导电聚哒嗪的电化学合成与表征

本工作用循环伏安法研究了哒嗪的电化学氧化聚合过程以及聚哒嗪的电化学行为,合成了电导率约为1s/cm的聚哒嗪,并采用光谱、能谱方法对它进行了表征,FTIR谱表明聚哒嗪中3,6-二取代哒嗪结构引起的吸收带位于1330,1120,1100和840cm~(-1),掺杂聚哒嗪的双极子能带的两个光吸收峰分别位于1.8,0.9eV。

稀土酞菁配合物的XPS研究

我们合成了稀土单酞菁配合物LnPcCl和LnPc(OAc)_2(Ln=Tb,Ho,Tm,Lu,Pc为酞菁根,OAc为乙酸根)。用XPS研究了它们的电子结构。结果指出,稀土酞菁配合物的化学键具有一定程度的共价性,其强度与电荷转移程度有关。L→Ln电荷转移不同于冠醚配合物,前者既有配位也含取代,后者纯系配位。且酞菁环系吸电子基团,电负性较高,故LnPc(OAc)_2中乙酸根的配位氧原子的Ols比Ln(OAc)_3的Ols结合能高。由于电荷转移程度与电负性、配位数等因素有关,LnPc(OAc)_2中Ln的配位数较高,LnPcCl中Cl的电负性较高,故LnPc(OAc)_2中Ln4d_(5/2)结合能低于LnPcCl。并讨论了配合物的分子组成及结构。

n-型聚乙炔复合膜电极性能的研究

自MacDiarmid等将聚乙炔(PA)做为二次电池的电极材料以来,其电化学特性和行为引起了人们的极大兴趣.随后的研究表明,p-型PA[(CH)~(y+)Ay~-]_x在电解液中不稳定,用ClO_4~-掺杂的PA充放循环时有降解发生.n-型PA[My~+(CH)~(y-)]_x(y≤0.10)在THF/LiClO_4电解质中较稳定,电化学还原完全可逆,目前已实现1100次充放循环.因此,它既可做电池的正极材料(碱金属为负极),又可做负极材料(TiS_2为正极).我们发现

A potent anti-oxidant property: fluorescent recombinant alpha-phycocyanin of Spirulina

To express and product a fluorescent antioxidant holo-alpha-phycocyanin (PC) of Spirulina platensis (Sp) with His-tag (rHHPC; recombinant holo-alpha-phycocyaninof Spirulina platensis with His-tag) in 5-l bench scale. A vector harbouring two cassettes was constructed: cpcA along with cpcE-cpcF in one cassette; ho1-pcyA in the other cassette. Lyases CpcE/F of Synechocystis sp. PCC6803 (S6) could catalyse the 82 site Cys in apo-alpha-PC of Sp linking with bilin chromophores, and rHHPC was biosynthesized in Escherichia coli BL21. The constant feeding mode was adopted, and transformant reached the biomass of rHHPC up to 0.55 g l(-1) broth in 5-litre bench scale. rHHPC was purified by Ni2+ affinity column conveniently. The absorbance and the fluorescence emission spectra of rHHPC had lambda(max) at 621 and 650 nm, respectively. The IC50 values of rHHPC were 277.5 +/- 25.8 mu g ml(-1) against hydroxyl radicals and 20.8 +/- 2.2 mu g ml(-1) against peroxyl radicals. Combinational biosynthesis of rHHPC was feasible, and the constant feeding mode was adopted to produce good yields of rHHPC. Fluorescent rHHPC with several unique qualitative and quantitative features was effective on scavenging hydroxyl and peroxyl radicals. A potent antioxidant rHHPC was co-expressed, produced and characterized for nutritional and pharmacological values, which would help to develop phycobiliproteins' applications in their fluorescent and biological activities.

