Activated carbon supported bimetallic CoMo carbides synthesized by carbothermal hydrogen reduction

A carbothermal hydrogen reduction method was employed for the preparation of activated carbon supported bimetallic carbide. The resultant samples were characterized by BET surface area measurement, X-ray diffraction, and temperature-programmed reduction-mass spectroscopy. The results showed that nanostructured beta-Mo2C can be formed on the activated carbon by carbothermal hydrogen reduction above 700 degreesC. The particle sizes of beta-Mo2C increase with increasing reaction temperatures and Mo loading. The bimetallic CoMo carbide can be synthesized by the carbothermal hydrogen reduction even around 600 degreesC. The bimetallic CoMo carbide is from carbothermal hydrogen reduction of CoMoO4 precursor and is easily formed when the Co/Mo molar ratio is 1.0. Separation of the bimetallic CoMo carbide phase into Mo carbide and Co metal occurs when the temperature of the reduction is above 700 degreesC. The addition of a second metal such as Co and Ni, decreases the formation temperature of carbide because the second metal promotes formation of CHx species from reactive carbon atoms or groups on carbon material and hydrogen, which further carburizes oxide precursors. (C) 2003 Elsevier Science Ltd. All rights reserved.

民勤湖区地下水资源时空变化对灌区景观生态安全的影响研究

以生态安全面临着严重威胁的我国干旱区民勤绿洲湖区灌区景观为例 ,研究地下水资源的时空变化对灌区生态安全的影响 .利用GIS进行地下水的空间插值得到地下水埋深与地下水矿化度的时空变化 .结果表明 ,地下水埋深在 14年间持续下降 ,且灌区中心地带的地下水埋深的下降速率较边缘地带快 ,导致地下水降落漏斗不断加深 ,并逐渐由灌区中心向边缘扩展 .大于 3m的地下水埋深面积比例逐年增加 ,由 1987年占湖区总面积的 81.2 %上升到 2 0 0 1年的 97.4 % .地下水埋深的持续下降导致土壤含水量降低是除人为破坏而引起林木自然衰败、死亡 ,并引起灌区自然生态安全水平降低的主要原因 .当地下水埋深超过 8m ,地下 2m处土壤含水率达到 12 %以下 ,大部分乔木林枯梢率达到 90 %以上 ,而灌木林枯梢率也达到 5 0 %以上 .受地下水位下降的影响 ,14年间有林地、灌木林地与疏林地的斑块面积分别减少了6 7%、5 4 %与 31% ,斑块数量减少 35、4 2与 5 0块 .地下水矿化度的上升导致作物的安全生长格局发生显著变化 ,导致农业经济效益降低、种植业结构调整受到严重制约 ,构成对灌区经济生态安全的严重影响 .合理分配流域中、下游水资源量 ,限制人类不合理的土地利用方式 ,减少灌区耕地面积 ,构建安全的景观格局 ,逐渐恢复地下水

Density functional study on the reaction mechanism of palladium-catalyzed addition of cyanoboranes to Alkynes

The B3LYP hybrid density functional method has been carried Out to Study theoretically the mechanisin of Pd(0)-catalyzed alkyne cyanoboration reaction. Both the intermolecular and intramolecular alkyne cyanoboration reactions were studied. For each reaction, three paths were proposed. In path A of each reaction, the first step is B-CN bond oxidative addition to bisphosphine complex Pd(PH3)(2), in path B of each reaction, the first step is alkyne coordination to bisphosphine complex Pd(PH3)2, and in path C of each reaction, the first step is the PH3 dissociation front Pd(PH3)2 to form monophosphine complex Pd(PH3) For both reactions, path B is favored.

Direct electrochemistry and electrocatalysis of horseradish peroxidase immobilized in sol-gel-derived ceramic-carbon nanotube nanocomposite film

The sol-gel-derived ceramic-carbon nanotube (SGCCN) nanocomposite film fabricated by doping multiwall carbon nanotubes (MWNTs) into a silicate get matrix was used to immobilize protein. The SGCCN film can provide a favorable microenvironment for horseradish peroxidase (HRP) to perform direct electron transfer (DET) at glassy carbon electrode. The HRP immobilized in the SGCCN film shows a pair of well-defined redox waves and retains its bioelectrocatalytic activity to the reduction of O-2 and H2O2, which is superior to that immobilized in silica sol-gel film.

