W-183 NMR characterization of rare earth heteropolymetalates in aqueous solution

W-183 NMR spectra were obtained for [La(AsW11O39)(2)](11-), [La(As2W17O61)(2)](17-), [La(SiW9Mo2O39)(2)](13-), [LaSb9W21O86](16-), [LaAs4W40O140](25-) and alpha-, beta-[(CeO)(3) . (SiW9O34)(2)](14-) complexes, Tungsten NMR studies showed that the C-s symmetry of the square antiprism for [La(ASW(11)O(39))(2)](11-) and [La(As2W17O61)(2)](17-) anions keep constant in aqueous solution; the lanthanide accupied the central S-1 site in [LnSb(9)W(21)O(86)](16-) and [LnAs(4)W(40)O(140)](25-) complexes, respectively, and lanthanide metal cations gave [(CeO)(3) . (SiW9O34)(3)](14-) type of complexes with SiW9O3410-.

稀土杂多化合物在溶液中的￣（183）W���磁共振表征

~（１８３）Ｗ核磁共振研究确认，Ｌａ（ＡｓＷ_（１１））_２、Ｌａｍ（Ａｓ_２Ｗ_（１７））_２在溶液中仍保持其四方反棱柱的Ｃ_３结构，Ｌａ（ＳｉＷ_９ＭＯ_２）_２阴离子中，２个Ｍｏ原子取代了２个等价的Ｗ原子，在穴状杂多阴离子ＬｎＡｓ_４Ｗ_（１０）和ＬｎＳｂ_９Ｗ_（２１）中，稀土离子占据中心Ｓ_１位置，ＳｉＷ_９与稀土离子生成（ＬｎＯ）_３（ＳｉＷ_９）_２型杂多阴离子。

Dawson结构杂多阴离子~（183）W���NMR谱的研究──“极位”W���子~（183）W���NMR谱化学位移值的预测

本文研究了Ｄａｗｓｏｎ结构取代原子数与相应的１８３ＷＮＭＲ谱中“极位’Ｗ原子的化学位移值间的关系，预测广α－１，２－［Ｐ２Ｗ１６Ｎｂ２Ｏ６２］８－α－１－２，３－［Ｐ２Ｗ１５ＭｏＮｂ２Ｏ６２］８－“极位”Ｗ原子１８３ＷＮＭＲ谱化学位移们，结果α－１，２－［Ｐ２Ｗ１６Ｎｂ２Ｏ６２］８－中与取代Ｎｂ相连“极位”Ｗ原子的化学位移值为－８８ｐｐｍ，与取代Ｎｂ书对称“极位”Ｗ原了的化学位移值为－１４４．７ｐｐｍ，与取代Ｎｂ不对称“极位”Ｗ原子的化学位移值为－１３０．５ｐｐｍ，α－１－２，３－［Ｐ２Ｗ１５ＭｏＮｂ２Ｏ６２］８－中与取代Ｍｏ对称“极位”Ｗ原子的化学位移值为－１３４．７ｐｐｍ，与取代Ｎｂ对称“极位”Ｗ原子的化学位移值为－１４５．６ｐｐｍ．

Dawson结构钨铌磷杂多配合物~(183)W NMR谱的研究

过渡金属离子取代的杂多钨酸盐,具有金属叶啉的类似结构,在烯烃环氧化反应中具有比金属叶啉更优异的催化活性和选择性,特别重要的是其抗氧化性能强,在烯烃基质存在下比金属叶啉稳定,催化寿命持久,并称其为无机金属叶啉,因而引起人们的极大关注.