Heinrich event imprints in the Okinawa Trough: evidence from oxygen isotope and planktonic foraminifera

Planktonic foraminiferal faunas, oxygen isotope and modern analog technique sea surface temperature records were obtained in piston core DGKS9603 (28degrees08.869'N, 127degrees16.238'E, water depth 1100 in) collected from the middle Okinawa Trough. During the last glaciation, four cold events were identified and correlate Heinrich events (HE) H2-5 of the last 45 ka. During the last deglaciation, core DGKS9603 has begun to be influenced by the Kuroshio since about 16 cal ka BP. Three weakenings of this warm current occurred at about 2.8-5.3, 11.4 and 15.5 cal ka BP respectively. Among the three fluctuations, the oldest one is synchronous with HE1 and could be a response to the strong cooling observed in the North Atlantic Ocean. The fluctuation occurring at about 11.4 cal ka ago corresponds to the Younger Dryas within the age error bars. Our observations provide new evidence that the HEs documented from Greenland and the northern North Atlantic had a global climatic impact. Changes in the intensity of the East Asian monsoon could be the main mechanism responsible for the paleoccanographic variations observed in the Okinawa Trough. (C) 2001 Elsevier Science B.V. All rights reserved.

青蟹属的系统进化和中国沿海拟穴青蟹的群体遗传结构研究

为了进一步研究青蟹属系统进化的科学问题，并揭示我国东南沿海青蟹群体遗传结构和群体进化细节信息，本论文主要开展了以下两个方面的研究：（1）基于线粒体12S rRNA、16S rRNA和COI三种基因序列探讨中国东南沿海青蟹的种类归属与青蟹属的系统进化；（2）利用线粒体COI基因标记分析中国东南沿海拟穴青蟹的群体遗传结构。序列特征、遗传距离和系统进化分析结果都表明本文研究的青蟹均为S. paramamosain。NJ、BAYES和ML系统进化树显示S. paramamosain与S. tranquebarica互为姐妹种，S. olivecea应该是4种青蟹中最早分化出来的种类。10个地理群体130只拟穴青蟹的线粒体DNA（mitochondrial DNA，mtDNA）细胞色素氧化酶亚基I（COI）基因序列Mantel检验结果显示群体间的遗传分化程度与地理距离没有显著的相关性。分子进化中性检验结果表明自然选择在分子进化过程中起了重要作用，并暗示该物种在最近经历了一个快速的群体爆发及扩张事件。

黑颈鹤（Grus nigricollus）种群生态及濒危等级评估

黑颈鹤的种群总量有5000～6000 只个体,主要分布在青藏高原和云贵高原,分布区约22 ×105km2 ,占有面积约5400 km2 。青藏高原北部和西部为其繁殖区,越冬区主要在雅鲁藏布江河谷中段、喜马拉雅山脉南坡及云贵高原部分区域,青藏高原东部为其迁徙途径之地。越冬时以家族、同种群及混合群(主要与灰鹤Grus grus 和斑头雁A nser indicus) 形式集群活动。繁殖期分化为非繁殖群和繁殖对(Breeding pair) 两种类型。繁殖对能否成功地占有领域是繁殖成败的关键。笔者认为该物种依IUCN(1994) 标准应列为易危级(Vulnerable ,VU)

