An organic-inorganic vanadium oxide with one-dimensional ladder-type structure: hydrothermal synthesis, structure and characterization of [V4O10(o-phen)(2)]

A novel organic-inorganic hybrid vanadium oxide [V4O10(o-phen)(2)], involving all vanadium atoms present in +5 oxidation, has been hydrothermally synthesized and characterized by elemental analysis, IR, UV-vis, ESR, XPS spectra and TG-DTA thermal analysis. The single-crystal X-ray diffraction shows that the red-brown crystal is formed in the triclinic system, space group P (1) over bar, a = 9.782(2), b = 6.5124(14), c = 19.765(4) Angstrom, alpha = 89.94(2)degrees, beta = 100.66(2)degrees, gamma = 89.86(2)degrees. The title compound exhibits an infinite one-dimensional ladder-type tetravanadate skeleton with organonitrogen donors of o-phenanthroline ligands coordinated directly to the vanadium oxide framework.

Electrospray ionization multiple-stage tandem mass spectrometric analysis of diglycosyldiacylglycerol glycolipids from the bacteria Bacillus pumilus

Electrospray ionization (ESI) combined with multiple-stage tandem mass spectrometry (MSn) was used to directly analyze the glycolipid mixture from bacteria Bacillus pumilus without preliminary separation. Full scan ESI-MS revealed the composition of picomole quantities of glycerolglycolipid species containing C-14-C-19 fatty acids, some of which were monounsaturated, Two main components were identified from their molecular masses and fragmentation pathways. The fragmentation pathway of the known compound compared with the investigated compound verified the proposed structure as 1(3)-acyl-2-pentadecanoyl-3(1)-O-[beta-D-glucopyranosyl-(1-->6)-O-beta-D-glucopyranosyl]-sn-glycerols. A comparison of the multiple tandem mass spectra of the different alkali-metal cation adducts indicates that the intensity of fragments and the dissociation pathways are dependent on the alkali-metal type, The basic structures of glycerolglycolipids were reflected clearly from the fragmentation patterns of the sodium cations, The intense fragments of the sugar residue from the precursor ions were obtained from the lithiated adduct ions. ESI-MSn spectra of [M + K](+) ions did not provide as much fragmentation as [M + Na](+) and [M + Li](+) adducts, but their spectra allow the position of glycerol acylation to be determined. On the basis of MS2 spectra of[M + K](+) ions, it was established that all components have a C-15:0 fatty acid at the sn-2 position of the glycerol backbone and C-14-C-19 acids at the sn-1 position of the glycerol backbone. Copyright (C) 1999 John Wiley & Sons, Ltd.

PHOTOELECTRON-SPECTRA OF VARIOUS CORE LEVELS IN SOME RARE-EARTH N-ACETYLVALINE BIOINORGANIC COMPLEXES

X-ray photoelectron spectra of some bioinorganic complexes of La, Pr, Nd, Sm, and Gd with N-acetylvaline have-been measured. The complex formation does not give any detectable influence on the binding energy of the N 1s peak in the amino group, but has some appreciable effect on the binding energy of the C 1s peak and the O 1s peak in the carboxyl and carbonyl group of the biological ligand. The spin-orbit splitting between the 3d5/2 and 3d3/2 core level of the rare earth ion in these bioinorganic complexes also becomes slightly larger than that of the free rare earth atom due to the effect of the crystal field from the biological ligands.

(LaCl)(THF)_2(μ-Cl)_4[Li(THF)_2]_2配合物的合成及晶体结构

LaCl_3和LiCl在THF中于室温反应,以已烷为沉淀剂,在-78℃得到晶体,经色谱、元素分析及X射线晶体结构测定,得到了组成为(LaCl)(THF)_2(μ-Cl)_4[Li(THF)_2]_2的配合物.在约-80℃收集该配合物晶体的衍射强度数据,计算结果表明属于单斜晶系,P2_1/c空间群,其晶胞常数a=10.542(4)(?),b=32.236(14)(?),c=11.182(6)(?);β=113.50(3)°,最后R值为0.0477.四个氯桥键构成了分子的基本骨架,表明桥键在小配体轻希土双金属配合物结构中具有稳定作用.

