A STUDY ON CH5O+ IONS IN GAS PHASE CID EYPERIMENT AND QUANTUM CHEMISTRY CALCULATION

The structures of CH5O+ from two different reactions which are protonation of CH3OH from the above two pathways possess the same structures, CH3OH2+. The value of kinetic energy release for the metastable decomposition CH2OH3+-> CH2OH+ + H-2 determined from the experiment is in good agreement with that from theoretical calculations. The transition state of above reaction were disscussed.

CYCLIC VOLTAMMETRIC STUDY ON THE TRANSFER MECHANISM OF ALKALI-METAL IONS ACROSS LIQUID LIQUID INTERFACE FACILITATED BY TRITON X-100

The transfer behavior of alkali motal ions K~+ and Na~+ across the interfaces of water/nitrobenzene and water/1, 2-dichloroethane facilitated by Triton X-100 is investigated by cyclic voltammetry with four electrodes. The equations of interfacial half-wave potential derived in terms of the mechanism proposed isverified by the experimental data and consistent with the practical △_0~wφ_p-pM curves.

STUDY ON C2H62+ DOUBLY CHARGED IONS - EVIDENCE FOR THE EXISTENCE OF C2H62+ IN GAS-PHASE

Collision-Induced Dissociation (CID) or Collision Activation (CA) of ion involves high kinetic energy colliding with neutral gas molecules. In part of the ions, the translational energy is converted into excitation energy, Which may lead to subsequent ion decomposition. CID has developed into an important technique for elucidating the

A fibrinogen-related protein from bay scallop Argopecten irradians involved in innate immunity as pattern recognition receptor

The family of fibrinogen-related proteins (FREPs) is a group of proteins with fibrinogen-like domains. Many members of this family play important roles as pattern recognition receptors in innate immune responses. The cDNA of bay scallop Argopecten irradians FREP (designated as AiFREP) was cloned by rapid amplification of cDNA ends (RACE) method based on the expressed sequence tag (EST). The full-length cDNA of AiFREP was of 990 bp. The open reading frame encoded a polypeptide of 251 amino acids, including a signal sequence and a 213 amino acids fibrinogen-like domain. The fibrinogen-like domain of AiFREP was highly similar to those of mammalian ficolins and other FREPs. The temporal expression of AiFREP mRNA in hemolymph was examined by fluorescent quantitative real-time PCR. The mRNA level of scallops challenged by Listonella anguillarum was significantly up-regulated, peaked to 9.39-fold at 9 h after stimulation, then dropped back to 4.37-fold at 12 h, while there was no significant change in the Micrococcus luteus challenged group in all periods of treatment. The function of AiFREP was investigated by recombination and expression of the cDNA fragment encoding its mature peptide in Escherichia coli Rosetta gami (DE3). The recombinant AiFREP (rAiFREP) agglutinated chicken erythrocytes and human A, B, O-type erythrocytes. The agglutinating activities were calcium-dependent and could be inhibited by acetyl group-containing carbohydrates. rAiFREP also agglutinated Gram-negative bacteria E. coli JM109, L anguillarum and Gram-positive bacteria M. luteus in the presence of calcium ions. These results collectively suggested that AiFREP functions as a pattern recognition receptor in the immune response of bay scallop and contributed to nonself recognition in invertebrates, which would also provide clues for elucidating the evolution of the lectin pathway of the complement system. (C) 2008 Elsevier Ltd. All rights reserved.