三门峡宋家店黄土－古土壤序列的地层学研究及其古环境记录

The Sanmen Gorge area is located in the southernmost margin of the Chinese Loess Plateau with well developed eolian deposit sequence for the past 2.6 Ma, providing a key site for further understanding of the evolution history of the East Asian monsoon since late Pliocene. This study attempted to characterize the stratigraphy and paleoclimate record of the loess-paleosol sequence in the Songjiadian section. The work involved includes systematic field investigation, paleomagnetic and rock magnetic analyses, grain size and major chemical composition analyses, and multiple proxy measurements of magnetic susceptibility, color reflectance and the ratio of CBD-dissolvable iron to the total iron (FeD/FeT). By comparisons of the Songjiadian section with well studied loess sections in the west of the Sanmen Gorge, the spatial variations of the East Asian monsoon was evaluated for some periods during which typical loess or paleosols developed. The following conclusions have been obtained. 1. Stratigraphic correlation and paleomagnetic result demonstrate that the loess-paleosol sequence in the Songjiadian section was accumulated from 2.6Ma, and is generally a complete and continuous loess sequence. However, notable differences from type loess sections have been identified for a few loess and paleosol units, featured by absence or anomalous thickness in the Songjiadian section. 2. Magnetic susceptibility and chromaticity records clearly reveal the loess-paleosol cycles, and indicate that the Sanmen Gorge area has been warmer and more humid than the Lingtai and Jingchuan sections in the western central Loess Plateau since the Early Pleistocene. 3. Grain size distribution patterns are typical of eolian dust, and show a great similarity between various units of loess and paleosols, and between the S32 and the underlying Red Clay through the Songjiadian profile, suggesting the eolian origin for the loess, paleosols and the Red Clay. 4. Comparison of the FeD/FeT curves from different loess sections indicates a stronger chemical weathering in the Songjiadian section and notable enhancement around 1800, 800 and 600 ka BP, implying the strengthening of the East Asian monsoon during these periods. In contrast, it was weakened at 1100 ka BP. Generally, the summer monsoon shows a gradually decreasing trend during the entire Pleostocene, but the spatial pattern typified by an increasing trend in weathering intensity from north to south remained the same. 5. The loess unit L9 in the Songjiadian section displays two geomagnetic field anomalies with the midpoint ages of 0.917 and 0.875 Ma respectively, with a segment of 12 ka. They are demonstrated to be equivalent to the Santa Rosa and Kamikatsura geomagnetic excursions. 6. Magnetite is the main magnetic carrier for both loess and paleosols. Maghemite concentration is higher in paleosols than in loess, and is an important carrier for the enhanced magnetic susceptibility in paleosols. Magnetic fabric analysis suggests a dominant N-S wind direction prevailing in the L9 and L15, while the summer winds were dominantly in NNE-SSW direction during the S8 period, notably differing from previous studies.