Relative paleointensity of the geomagnetic field during the past 200 ka from the West Philippine Sea and its chronological significance

Our rock magnetic analysis of core Ph05 from the West Philippine Sea demonstrates that the core preserves a strong, stable remanent magnetization and meets the magnetic mineral criteria for relative paleointensity (RPI) analyses. The magnetic minerals in the sequence are dominated by pseudosingle-domain magnetite, and the concentration of magnetic minerals is at the same scale. Both the conventional normalizing method and the pseudo-Thellier method were used in conjunction with the examination of the rock magnetic properties and natural remanent magnetization. Susceptibility (chi), anhysteretic remnant magnetization (ARM) and saturation isothermal remnant magnetization (SIRM) were used as the natural remanent magnetization normalizer. However, coherence analysis indicated that only ARM is more suitable for paleointensity reconstruction. The age model of core is established based on oxygen isotope data and AMS(14)C data, which is consistent with the age model estimated from RPI records. The relative paleointensity data provide a continuous record of the intensity variation during the last 200 ka, which correlates well with the global references RPI stacks. Several prominent low paleointensity values are identified and are correlated to the main RPI minima in the SINT-200 record, suggesting that the sediments have recorded the real changes of geomagnetic field.

Preservation of black carbon in the shelf sediments of the East China Sea

Concentrations and carbon isotopic (C-14, C-13) compositions of black carbon (BC) were measured for three sediment cores collected from the Changjiang River estuary and the shelf of the East China Sea. BC concentrations ranged from 0.02 to 0.14 mg/g (dry weight), and accounted for 5% to 26% of the sedimentary total organic carbon (TOC) pool. Among the three sediment cores collected at each site, sediment from the Changjiang River estuary had relatively high BC contents compared with the sediments from the East China Sea shelf, suggesting that the Changjiang River discharge played an important role in the delivery of BC to the coastal region. Radiocarbon measurements indicate that the ages of BC are in the range of 6910 to 12250 years old B. P. (before present), that is in general, 3700 to 9000 years older than the C-14 ages of TOC in the sediments. These variable radiocarbon ages suggest that the BC preserved in the sediments was derived from the products of both biomass fire and fossil fuel combustion, as well as from ancient rock weathering. Based on an isotopic mass balance model, we calculated that fossil fuel combustion contributed most (60%. 80%) of the BC preserved in these sediments and varied with depth and locations. The deposition and burial of this "slow-cycling" BC in the sediments of the East China Sea shelf represent a significant pool of carbon sink and could greatly influence carbon cycling in the region.

Carbonate cycle and its control factors in Kuroshio source region during the last 190ka BP

Two deep sea cores (Ph05-5, 16.05 degrees N, 124.34 degrees E, water depth 3382m and WP3: 22.15 degrees N, 122.95 degrees E, water depth 2700m) retrieved from the Kuroshio source region of the western Philippine Sea were selected to carry out the CaCO3 and calcareous nannofossil faunas study. Based on AMS(14)C data and comparing tire oxygen isotope curve with SPECMAP delta O-18 (Martinson et al., 1987) a stratigraphy was established. And, combining the changes of primary productivity and dissolution index of carbonate, the carbonate cycle and its control factors were analyzed in this region during the last 190ka BP. The carbonate contents showed higher values in the glacial periods and lower values during the interglacial and Holocene periods, which characteristics was similar to the tendency of "Pacific Type" carbonate cycle. However, there were high carbonate contents in the warm period and low values during the cold interval, which displayed the same tendency with the "Atlantic Type" carbonate cycle during the last glacial period (MIS4-2) in the east of Phillipines. The variations of primary productivity and carbonate dissolution index indicated that the carbonate dissolution was a major factor controlling the carbonate content in tire cast of Philippines, and the variations in carbonate contents were mainly affected by the productivity of calcareous organism in the Southeast of Taiwan. The "Atlantic Type" carbonate cycle in the cast of Phillipines during the last glacial period (MIS4-2) was an effect of the process of dissolution combined with the change of primary productivity.