掺W���Bi系中高Tc超导相的影响

自Maeda发现高Tc超导体BiSrCaCuO以来,引起了人们广泛兴趣;由于它有较高的超导转变温度(Tc>100K),无剧毒、价廉和自高温冷却到室温无结构相变等特点,Bi系是一很有实用前景的高Tc超导体;已经确定Bi系中含有三个超导相(2201,2212,2223相),但是迄今要制得较纯的2223高Tc相还有一定困难,无疑这对它的基础研究和实用开发都受到了限制,因此制备更纯的Bi系2223相具有重要的意义。

Extraction behavior of Mo and W as homologs of Sg with α-benzoinoxime

Solvent extraction of molybdenum and tungsten as homologues of Sg with a-benzoinoxime from HCl solutions has been investigated. The extraction equilibration was achieved at 20s for Mo and W. Molybdenum was almost quantitatively extracted from 0.001 to 4M HCl solutions, and the extraction yields decreased at higher and lower acid concentrations due to the formation of anionic oxychloride complex and anionic species MO42-, respectively. The extraction yield of W was lower than that of Mo during the whole range of acid concentration. The composition of the extracted species was determined by using the slope method in present experiment. The elemental analysis, IR and 1H NMR spectra of the extracted species suggest that the extracted complex contain one MoO22+or WO22+ groups bonded with two a-benzoinoxime molecules.

Effects of increased pCO(2) and temperature on the North Atlantic spring bloom. I. The phytoplankton community and biogeochemical response

The North Atlantic spring bloom is one of the largest annual biological events in the ocean, and is characterized by dominance transitions from siliceous (diatoms) to calcareous (coccolithophores) algal groups. To study the effects of future global change on these phytoplankton and the biogeochemical cycles they mediate, a shipboard continuous culture experiment (Ecostat) was conducted in June 2005 during this transition period. Four treatments were examined: (1) 12 degrees C and 390 ppm CO2 (ambient control), (2) 12 degrees C and 690 ppm CO2 (high pCO(2)) (3) 16 degrees C and 390 ppm CO2 (high temperature), and (4) 16 degrees C and 690 ppm CO2 ('greenhouse'). Nutrient availability in all treatments was designed to reproduce the low silicate conditions typical of this late stage of the bloom. Both elevated pCO(2) and temperature resulted in changes in phytoplankton community structure. Increased temperature promoted whole community photosynthesis and particulate organic carbon (POC) production rates per unit chlorophyll a. Despite much higher coccolithophore abundance in the greenhouse treatment, particulate inorganic carbon production (calcification) was significantly decreased by the combination of increased pCO(2) and temperature. Our experiments suggest that future trends during the bloom could include greatly reduced export of calcium carbonate relative to POC, thus providing a potential negative feedback to atmospheric CO2 concentration. Other trends with potential climate feedback effects include decreased community biogenic silica to POC ratios at higher temperature. These shipboard experiments suggest the need to examine whether future pCO2 and temperature increases on longer decadal timescales will similarly alter the biological and biogeochemical dynamics of the North Atlantic spring bloom.

Distribution of calcifying and silicifying phytoplankton in relation to environmental and biogeochemical parameters during the late stages of the 2005 North East Atlantic Spring Bloom

The late stage of the North East Atlantic (NEA) spring bloom was investigated during June 2005 along a transect section from 45 to 66 degrees N between 15 and 20 degrees W in order to characterize the contribution of siliceous and calcareous phytoplankton groups and describe their distribution in relation to environmental factors. We measured several biogeochemical parameters such as nutrients, surface trace metals, algal pigments, biogenic silica (BSi), particulate inorganic carbon (PIC) or calcium carbonate, particulate organic carbon, nitrogen and phosphorus (POC, PON and POP, respectively), as well as transparent exopolymer particles (TEP). Results were compared with other studies undertaken in this area since the JGOFS NABE program. Characteristics of the spring bloom generally agreed well with the accepted scenario for the development of the autotrophic community. The NEA seasonal diatom bloom was in the late stages when we sampled the area and diatoms were constrained to the northern part of our transect, over the Icelandic Basin (IB) and Icelandic Shelf (IS). Coccolithophores dominated the phytoplankton community, with a large distribution over the Rockall-Hatton Plateau (RHP) and IB. The Porcupine Abyssal Plain (PAP) region at the southern end of our transect was the region with the lowest biomass, as demonstrated by very low Chla concentrations and a community dominated by picophytoplankton. Early depletion of dissolved silicic acid (DSi) and increased stratification of the surface layer most likely triggered the end of the diatom bloom, leading to coccolithophore dominance. The chronic Si deficiency observed in the NEA could be linked to moderate Fe limitation, which increases the efficiency of the Si pump. TEP closely mirrored the distribution of both biogenic silica at depth and prymnesiophytes in the surface layer suggesting the sedimentation of the diatom bloom in the form of aggregates, but the relative contribution of diatoms and coccolithophores to carbon export in this area still needs to be resolved.