羟基自由基降解琼胶及其产物的活性研究

琼胶是一种从石花菜等红藻中提取的，目前生产工艺和结构等方面研究比较成熟的海藻多糖，广泛应用于医药、仪器等行业。但是，海藻多糖因为具有分子量大，粘度大，溶解度较小的等特点，而使其应用范围受到限制。利用降解的手段对其进行修饰，降低分子量和粘度，改善溶解性，可以拓展其应用范围。并且根据文献报道，琼 胶寡糖具有一些特殊的生物活性，如抗氧化性，抗炎症等。因此，对琼胶降解的研究具有生要意义。本研究中，为了选择一种合适的降解方法，进行了几种水解方法的尝试，其中包括在不同湿度和酸度下盐酸水解，过氧化氢和醋酸催化水解，Fenton体系羟基自由基降解。对于酸水解和Fenton体系氧化还原降解方法，通过粘度法对反应的速度进行了比较，表明氧化还原降解反应中琼胶的粘度降低比较快，并且具有代表性和新意，确定为本实验的降解琼胶的方法并对氧化还原降解所得的产物进行了活性实验。通过模仿自然界普遍存在的氧化还原降解反应，利用Vc诱导的Fenton体系产生的羟基自由基氧化还原降解琼胶得到低分子量的琼胶。降解产物经过高速离心、60％乙醇沉淀，除去分子量比较大的降解产物和磷酸盐，得到可溶于60％乙醇的分子量估计小于3000的降争产物，其产率为85％。利用经Sephadex-G25凝胶色谱分离所香的不同分子量的级分进行分子量和α－葡萄糖苷酶抑制活性关系的实验。降解产物对α－葡萄糖苷酶的抑制率和各级分的浓度呈线性正相关，并且各级分的IC_(50)则随着分子量的降低而降低。另外，对所得的降解产物混合物进行了红外吸收光谱、质子去偶核磁共震碳谱和负离子基质辅助激光诱导－飞行时间质谱结构分析。结果表明，氧化还原降解反应的专一性差，在得到寡糖的同时，在光谱图中出现一些比较复杂的副产物的结构信息。最后，根据MTT法的原理，以有体皮肤成纤维细胞为材料，通过紫外线辐射产生自由基造成氧化损伤，研究降解产物对成纤维细胞的保护作用。当无紫外线辐射时，降解产物对成纤维细胞具有显著的促进生长增殖作用：当经UVa、UBb辐射时则可以显著地表现出对损伤的保护作用，并且这种促进生长和保护作用呈显著的量效关系，表明降解产物具有清除基自由基的作用。但是，因为氧化还原降解以应的机理尚不十分明的以及琼羟胶的特殊结构，使得反应的副产物很难预测，也就使得分离工作难以进行，所以，根据目前所得的信息，尚不能确定是降解产物的什么级分产生的以上两种生物活性。