北黄海西部泥质沉积特征与成因探讨

本文的研究的主要目的是了解北黄海泥质区的沉积特征和形成的动力过程。基于此目的，在北黄海西部海区进行了两次海洋地质与地球物理调查，并根据对浅钻样品的粒度分析和~（210）Pb沉积速率的测定，结合浅地层剖面的解译以及ADCP流速资料的处理，探讨了北黄海西部的沉积层序，讨论了泥质区的物质来源与形成原因，分析了北黄海中部泥质沉积的~（210）Pb沉积速率在一定的动水条件下的可信度，并对柱状样粒度参数的相关分析与地层对比之间的关系进行了初步的阐述。浅地层剖面与岩芯粒度分析表明，北黄海西部的地层划分为三层：上层为粘土沉积，位于北黄海中部、山东半岛沿岸和辽东半岛东南岸；中层为粉砂沉积，分布区域与粘土沉积类似，或者位于粘土沉积之下，或者直接出露海底；下层为粗颗粒砂质沉积，颁上于整个海区，在粘土沉积和/或粉砂沉积存在的海域，砂质沉积位于这些沉积的下部，而在其他海域则直接出露海底。粘土沉积与粉砂沉积统称为泥质沉积，内部结构较均一，粒度的垂向变化不大，但两层之间在粒度和地层反射信号等方面的差异还是很明显的，在山东半岛沿岸构成了泥质沉积的两相结构。粗颗粒沉积的粒度垂向变化较大，与上层细颗粒沉积之间的差异显著。泥质沉积的厚度以山东半岛东端最大，约30m。而沉积速率却很小，在mm/a的量级上，因此在全新世最大海侵后的几千年内形成巨厚的沉积是不可能的，其主要物源可能是古河流。渤海海峡区泥质沉积厚度从南向北、从西向东逐渐变薄，从西向东沉积速率逐渐减小，但沉积速率的绝对值较大，可以在全新世最大海侵后的几千年内形成如此厚的沉积。北黄海中部泥质沉积厚度约在8m左右，位于泥质沉积边缘岩芯中泥炭层的~（14）C年代约10000aBP，而且~（210）Pb沉积速率较小，无法满足几千年内堆积厚层沉积的需要，因此，该处泥质沉积的主体并非全新世最大海侵后形成的，而是早全新世海侵过程中的海岸侵蚀与海底物质的再改造作用提供了沉积物质。整个北黄海西部的泥质沉积总量约有4.41 * 10~（11）t。对于两个沉积环境可能相似的柱状岩芯，利用粒度参数求取各个层位的最大相关系数，可以找到具有良好对应关系的层位，其沉积年龄相近。或者说，在已知一个岩芯的粒度参数和层位年龄的情况下，可以应用柱状样粒度参数的相关分析，推得另一个粒度参数已知的岩芯的年龄。理论上，这种方法适用于来自相同动力环境的岩芯。利用水动力条件与悬沙浓度计算北黄海中部泥质区的沉降通量，与~（210）Pb测得的结果对比，发现对于粘性颗粒两者的值非常近似，说明在该区的动水条件下~（210）Pb测年法对粘性沉积物的测定结果有很好的可信度。