The influence of arrangement of St in MBS on the properties of PVC/MBS blends

Three series of MBS core-shell impact modifiers were prepared by grafting styrene and methyl methacrylate onto PB or SBR seed latex in emulsion polymerization. All the MBS modifiers were designed to have the same total chemical composition, and MMA/Bd/St equals 30/42/28, which is a prerequisite for producing transparent blends with PVC. Under this composition, there were three different ways of arrangement for styrene in MBS, which led to the different structure of MBS modifier. The concentration of MBS in PVC/MBS blends was kept at a constant value of 20 wt.%. The effects of arrangement of St in MBS on the mechanical and optical properties of PVC/MBS blends were studied. The notched Izod impact test results showed that the MBS with a PB homopolymer core grafted with St had a lowest brittle-ductile transition (BDT) temperature and BDT temperature increased with the amount of St copolymerized with Bd in the core of MBS. The transparency of blends also increased with the amount of St copolymerized with Bd in the core. TEM results showed that the arrangement of St in MBS influenced the deformation behavior. Two deformation modes were observed in the blends: cavitation and shear yielding.

Effect of electron radiation on crystal structure transition of trans-1, 4-polybutadiene

trans-1,4-Polybutadiene (PTBD) was synthesized by rare earth catalyst system, The effect of electron radiation on phase transition from monoclinic phase to hexagonal phase was observed by TEM, Electron diffraction patterns of monoclinic phase, hexagonal phase and two coexistent phases were recorded, The mechanism of phase transition was also discussed in this paper.

Two-step-method extraction of endohedral metallofullerenes

A new and efficient extraction method of endohedral metallofullerenes, especially of rare-earth elements encapsulated metallofullerenes, has been reported in this paper. Soxhlet-extraction of raw soot with toluene was used in the first step to wash away most accompanying C-60, C-70. Then pyridine was chosen as solvent to obtain high-temperature and high pressure extract. Two kinds of extract were analysed by DEI-MS and LDI-MS, the results indicate that this two-step method can provide the extract which has the highest fraction of endohedral metallofullerenes. So it will greatly simplify the following separation and purification processes of metallofullerenes.

两步法提取笼内金属富勒烯

两步法提取笼内金属富勒烯郝春雁，刘子阳，徐文国，郭兴华，刘淑莹（中国科学院长春应用化学研究所，吉林大学化学系，长春，１３００２２）关键词金属富勒烯，索氏提取，ＤＥＩ－ＭＳ，ＬＤＩ－ＭＳ目前笼内包含金属的富勒烯化合物以其新颖独特的结构和性质而格外引人注...

Pervasive autocorrelation of the chemical index of alteration in sedimentary profiles and its palaeoenvironmental implications

The chemical index of alteration has been used widely for reconstruction of the palaeoclimate. However, the mechanisms and environmental factors controlling the chemical index of alteration of sediments are not yet fully understood. In this study, autocorrelations of the chemical index of alteration in nine sedimentary profiles, from both the land and the sea, spanning different geological times, are discussed. The sediments of these profiles have different origins (dust, fluvial or ocean sediments) and are from various climate situations and sedimentary environments. Autocorrelations of chemical index of alteration series are ubiquitously evident in all profiles. It is suggested here that autocorrelations may be caused by post-depositional changes such as persistent weathering and diagenesis. As a result, the chemical index of alteration may not reflect climatic conditions during the time of sediment deposition. This study strongly recommends the confirmation of the reliability and veracity of the chemical index of alteration before it is adopted to evaluate the weathering degree of parent rocks and to reconstruct the past climate. Significant autocorrelations in loess profiles were specifically observed, suggesting that the existing understanding of loess deposition in terms of climate conditions requires re-examination, and that previous reconstructions of rapid climate changes (for example, in centennial-millennial scales) should be treated with caution.