海相碳酸盐－稀土元素共沉淀过程中的分异作用研究

本文主要运用稳定加液－反应系统对海水中方解石和文石形成时稀土元素的共沉淀现象进行了分析，研究了稀土元素在固-液体系中的迁移、转化和分配。进而在对其定量描述的前提下，研究了稀土元素共沉淀对各种反应条件的响应，并对共沉淀行为的机制进行了探讨。 本实验首先运用pH测试、高精度滴定分析等手段测定了实验中的一些基本参数，如[H+]、碱度和[Ca2+]，根据计算结果获得了各碳酸体系要素，并以此为基础建立了5℃、15℃和25℃及pCO2=0.003atm下海水中方解石或文石的沉淀动力学方程。实验结果表明： 1）在各条件下，方解石或文石的沉淀速率（R）和其在海水中过饱和度（Ω）存在很好的线性相关性，即海相碳酸盐的沉淀动力学方程可以通过下面的基本表达式来表示：LogR=k*Log(Ω-1)+b ； 2）过高的稀土元素浓度会对文石或方解石的沉淀产生抑制作用，进而对共沉淀过程中YREEs的分异和分馏产生一定的影响。相比方解石而言，文石的沉淀动力学过程承受稀土元素的干扰能力更强； 3）不同温度下得到的方解石或文石各自的沉淀动力学方程存在明显的差异，表明这一过程受热力学因素控制。相对于方解石而言，温度对文石的沉淀动力学的影响更为显著。 与前人研究不同的是，本实验中YREEs的浓度设定在非常低的范围内，从而避免了过高浓度YREEs对方解石或文石沉淀动力学过程的干扰。在最终的反应液中，各种实验条件非常接近自然环境。有关稀土元素的共沉淀行为主要得出以下定性或定量化结论： 1）YREEs在随方解石或文石的共沉淀过程中，均发生了强烈的分异作用。在方解石实验中，稀土元素的分异系数分布曲线呈凸状分布；而在文石实验中，稀土元素的分异系数随原子序数的增加逐渐减小，遵循镧系收缩的规律。总的来说，稀土元素，尤其轻稀土元素在文石中的分异作用要强于方解石。 2）无论是方解石还是文石，沉淀速率对YREEs的分异作用都有着明显的影响。在方解石中，YREEs的分异系数随沉淀速率的增加呈一致性递减趋势；而在文石中，其分异系数对文石沉淀速率有着截然不同的响应：轻稀土元素（La, Ce, Nd, Sm, Eu, Gd）的分异系数随文石沉淀速率的增加而下降，而重稀土元素（Ho, Y, Tm, Yb , Lu）的分异系数则随文石沉淀速率的增加呈上升趋势。 3）在方解石中YREEs的分异系数之间存在非常好的相互关系，表明这些元素是以成比例的方式参与共沉淀。整个谱系呈现中等强度的分馏，MREE相对于LREE和HREE要更为富集；在文石中由于沉淀速率的作用不同，只有Y、Ho、Yb、Lu等元素的分异系数之间有较好的相互关系。YREEs出现了差异性的强烈分馏，在新生成沉淀中轻稀土元素相对于重稀土元素强烈富集。 4）YREEs在溶液中和碳酸盐晶体表面的碳酸根配位形式对YREEs在共沉淀过程中的分异作用极为重要，YREEs在碳酸盐晶体表面的吸附是整个谱系发生分馏效应的关键环节。对于文石来讲，晶体中有效YREE离子和Ca离子半价大小之间的相近程度是其分馏效应的关键因素；而对于方解石来说，YREEs在方解石晶格中的安置就是其分馏效应的关键控制因子，但在晶格安置中起到关键作用的是YREEs和方解石中O原子之间离子键M-O的键长，而非离子半径。 5）综合YREEs在方解石中的分异作用和分馏效应，我们认为M2(CO3)3-CaCO3和MNa(CO3)2-CaCO3是最为可能的两种固体溶液形成模式。 最为重要的是，对比我们的实验结果与前人在灰岩、叠层石、微生物成因碳酸盐等方解石质载体中的研究成果，两者之间出现了非常好的一致性。我们认为方解石质载体将是重建古海水中稀土元素相关信息的重要工具。相比之下，文石质载体不适合作为类似的载体。

The electrochemical reduction reaction of dissolved oxygen on Q235 carbon steel in alkaline solution containing chloride ions

Cyclic voltammetry, electrochemical impedance spectroscopy, and rotating disk electrode voltammetry have been used to study the effect of chloride ions on the dissolved oxygen reduction reaction (ORR) on Q235 carbon steel electrode in a 0.02 M calcium hydroxide (Ca(OH)(2)) solutions imitating the liquid phase in concrete pores. The results indicate that the cathodic process on Q235 carbon steel electrode in oxygen-saturated 0.02 M Ca(OH)(2) with different concentrations of chloride ions contain three reactions except hydrogen evolution: dissolved oxygen reduction, the reduction of Fe(III) to Fe(II), and then the reduction of Fe(II) to Fe. The peak potential of ORR shifts to the positive direction as the chloride ion concentration increases. The oxygen molecule adsorption can be inhibited by the chloride ion adsorption, and the rate of ORR decreases as the concentration of chloride ions increases. The mechanism of ORR is changed from 2e(-) and 4e(-) reactions, occurring simultaneously, to quietly 4e(-) reaction with the increasing chloride ion concentration.

Global negative vegetation feedback to climate warming responses of leaf litter decomposition rates in cold biomes

Whether climate change will turn cold biomes from large long-term carbon sinks into sources is hotly debated because of the great potential for ecosystem-mediated feedbacks to global climate. Critical are the direction, magnitude and generality of climate responses of plant litter decomposition. Here, we present the first quantitative analysis of the major climate-change-related drivers of litter decomposition rates in cold northern biomes worldwide. Leaf litters collected from the predominant species in 33 global change manipulation experiments in circum-arctic-alpine ecosystems were incubated simultaneously in two contrasting arctic life zones. We demonstrate that longer-term, large-scale changes to leaf litter decomposition will be driven primarily by both direct warming effects and concomitant shifts in plant growth form composition, with a much smaller role for changes in litter quality within species. Specifically, the ongoing warming-induced expansion of shrubs with recalcitrant leaf litter across cold biomes would constitute a negative feedback to global warming. Depending on the strength of other (previously reported) positive feedbacks of shrub expansion on soil carbon turnover, this may partly counteract direct warming enhancement of litter decomposition.