青岛晚白垩世岩石圈结构特征：劈石口晚白垩世基性脉岩及其捕虏体提供的证据

The occurrence of Late Cretaceous mafic dykes and their entrained peridotite and granulite xenoliths as well as clinopyroxene xenocrysts in the Qingdao region provide us a precious opportunity to unveil the nature and characteristics of the Late Mesozoic lithospheric mantle and lower crust beneath the Jiaodong region, and the change of the magma sources. These studies are of important and significant for understanding the lithospheric evolution in the eastern North China Craton. There were two periods of magma activities in Late Mesozoic in Qingdao Laoshan region, one was around 107Ma in the Early Cretaceous and the other around 86Ma in the Late Cretaceous according to the whole rock K-Ar age determination. The Early Cretaceous mafic dykes and the Late Cretaceous mafic dyke (i.e. Pishikou mafic dike) have completely different geochemical characteristics. The Early Cretaceous mafic dykes are enriched in LILE, strongly depleted in HFSE (Nb, Ta, Zr, Hf) and characterized by the highly radiogenic Sr and Nd isotopic compositions. These geochemical features indicate that the Early Cretaceous mafic dykes were derived from an enriched lithospheric mantle. In contrast, the Late Cretaceous mafic dyke is enriched in LILE, without HFSE depletion (Nb, Ta, Zr, Hf) and has less radiogenic Nd and Sr isotopic compositions. These geochemical features indicate that the Late Cretaceous mafic dyke was derived from the asthenosphere modified by subducted pelagic sediment contamination. The intrusive age of the Late Cretaceous mafic dyke provides further information for the termination of the lithosphere thinning for the eastern North China Crtaon. Pishikou Late Cretaceous mafic dyke contains abundant peridotitic xenoliths, granulite xenoliths and clinopyroxene xenocrysts. The peridotitic xenoliths can be divided into two types: high Mg# peridotites and low Mg# peridotites, according to their textural and mineral features. The high-Mg# peridotites have high Fo (up to 92.2) olivines and high Cr# (up to 55) spinels. The clinopyroxenes in the high# peridotites are rich in Cr2O3 and poor in Al2O3. The low-Mg# peridotites are typified by low Mg# (Fo <90) in olivines and low Cr# (Cr# <0.14) in spinels. The clinopyroxenes in the low-Mg# peridotites are rich in Al2O3 and Na2O and poor in Cr2O3. These two type peridotites have similar equilibrated temperatures of 950C-1100C. The Clinopyroxenes in the high-Mg# peridotites generally have high and variable REE contents (REE = 5.6-84 ppm) and LREE-enriched chondrite-normalized patterns ((La/Yb)N>1). In contrast, the clinopyroxenes in the low-Mg# peridotites have low REE contents (REE = 12 ppm) and LREE-depleted patterns ((La/Yb)N<1). The textural, mineral and elemental features of the low-Mg# peridotites are similar to those of the low-Mg peridotites from the Junan, representing the newly-accreted lithospheric mantle. However, the mineralogical and petrological features of the high-Mg# peridotites are similar to those of the high-Mg# peridotites from the Junan region, representing samples from the old refractory lithospheric mantle that was strongly and multiply affected by melts of different origins Late Cretaceous mafic dike in the Qingdao region also contains two types of granulite xenoliths according to the mineral constituents: the pyroxene-rich granulites and the plagioclase-rich granulites. Equilibrated temperatures calculated from the cpx-opx geothermometers are in a range of 861C - 910C for the pyroxene-rich granulites and of 847C - 890C for the plagioclase-rich granulites. The equilibrated pressure for the plagioclase-rich granulites is in a range of 9.9-11.7 kbar. Combined with the results of the peridotitic xenoliths, a 40C temperature gap exists between the peridotite and the granulite. The petrological Moho was 33~36 km at depths, broadly consistent with the seismic Moho estimated from the geophysical data. This indicates that there was no obvious crust-mantle transition zone in the Qingdao region in the Late Mesozoic. Pishikou Late Cretaceous mafic dyke entrained lots of clinopyroxene xenocrysts which are characterized by the chemical zoning. According to the zoning features, two types of clinopyroxene xenoliths can be classified, the normal zoning and the revise zoning. The normally-zoned clinopyroxene xenocrysts have LREE-depleted REE patterns in the cores. In contrast, the revisely-zoned clinopyroxenes have LREE-enriched REE patterns in the cores. According to the rim and core compositions of xenocrysts, all the rims are balanced with the host magma. Meanwhile, the origins of the cores were complicated, in which the normally-zoned clinopyroxenes were derived form the lithospheric mantle and some of the reversely-zoned clinopyroxnes were originated from the lower crust. Other revisely-zoned clinopyroxenes had experienced complex geological evolution and need to be further investigated. According to the above results, a simplified lithospheric profile has been established beneath the Qingdao region and a constraint on the nature and characteristics of the lithospheric mantle and lower crust has been made.

陆地生态系统植物的氮源及氮素吸收

氮是植物生长发育所必需的营养元素,也是其主要的限制因子之一。陆地生态系统植物所需氮的来源及植物对氮素的吸收利用均受控于其种类和生长环境。环境条件的改变,一方面可能改变植物生长区原有氮的形态、浓度、赋存方式等,从而改变氮对植物的供给状况;另一方面可能引起植物生长区土壤质量、水分利用状况、光照等的改变,从而产生耦合现象,直接影响植物的生理生态特性,使植物对氮素的吸收利用发生改变,导致植物生长区的种群类型及物种多样性发生改变,并直接影响到生态系统的功能及演替。本文主要对陆地生态系统中高等植物生长发育所需氮素的来源及植物对氮素吸收利用过程中的影响因素进行了综述和讨论,并结合国内外在该领域的研究现状对其研究前景进行了展望。

苏州高岭石的热变过程研究

运用X射线衍射、红外光谱及固体高分辨核磁共振等手段，研究了苏州高岭石560～1600℃热变产物，结果显示：①高岭石．偏高岭石．莫来石的转变系列存在结构上的连续性，其转变经历了脱羟阶段（约400～600℃），偏高岭石阶段（600～800℃），相分离阶段（800～1100℃），莫来石阶段（1100～1600℃）；②莫来石形成过程没有出现AlO3的大量分凝，但存在SiO2分凝；③偏高岭石．莫来石转变过程的中间相为Al-Si尖晶石和准莫来石；④引起1000℃放热反应的主要因素是SiO2的大量分凝，其次是准莫来石等过渡相的形成。