黄海冷水团及邻近海域小型底栖动物多样性及其环境效应

2007年夏季对黄海冷水团及邻近海域共48个站位的小型底栖动物组成、丰度和生物量，以及环境因子进行了科考研究。所调查站位的小型底栖动物平均丰度达2194 ± 1598 inds./10cm2，其中北黄海17个站位平均丰度为3408 ± 1578 inds./10cm2，南黄海31个站位平均丰度为1529 ± 1121 inds./10cm2。调查站位平均生物量为1839 ± 1289 g dwt/10cm2，其中北黄海站位平均生物量为2760 ± 1340g dwt/10cm2，南黄海平均生物量为1335 ± 902g dwt/10cm2。在分选出的共18个小型底栖动物类群中，丰度上均以自由生线虫占绝对优势，达总量的88%，且在南（88.3%）、北黄海（87.7%）基本无差异。在生物量上，同样以自由生线虫贡献最多（42％），多毛类居次（22%），其他生物量较多的还有桡足类（13%）和甲壳类幼体（12%）。在小型底栖动物的垂直分布上，分布于沉积物表层0-2cm的小型底栖动物占79%，次表层2-5cm占17%，最底层5-8cm仅占4%。统计分析表明研究站位小型底栖动物丰度和生物量与沉积物叶绿素a、有机质含量、中值粒径显著或极显著正相关，与水深呈极显著负相关，此外小型底栖动物生物量与沉积物粉砂粘土含量显著负相关。 同年秋季搭载开放航次对黄海5个站位、东海3个站位、南海2个站位的小型底栖动物组成、丰度和生物量，以及环境因子进行了调查研究。对三个海域小型底栖动物的比较研究发现，平均丰度以黄海最高，达2132 ± 946 inds./10cm2，东海次之，为1954 ± 2047 inds./10cm2，而南海仅156 ± 56 inds./10cm2；三海域的平均生物量依次为2193 ± 1148 g dwt/10cm2、1865 ± 1555 g dwt/10cm2和212 ± 22 g dwt/10cm2。在分选出的共14个小型底栖动物类群中，丰度上均以自由生线虫占绝对优势，分别占总量的85%、89%、85%。在生物量上，黄海以自由生线虫贡献最多（33％），多毛类居次（18%）；东海二者比例相近（约37％），而南海则以多毛类占绝对优势（56％），线虫居次（25%）。在小型底栖动物的垂直分布上，三个海区差异较大：分布于沉积物表层0-2cm的小型底栖动物在黄海高达90%，东海仅46%，在南海为63%。统计分析表明，本研究站位小型底栖动物丰度与沉积物中的叶绿素a及脱镁叶绿素a含量和底温呈显著正相关，与水深呈显著负相关。该结果与本航次之后在广东湛江和海南以东的南海海域开展的908调查结果形成了鲜明对照，后者的小型底栖动物及线虫丰度与沉积物中有机质含量呈显著正相关，与水深呈显著负相关，表明近海受人类干扰影响较大。 本文利用微宇宙实验方法，来确定不同浓度梯度的Cu、Pb以及Cu/ Pb混合重金属污染物对青岛湾小型底栖动物（主要是线虫）的影响。加入污染物后，分别在1、3、7、14、21天进行取样分析。结果显示，Cu和Cu/Pb混合高浓度实验单元组的线虫丰度除在第21天有较明显减少外，在整个实验周期内基本没有变化，分析可能系高浓度Cu的固定作用从而使小型底栖动物无法腐烂降解造成的。同一时间尺度上，各重金属污染物实验单元的线虫丰度均高于（或接近于）空白对照组，较高浓度的重金属污染物实验单元的线虫丰度高于（或接近于）较低浓度重金属污染物实验单元，Cu/Pb混合低浓度实验单元的线虫丰度高于同一时间尺度Cu低浓度和Pb低浓度实验单元。推测是由于采样点的线虫群落中存在对Cu和Pb的耐受种或者“机会种”造成的。

Morphological and ultrastructural characterization of the coelomocytes in Apostichopus japonicus

The coelomocytes suspended in the coelomic fluid and occurring in the coelomic epithelial layer of the sea cucumber Apostichopus japonicus (Selenka) (Holothuroidea: Aspidochirota: Stichopodidae) function as mediators of the immune system, trephocytic cells and nutrient transport cells. Types of coelomocytes are characterized based on their morphological and ultrastructural features. Flow cytometry plus light and electron microscopic analyses were conducted in order to characterize the coelomocytes of A. japonicus. Six types of coelomocytes were identified: lymphocytes, morula cells, amoebocytes, crystal cells, fusiform cells and vibratile cells. Within these major categories, several distinctive cell types occurred that might represent developmental stages. The mean +/- SD coelomocyte concentration in the individuals (body length: 10 to 15 cm; weight: 100 to 150 g) was (3.79 +/- 0.65) X 10(6) cells ml(-1). The coelomic fluid contained mainly hyalinocytes (76.69%) and granulocytes (23.31 %).