冲绳海槽黑潮流域近4万年以来的古海洋环境演化

本文采用取自冲绳海槽的91个站位的表层样品和2个柱状岩芯，通过微体古生物有孔虫分析、氧碳同位素测试、AMS~(14)C测年、沉积物粒度和地球化学分析，探讨了现代生物群落、表层沉积物氧同位素与现代海洋环境之间的关系，进而对冲绳海槽区域近4万年来的古海洋环境和古黑潮演化进行了详细的研究。表层沉积物中的浮游有孔虫氧同位素与现代海洋环境之间的关系密切，浮游有孔虫从G.ruber到G.sacculifer到N.dutertrei其δ~(18)O值由轻变重，表明三种有孔虫其生活水层依次由浅到深。在横穿海槽的剖面上浮游有孔虫δ~(18)O在近陆端因受冲淡小影响较强而变轻，而在东侧站位，受黑潮暖流或其支流的影响氧同位素同样有变轻的趋势。N. dutertrei和G.ruber的氧同位素差值表明了冲绳海槽北部区域黑潮支流对表层水体的影响要大于次表层水体，而在冲绳海槽南部区域，黑潮暖流对次表层水体有相对较强的影响。冲绳海槽南部表层沉积物中的浮游有孔虫整体上属于赤道区组合，溶解作用对该区的浮游有孔虫群落有显的影响，冲绳海槽北部区浮游有孔虫组合对具有温带群落的特征。浮游有孔虫分布与海洋环境密切相关，南北区的浮游有孔虫分布都明显受暖流的影响，在暖流的主流轴处浮游有孔虫丰度通常较高。冲绳海槽具有相对较浅的碳酸盐溶跃面，浮游有孔虫丰度和底栖有孔虫深水胶结壳的含量都进一步表明了该区碳酸钙溶跃面大约在1700 m水深左右，比开放大洋明显要浅得多。表层沉积物中的底栖有孔虫主要受水深和水团等因素的制约。水深制约着有孔虫属种的分带，也影响底栖有孔虫的组合。根据Q型因子分析，冲绳海槽南部表层沉积物中的底栖有孔虫从陆架连缘到海槽底部可以划分为5个特定的组合，分别对应黑潮表层水和次层水影响环境、黑潮中层水影响环境、溶跃面以上的黑潮深层水影响环境、黑潮底层水团影响环境和溶解作用较强的槽底环境；北部区的底栖有孔虫群落反映了四个组合，分别代表了陆架混合水团影响环境、黑潮暖流中层水影响环境、冷涡沉积和上升流区影响环境以及对马暖流水团影响下的环境。以氧同位素曲线为基础，结合AMS~(14)C测年和生物地层学对柱状岩芯进行了地层划分和对比，E107孔记录了冰消期以来大约15,000 a来的古环境演化记录，具有较高的沉积速率，DOC－42孔保存在主要是末冰期中40－10ka BP期间的古环境沉积记录，沉积物记录的分辨率相对较低。浮游有孔虫有碎壳比和底栖有孔虫深海胶结壳含量表明了现代冲绳海槽的浅溶跃面是大约最近2000 a BP才开始突然变浅形成的，碳酸盐的溶解作用从冰消期到现在逐增强。冲绳海槽南部E107孔的底栖有孔虫组合把映了15,000 a来的底层水团具有两种完全不同的营养状况，约6500 a BP以前有机质通量较高，6500 a BP以后有机质通量则明显降低。DOC－42孔的底栖有孔虫组合反映该区约4万年以来的底部水团演化主要受有机质通量和氧含量的共同制约，氧同位素3期主要为高有机质通量的沉积环境，伴随有氧含量水平的较大波动；氧同位素2期有机质通量有所降低，氧含量整体为中等水平；氧同位素1期早期义部水体则较高氧含量为主。浮游有孔虫温跃层转换函数反映了冲绳海槽中部的温跃层在约13100 a BP有一个明显的变化，在这之前产温跃层深度较浅，平均89 m，而在该时间以后，温跃层平均深度变为166 m。此外在160 cm处和100 cm的温跃层深度的两次明显的降低，分别对应于新仙女木事件和黑潮暖流的重新入侵，表明这两个事件导致了海洋上层水体结构的突然变化。冲绳海槽北部浮游有孔虫转换函数古温度和浮游有孔虫的低温、低盐特征种反映了在氧同位素3期早期约40000a BP和氧同位素2期间存在两个明显的低温、低盐阶段，可能与沿岸水在该期间加强有关。其中氧同位素3期早期的表层海水古水温比末次冰期还要低，反映了区域海洋环境的重大变化。冲绳海槽南部E107孔的沉积物粒度、地球化学特征、黑潮特征指示种、表层古水温以及底层水团的性质在6500 a BP左右发生了重大的改变，与冲绳海槽南部的其他岩芯反映的古环境化基本一致，表明了南部海槽在6500 a BP前后古黑潮流径发生了重大变化。而冲绳海槽北部区域2万年以来的古环境则与南部有明显差异，总结前人对冲绳海槽古黑潮流径的研究，笔者对未次冰盛期古黑潮流径提出了新的推测。

