mRNA 的表达量在鳗弧菌刺激后3h明显上升，达到空白组的43.6倍；然后在6h时有所下降，为空白组的15.0倍；随着菌刺激时间的增长，CfKZSPI基因的 mRNA 表达量急剧增加，在刺激后8h，12h，24h分别达到空白组的174.1，207.8，675.4倍。统计分析发现3h（P=0.019<0.05）和12h（P=0.020<0.05）时，CfKZSPI基因mRNA表达量与空白组差异均显著。为了研究栉孔扇贝CfKZSPI的蛋白活性，将其第十二个结构域克隆到pET-32a（+）载体中，转化大肠杆菌Rosetta-gami（DE3）表达菌株，获得可溶性表达的蛋白rCfKZSPI-12，对其进行抑制蛋白酶活性的分析，发现其对胰蛋白酶有很强的抑制活性，而对凝血酶没有抑制活性。当rCfKZSPI-12与胰蛋白酶分子比率为1：1时，约90%的蛋白酶活性被抑制。运用狄更斯作图法研究rCfKZSPI-12对胰蛋白酶的抑制能力，结果发现其对胰蛋白酶的抑制常数为173 nmol L-1。 采用同样方法从海湾扇贝cDNA文库中克隆出一个Kunitz型丝氨酸蛋白酶抑制剂基因，定名为Aikunitz。该基因全长632 bp，其中5' UTR 为105 bp，3' UTR 为 245 bp，有一个典型的多聚腺苷酸信号序列（AATAAA）和一个ploy A 尾巴，ORF 含有282 bp，编码93 个氨基酸残基。推测的氨基酸序列N末端有一个20个氨基酸残基组成的信号肽序列，成熟蛋白包括一个Kunitz型丝氨酸蛋白酶抑制剂结构域。采用QRT-PCR对鳗弧菌和藤黄微球菌感染后海湾扇贝血淋巴中Aikunitz 的mRNA的表达量进行了检测，结果发现其在鳗弧菌刺激后3h到9h持续上升，9h时表达量为PBS对照组的4.49倍（P=0.008<0.05），然后开始下降，在72h时表达量为对照组的0.24倍（P=0.021<0.05）；而在藤黄微球菌刺激后3h到12h其表达量上升，其中6h时为空白组的5.95倍（P=0.0004<0.01）；12h以后迅速下降，其中24h的表达量为对照组的0.38倍（P=0.028<0.05）。将Aikunitz基因编码的成熟蛋白按照重组CfKZSPI-12的方法进行重组表达，并对重组蛋白进行抑制蛋白酶和抑菌活性分析。结果发现其对胰蛋白酶和弹性蛋白酶两种丝氨酸蛋白酶都没有抑制作用。抑菌实验同样发现，重组Aikunitz 对供试的革兰氏阳性菌藤黄微球菌和革兰氏阴性菌鳗弧菌和大肠杆菌都不显示明显抑菌活性。

高位虾池水色及其它环境因子变化对凡纳滨对虾生长的影响

本文研究了16口虾塘的饲料投喂量、水位、盐度、透明度、水温、pH、溶解氧浓度、NH3-N浓度、水色、对虾体长及浮游植物的种类和数量等水体理化因子和生物因子的变化。经过统计分析结果如下： 在养殖前4个月饲料的日平均投喂量基本上呈一个倒“U”型。即随着养殖时间的推移，饲料日平均投喂量逐渐增大，到养殖60 d左右，饲料日平均投喂量达到了最大值，然后进入一个平台期，平台期大约维持30 d左右，随后饲料日平均投喂量逐渐减少。在120 d~130 d饲料日平均投喂量降到最低点后又逐渐回升。 水位平均值变化趋势基本相同，均为前浅后深，即随着养殖时间的推移养殖水位平均值逐渐加深 。 盐度变化趋势基本相同，均为前低后高，即随着养殖时间的推移养殖水体盐度逐渐升高。 透明度的总体变化趋势为：早上透明度比下午大，前期透明度比后期大。 水温基本上是随着养殖时间的推移而逐渐下降。6:30的水温比17:30的水温低。且6:30水温与17:30水温基本上呈平行趋势。 pH变化的总体趋势为：前期较高，随着养殖时间的推移pH逐渐下降，到中期（90d左右）pH降到最低点，尔后又逐渐上升，略呈“V”字形。早上的pH比下午的低。且早上的pH与下午的pH基本上呈平行趋势，间或有较大波动。 6:30时溶解氧浓度的平均值随着养殖时间的推移而逐渐增高。17:30时溶解氧浓度的平均值在整个养殖过程中比较平稳。同时，17:30时溶解氧浓度的平均值高于6:30，养殖前期（前90d）这种趋势更明显。 NH3-N浓度的平均值随着养殖时间的推移而逐渐增高。在养殖后期NH3-N浓度的波动较大。同时，养殖过程中17:30时NH3-N浓度的平均值高于6:30。 6:30时出现9~21号水色，它们出现的比例分别为：9号占0.1%，10号占0.3%，11号占1.1%， 12号0.6%，13号1.5%，14号占3.7%，15号占7.1%，16号占17.5%，17号占22.0%，18号占15.9%，19号占13.7%，20号10.9%，21号占5.8%；17:30时出现11~21号水色，它们出现的比例分别为11号占0.1%， 12号占0.3%，13号占1.2%，14号占4.0%，15号占6.0%，16号占17.8%，17号占24.7%，18号占18.1%，19号占11.8%，20号占9.7%，21号5.7%。 在11种典型水色中共检出浮游植物67种。其中11号水色检出16种，优势种为诺马斜纹藻（占总数47.1%）和菱形海线藻（占总数29.8%）。12号水色共检出16种，优势种为原甲藻（占总数40.85%）和圆筛藻（占总数20.73%）。13号水色共检出16种，优势种为颤藻（占总数45.58%）。14号水色共检出18种，优势种为拟货币直链藻（占总数56.73%）和膝沟藻（占总数12.87%）。15号水色共检出18种，优势种为诺马斜纹藻（占总数64.76%）。16号水色共检出16种，优势种为拟货币直链藻（占总数69.93%）。17号水色共检出14种，优势种为诺马斜纹藻（占总数62.56%）和膝沟藻（占总数15.76%）。18号水色共检出21种，优势种为拟货币直链藻（占总数71.19%）。19号水色共检出18种，优势种为圆筛藻（占总数94.99%）。20号水色共检出18种，优势种为圆筛藻（占总数87.14%）。21号水色共检出15种，优势种为拟货币直链藻（占总数59.80%）和萎软几内亚藻（占总数17.57%）。 相关分析结果表明高位池理化因子中对水色的主要影响因素：17:30PH值、养殖生物量、17:30NH3-N、17:30 透明度、水交换量。 对体长的主要影响因素为 6:30溶解氧、水交换量、17：30水色、饲料投喂量、盐度、17:30透明度、17:30水温、6:30NH3-N。 对对虾本身生物学形状对体重的影响研究表明体长、头胸甲长、胸宽、额剑下缘刺数目对体重的通径系数达到显著水平，它们是直接影响体重的重要指标，其中体长对体重的直接影响（0.428**）最大，是影响体重的最主要因素，其次为头胸甲长（0.290**）和胸宽（0.245**），额剑下缘刺数对体重的直接影响（0.070*）较小；胸高与体重的相关程度很大（0.7923），但它与额剑上缘刺数对体重的直接影响都非常小，主要通过其他性状间接影响活体重，是影响体重的次要因素。