Pollinator shift and reproductive performance of the qinghai-tibetan plateau endemic and endangered Swertia przewalskii (Gentianaceae)

Reproductive failure results in many plant species becoming endangered. However, little is known of how and to what extent pollinator shifts affect reproductive performance of endangered species as a result of the artificial introduction of alien insects. In this study we examined breeding systems, visitor species, visiting frequency and seed set coefficients of Swertia przewalskii in two years that had different dominant pollinator species (native vs. alien). Flowers of this species were protandrous and herkogamous and insects were needed for the production of seeds. The stigmatic receptivity of this species was shorter than for other gentians. No significant difference in seed set coefficient was found for hand-pollinated plants between the two years, indicating that pollinator shift only had a minor effect on this plant's breeding system. The commonest pollinators in 2002 were native bumblebees, alien honeybees and occasional solitary bees, however, only alien honeybees were observed in 2004. The flower visitation rate in both years was relatively high, although the total visit frequency decreased significantly in 2004. The control flowers without any treatment produced significantly fewer seed sets in 2004 than in 2002. In the past decade the seed production of this species may have partly decreased due to pollination by alien honeybees, however, we suggest that they might have acted as alternative pollinators ensuring seed production of S. przewalskii when native pollinators were unavailable. The main reason that this plant is endangered is probably the result of habitat destruction, but changes in land use, namely intensified agricultural practice and unfavorable animal husbandry have also contributed to its decline. We recommend that in-situ conservation, including the establishment of a protected area, is the best way to preserve this species effectively.

Determination of free fatty acids in soil and bryophyte plants by precolumn derivatization via HPLC with fluorescence detection and tandem mass spectrometry (HPLC-MS/MS)

A sensitive method for the determination of 30 kinds of free fatty acids (FFAs, C-1-C-30) with 1-[2-(p-toluenesulfonate)-ethyl]-2-phenylimidazole-[4,5-f] 9,10-phenan- threne (TSPP) as labeling reagent and using high performance liquid chromatography with fluorescence detection and identification by online postcolumn mass spectrometry with atmospheric pressure chemical ionization (APCI) source in positive-ion mode (HPLC/MS/APCI) has been developed. TSPP could easily and quickly label FFAs in the presence of K2CO3 catalyst at 90 degrees C for 30 min in N,N-dimethylformamide (DMF) solvent, and maximal labeling yields close to 100% were observed with a 5-fold excess of molar reagent. Derivatives were stable enough to be efficiently analyzed by high performance liquid chromatography. TSPP was introduced into fatty acid molecules and effectively augmented MS ionization of fatty acid derivatives and led to regular MS and MS/MS information. The collision induced cleavage of protonated molecular ions formed specific fragment ions at m/z [MH](+)(molecular ion), m/z [M'+CH2CH2](+)(M' was molecular mass of the corresponding FFA) and m/z 295.0 (the, mass of protonated molecular core structure of TSPP). Fatty acid derivatives were separated on a reversed-phase Eclipse XDB-C-8 column (4.6 x 150 mm, 5 mu m, Agilent) with a good baseline resolution in combination with a gradient elution. Linear ranges of 30 FFAs are 2.441 x 10(-3) to 20 mu mol/L, detection limits are 3.24 similar to 36.97 fmol (injection volume 10 mu L, at a signal-to-noise ratio of 3, S/N 3:1). The mean interday precision ranged from 93.4 to 106.2% with the largest mean coefficients of variation (R.S.D.) < 7,5%. The mean intraday precision for all standards was < 6.4% of the expected concentration. Excellent linear responses were observed with correlation coefficients of > 0.9991. Good compositional data could be obtained from the analysis of extracted fatty acids from as little as 200 mg of bryophyte plant samples.Therefore, the facile TSPP derivatization coupled with HPLC/MS/APCI analysis allowed the development of a highly sensitive method for the quantitation of trace levels of short and long chain fatty acids from biological and natural environmental samples.