土地利用变化对高寒草甸土壤有机质更新的影响

对青藏高原海北站区的自然土壤和扰动土壤进行高分辨率采样,测定土壤根系、有机碳及其~(14)C含量;用~(14)C示踪技术探讨土地利用变化对高寒草甸土壤有机质更新的影响.研究表明,土地利用变化对高寒草甸土壤碳循环影响显著. 耕作活动导致扰动土壤有机碳储量比自然土壤增加29.35%;扰动土壤剖面10～50 cm深土壤有机质的14C含量相对富集;自然土壤大多数有机碳储存在土壤表层,更新时间＜50 a,同一深度扰动土壤有机碳储量显著少,更新时间长(171～294 a);自然土壤10 cm以下有机碳主要为更新时间＞1 000 a的稳定碳所控制,扰动土壤的相应值出现在40 cm以下;自然土壤有机质更新产生的CO2通量为114 gC•m~(-2)•a~(-1),扰动土壤为48.7 gC•m~(-2)•a~(-1).

红原泥炭腐殖化度记录的全新世气候变化

腐殖化度作为气候代用指标首次用于我国泥炭的古气候研究,较好的记录了红原地区全新世的气候变化。对红原泥炭14 C 测年和腐殖化度分析,获得了距今12 000 年较高分辨率红原地区气候变化记录:11. 815～10. 9 kaB. P. ,气候干冷;10. 9～5. 6 kaB. P. ,气候湿暖;5. 6～3. 9 kaB. P. ,气候干冷;3. 9～1. 7 kaB. P. ,气候干冷、湿暖波动;1. 7～0 kaB. P. ,气候干冷。总体而言,大约5. 6 kaB. P. 是红原地区由早中全新世的湿暖气候向晚全新世干冷气候变化的转折点。同时,红原泥炭记录的降温事件在北半球具有普遍性,反映了青藏高原对全球气候变化的响应。

江苏固城湖近代沉积物中有机质的组成、演化及其古气候古环境意义

本文对江苏固城湖近代湖相沉积物可溶有机质中正烷烃、甾类、萜类、脂肪酸、醇类、酮类、芳烃等生物标志化合物的组成、分布及其在剖面上的演化进行了详细的研究。首次综合利用有机指标及参数、生物标志物的组成与变化特征，结合磁化率、硅藻、色素、~(14)C年龄推测10200-10600a.B.P.左右一低温突变事件的存在，与氧同位素的对比初步确定这一事件为国外普遍存在的晚仙女木冰期。研究亦表明了固城湖的生物输入具有湖生浮生物及陆生高等植物输入并存的特点；普遍存在的异构及反异构、不饱和脂胞酸、藿烯、蕨烯的存在，表明细菌的活动较为活跃；高含量的具生物构型的ββ藿烷系数、C_(27)-C_(29)甾烯醇、藿烯、蕨烯的存在显示出固城湖沉积有机质尚处于很低的演化阶段，但以C_(30)αβ为主峰及22S > 22R的藿烷分布又表明湖泊有源于周边古老岩石的风化产物；不饱和脂肪酸的与饱和脂肪酸的相对浓度之比C18：2/C18：0、C18：1/C18：0、C16：1/C16：0、TOC含量、C/N随剖面深度增加而降低及C_(27)、C_(29)甾烷醇/甾烯醇随埋深增加而增大表明了早期成岩作用的进行。本文不仅仅在于对湖相沉积物可溶有机质中各组分进行了全面的、详细地分析，更重要的是初次尝试了从有机地化的角度来确定分子标志物、古生物量与突变事件的关系。本研究将为第四纪古气候古环境变迁的研究提供更新的证据、开拓更为广阔的应用前景。