高岭石热转变产物^29Si、^27Al魔角旋转核磁共振研究

运用魔角旋转核磁共振结合红外光谱及X射线衍射等手段，研究了苏州高岭石的560－1600℃热转变产物，主要获得以下结论：（1）高岭石－偏高岭石－莫来石的转变系列的确存在结构上的连续性。其转变经历了几个阶段；脱羟阶段（400－600℃），偏高岭石阶段（600－800℃），相分离阶段（800－1100℃），莫来石阶段（1100－1600℃）。（2）莫来石形成过程没有出现Al2O3的大量分凝，但存在SiO2的分凝。（3）偏高岭石－莫来石转变过程的中间相为Al-Si尖晶石和准莫来石。（4）引起1000℃放热反应的主要因素是准莫来石的形成。

高岭石的结构缺陷,杂质元素存在形式及热转变研究

本研究主要研究了高岭石的结构缺陷、杂质元素(特别是铁、钒)的存在形式以 高岭石一奠来 石的热转变过程。应用先进的x射线衍射结合多重峰分离方法，解析了高蛉石的结构缺路，重新 修正了Hinkley结晶指数(HI)．使之更能反映实际的结构信息。首次在低温条件下观察到苏州高 岭石钒的顺磁共振谱的超精细结构线发生分裂的现象(这种现象尚未见诸报道)，这是由于四价钒 进入高岭石八面体晶格替代三价铝，且占据两种八面体位置的结果。 ’ 、 si魔角旋转核磁共振研 究证实，高蛉石脱羟变为偏高岭石后，铝的配位数由Ⅵ转为Ⅳ 、V和Ⅵ三种形式并存，且以V配位为 主；引起i000℃ 放热反应的主要因素为准莫来石的形成。奠来石约在1100℃ 开始生成。研究样品 采自贵州的丹寨、马场坪、小山坝和江苏苏州的阳山。贵州高岭土属含煤建造沉积型矿床，其中丹 寨和马场坪高岭土产自二叠系煤系地层，小山坝高岭土产自石炭系。阳山高岭土属古溶洞充填风 化型矿床。

高温高压下岩石部分熔融及熔体形态学研究

熔体形态学作为现代岩石学的前沿领域之一，其主要研究矿物颗粒之间熔体形态特征、连通性以及与周围矿物的相互作用关系。该学科在我国还不被广大地学工作者所熟悉。本论文以斜长角闪岩为初始物料，在850-1100℃和2.0-4.0 GPa条件下，进行了岩石的部分熔融实验，并对作为实验产物的熔体进行了形态学方面的研究。同时就目前形态学研究的基础理论和实验方法作了初步介绍。 利用YJ－3000吨六面顶高压装置，我们以天然的块状斜长角闪岩为样品，在高温高压条件下进行了斜长角闪岩的脱水部分熔融实验，测量了熔体与矿物相接触时所形成的二面角。结果表明： 1、熔体的形态分布与熔融程度具有明显依赖关系，当熔融程度小于5%时，熔体被矿物颗粒分隔开来，以熔块的形式相互独立；当熔融程度大于5%时，薄膜状或管状熔体沿矿物颗粒边缘形成一个相互连通的熔融网络。 2、当熔体相互隔离时，二面角平均值大于60°；当熔体相互连通时，二面角平均值小于60°。在熔体相互连通的测量实验中，英安质和安山质成分的熔体与石榴子石的二面角分布在56－58°之间，与单斜辉石的二面角分布在50－53°之间。 3、根据界面化学理论推导表面张力和界面能的最小化是推动熔体连通的两个驱动力。 4、二面角大小受体系温度、压力及物质组成等物理化学条件的影响，随着温度升高，固－液界面的表面张力减弱，二面角减小，熔体越容易相互连通。 5、通过对二面角的原位测量，不仅可以判断熔体的相互连通性，还能反演熔体的熔融过程。