东天山地区金矿床成矿流体地球化学及其成矿机制

The mechanism of gold ore formation in the eastern Tianshan Mountains, Xinjiang Uygur Autonomous Region, that has been dealt with from various aspects, remains unclear. On the basis of investigations of regional geology, ore deposit geology, and microscopic observations of ores and related rocks of the Jinwozi, the 210, and the Mazhuangshan gold ore deposits, this thesis made a systematic research on the microthermometry of gangue quartz-hosted fluid inclusions, gas, liquid ion and rare earth element compositions and hydrogen, oxygen isotope compositions of sulfide- and quartz-hosted fluid inclusions, and sulfur and lead isotope compositions of sulfide ore minerals from the major ores in the three deposits. On the basis of the above synthetic studies, sources of ore-forming fluids and metals, and mechanism of gold ore formation in the region were discussed. Gas compositions of pyrite- and sphalerite-hosted fluid inclusions were first analyzed in this thesis. Compared with gangue quartz-hosted fluid inclusions, the sulfide-hosted ones are richer in gaseous species CO2, CO, and CH4 etc. Both gas and liquid CO2 are commonly observed in fluid inclusions, whereas halite daughter minerals rarely occur. Ore-forming fluids for the three gold ore deposits are characteristically of medium to low temperatures, medium to low salinities, are rich in CO2 and Na+, K+, Cl" ions. Gas covariation diagrams exhibit linear trends that are interpreted as reflecting mixing between the magamtic fluid and meteoric-derived groundwater. Regarding rare earth element compositions, the Jinwozi and the 210 deposits show moderate to strong LREE/HREE fractionations with negative Eu anomalies. However, the Mazhuangshan deposit shows little LREE/HREE fractionation with positive Eu anomalies. Hydrogen and oxygen isotope compositions of pyrite-hosted fluid inclusions that were first analyzed in this thesis indicate the presence of magmatic water. Hydrogen and oxygen isotope compositions of pyrite- and quartz-hosted fluid inclusions suggest mixing between magmatic water and meteoric-derived groundwater. Sulfur and lead isotope compositions of sulfide ore minerals indicate multi-sources for the metallogenetic materials that range from the crust to the mantle. On the basis of the above synthetic studies, genesis of the gold ore deposits in the eastern Tianshan Mountains was approached. From the Middle-Late Hercynian to Early Indosinian, geodynamic regime of the region was changing from the collisional compression to the post-collisional extension. During the period, magmas were derived from the crust and the mantle and carried metallogenetic materials. Magma intrusion in the upper crust released the magmatic fluids, and drove circulation of groundwater. Mixing of magmatic fluid with groundwater, and extraction of metallogenetic materials from the country rocks are the mechanism for the gold ore formation in the eastern Tianshan Mountains.

Formation and dissociation of protonated pyridine-methanol cluster ions at 355 and 266 nm

The multi-photon ionization process of the hydrogen-bond cluster of pyridine-methanol has been investigated using a conventional and reflectron time-of-flight mass spectrometer (RTOF-MS) at 355 and 266 nm laser wavelengths, respectively. The sequences of the protonated cluster ions (CH3OH)(n)H+ and (C5H5Nn)(CH3OH)(m)H+ (n = 1,2) were observed at both laser wavelengths, while the sequence of the cluster ions (CH3)OHn (H2O)H+ was observed only at 355 nm laser wavelength. The difference between the relative signal intensities of the protonated methanol cluster ions at different laser wavelengths is attributed to different photoionization mechanisms. Some nascent cluster ions in metastable states dissociated during free flight to the detector. The dissociation kinetics is also discussed. (C) 2000 Elsevier Science B.V.