Simple derivatization method for sensitive determination of fatty acids with fluorescence detection by high-performance liquid chromatography using 9-(2-hydroxyethyl)-carbazole as derivatization reagent

A simple and sensitive method for the determination of short and long-chain fatty acids using high-performance liquid chromatography with fluorimetric detection has been developed. The fatty acids were derivatized to their corresponding esters with 9-(2-hydroxyethyl)-carbazole (HEC) in acetonitrile at 60 degreesC with 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride as a coupling agent in the presence of 4-dimethylaminopyridine (DMAP). A mixture of esters of C-1-C-20 fatty acids was completely separated within 38 min in conjunction with a gradient elution on a reversed-phase C-18 column. The maximum fluorescence emission for the derivatized fatty acids is at 365 nm (lambda (ex) 335 nm). Studies on derivatization conditions indicate that fatty acids react proceeded rapidly and smoothly with HEC in the presence of EDC and DMAP in acetonitrile to give the corresponding sensitively fluorescent derivatives. The application of this method to the analysis of long chain fatty acids in plasma is also investigated. The LC separation shows good selectivity and reproducibility for fatty acids derivatives. The R.S.D. (n = 6) for each fatty acid derivative are <4%. The detection limits are at 45-68 fmol levels for C-14-C-20 fatty acids and even lower levels for

Comparative X-ray photoelectron spectroscopic study on the desulfurization of thiophene by Raney Nickel and rapidly quenched skeletal nickel

The desulfurization of thiophene on Raney Ni and rapidly quenched skeletal Ni (RQ Ni) has been studied in ultrahigh vacuum (UHV) by X-ray photoelectron spectroscopy (XPS). The Raney Ni or RQ Ni can be approximated as a hydrogen-preadsorbed polycrystalline Ni-alumina composite. It is found that thiophene molecularly adsorbs on Raney Ni or RQ Ni at 103 K. At 173 K, thiophene on alumina is desorbed, while thiophene in direct contact with the metallic Ni in Raney Ni undergoes C-S bond scission, leading to carbonaceous species most probably in the metallocycle-like configuration and atomic sulfur. On RQ Ni, the temperature for thiophene dissociation is about 100 K higher than that on Raney Ni. The lower reactivity of RQ Ni toward thiophene is tentatively attributed to lattice expansion of Ni crystallites in RQ Ni due to rapid quenching. The existence of alumina and hydrogen may block the further cracking of the metallocycle-like species on Raney Ni and RQ Ni at higher temperatures, which has been the dominant reaction pathway on Ni single crystals. By 473 K, the C Is peak has disappeared, leaving nickel sulfide on the surface.

Capturing the overarm throw in darts employing wireless inertial measurement

This work employs a custom built body area network of wireless inertial measurement technology to conduct a biomechanical analysis of precision targeted throwing in competitive and recreational darts. The solution is shown to be capable of measuring key biomechanical factors including speed, acceleration and timing. These parameters are subsequently correlated with scoring performance to determine the affect each variable has on outcome. For validation purposes an optical 3D motion capture system provides a complete kinematic model of the subject and enables concurrent benchmarking of the 'gold standard' optical inertial measurement system with the more affordable and proactive wireless inertial measurement solution developed as part of this work.