Rediscovery of the sea cucumber "Toxodora" pacifica Ohshima, 1915 (Echinodermata : Holothuroidea : Apodida)

The apodous holothurian species originally described by Ohshima ( 1915) as Toxodora pacifica has been rediscovered, and its known geographic range extended from Suruga Bay, Japan to the western side of the Yellow Sea, China. As the genus name Toxodora is no longer available, a new genus name, Neotoxodora Liao, Pawson, and Wei, is proposed. The type material of Neotoxodora pacifica is lost, and a Neotype is named for this species.

生长条件对苔藓硫含量和硫同位素组成指示大气硫沉降的影响

对相同大气沉降和土壤背景但生长条件不同的苔藓w���S）和δ（34S）进行了分析.土生苔藓w���S）高于石生苔藓,表明土壤对苔藓w���S）指示大气硫沉降有影响.受树冠遮挡的苔藓w���S）偏低反映了树冠吸收会削弱冠下的大气硫输入,而不同类型树冠对大气硫的截留吸收程度不同,这可能是造成树冠下方苔藓w���S）存在差异的主要原因,但随树冠厚度变化无明显规律.石生苔藓δ（34S）与大气硫δ（34S）吻合,而土生苔藓δ（34S）明显受土壤硫的影响而偏正.此外,树冠下苔藓δ（34S）偏高还与树冠吸收大气硫的过程中发生34S歧视有关,苔藓δ（34S）随树冠厚度增加而偏正,进一步证实了树冠的长期吸收会使沉降到树冠下的大气硫源δ（34S）偏正.因此,受生长条件歪曲了的苔藓w���S）和δ（34S）不能用于解释大气硫沉降的变化和来源,开阔地的石生苔藓比土生苔藓和受树冠遮挡的苔藓更具有大气指示意义.

湘西沃溪Au-Sb-W���床中白钨矿Sm-Nd和石英Ar-Ar定年

利用白钨矿对金属矿床进行了Sm-Nd同位素定年. 研究结果表明, 湘西沃溪Au-Sb-W���床中白钨矿的Sm, Nd含量较高, Sm/Nd值较大. 在147Sm/144Nd-143Nd/144Nd图解中, 浸染状白钨矿样品呈良好的线性分布, 其对应的等时线年龄为402±6 Ma, εNd(t)值为−30.7. 该矿两个石英样品的40Ar-39Ar年龄谱均呈“马鞍型”, 样品的最小视年龄、坪年龄和等时线年龄基本一致, 其最小视年龄(420±20和414±19 Ma)与白钨矿的Sm-Nd同位素数据相当吻合. 白钨矿的Sm-Nd年龄和石英Ar-Ar年龄均表明沃溪矿床形成于加里东晚期, 这与湖南雪峰山地区的构造演化和一些金锑钨矿床的同位素年代数据相吻合. 白钨矿的初始εNd值异常低, 远低于湖南元古宇地层的相应值, 成矿流体中的Nd很可能来自下伏的更老的陆壳基底. 对该矿成矿时间的厘定和对其成矿物源的制约为进一步认识其矿床成因奠定了基础.