La_(1-x)Pr_xP_5O_(14)晶体的发光

Pr~(3+)离子的能级结构丰富,在紫外可见区有很好的荧光发射。因此,以Pr~(3+)为激活离子的发光材料研究工作引起了人们的关注。轻稀土五磷酸盐晶体结构为单斜晶系,空间群为P_(1/2)/C,稀土离子处在隔离的多面体中,离子间的作用减弱,即使在化学计量比的PrP_5O_(14)仍得到激光输出。本文采用水热法生长出La_(1-x)Pr_xP_5O_(14)

SYNTHESIS, SOLUTION DYNAMICS AND X-RAY CRYSTAL-STRUCTURES OF NEODYMIUM-YLIDE COMPLEXES, [(C(5)H(4)R)(3)NDCH2P(ME)PH(2)] (R=H, BU(T))

The interaction of [(C(5)H(4)R)(2)NdCl.2LiCl] (R = H, Bu(t)) with one equivalent of Li[(CH2)(CH2)PPh(2)] in refluxing tetrahydrofuran gave the purplish-blue complex [(C(5)H(4)R)(3)NdCH2P(Me)Ph(2)] in 50% yield. The compounds have been fully characterized by analytical, spectroscopic and X-ray diffraction methods. Variable temperature P-31{H-1} NMR spectroscopy indicated the existence of the following equilibrium: [(C(5)H(4)R)(3)NdCH2P(Me)Ph(2)] + THF reversible arrow (C(5)H(4)R)(3)Nd(THF) + CH2=P(Me)Ph(2). At room temperature, the exchange between the coordinated and free ylide ligand is slow on the NMR time scale.

细胞色素C在单糖修饰金电极上的直接电化学

Hill等发现在4,4′-联吡啶存在时,细胞色素C在金电极上能进行准可逆的电化学反应。在研究细胞色素C的直接电化学过程中,人们又发现一些生物小分子如氨基酸、嘌呤等对细胞色素C的电化学反应有促进作用,但迄今未见有关糖类分子对细胞色素C电化学反应促进作用研究的报道。本文研究了5种单糖对细胞色素C电化学反应的促进作用。

Ce_xGd_(1-x)P_5O_(14)晶体的生长及其发光特性的光谱研究

本文采用蒸发溶液法生长出一系列 Ce_xGd_(1-x)P_5O_(14)晶体,测定了它们的结构均属于单斜晶系、空间群 P2_1/c,用稳态和时间分辨荧光光谱法研究了该晶体中不同 Gd 含量时的发光性能,观察到随着(1-x)值增加,包含有 Gd~(3+)发射在内的314nm 峰增强和 Ce~(3+)的荧光寿命的有规律递减,说明了存在着 Ce~(3+)至 Gd~(3+)的能量传递。

水溶性聚合物和两亲聚合物:14.丙烯酰胺/2-丙烯酰胺基十六烷磺酸铵无规共聚物

水溶液中用硫酸亚铁-异丙苯过氧化氢氧化还原引发体系合成了丙烯酰胺(AM)/2-丙烯酰胺基十六烷磺酸铵(AMC_(16)SNH_4)无规共聚物。用元素分析、IR、~(13)C-NMR和~1H-NMR对其进行了表征。对水溶液性质的研究结果表明,与部分水解聚丙烯酰胺相比,这种新型共聚物有着优异的耐盐性、耐温性和贮存稳定性。

LnP_5O_(14)(Ln=La—Tb)晶体的相变和缺陷

本文用X射线衍射方法研究 LnP_5O_(14)(Ln=La,Pr,Nd,Sm,Tb)晶体相变表明,相变是晶轴 c 和α夹角β随温度升高逐渐减小的过程,也就是晶体的畸变角δ随温度下降而增加。相变温度随稀土离子半径由 La 到 Tb 减小呈线性增加,最后讨论了晶体缺陷随温度的变化关系。

PrP_5O_(14)的晶体结构与铁弹畴

本文用X射线衍射方法研究了PrP_5O_(14)的晶体结构和铁弹相变。晶体空间群为P2_1/c,晶胞参数a=8.777(1)A,b=9.029(2)A,c=13.068(2)A,β=90.35°(1),z=4,最终R值为0.046。在130±5℃转变成正交晶系,空间群为P_(ncm),a=8.813(7)A,b=9.075(2)A,c=13.119(10)A。高温相变使晶体产生了铁弹性孪晶,室温下晶体属mmmF2/m类铁弹体。

Ce_xGd_yTb_(1-x-y)P_5O_(14)晶体生长及其光谱

采用蒸发溶液法从磷酸溶液中生长出一系列Ce_xGd_yTb_(1-x-y)P_5O_(14)晶体.测定了它们的结构.它们属于单斜晶系,空间群P2_(1/c).测定了Ce_(0.9)Gd_(0.1)P_5O_(14)、Ce_(0.9)Tb_(0.1)P_5O_(14)和La_(0.8)Gd_(0.1)Tb_(0.1)P_5O_(14)等晶体的光谱.首次观察到,将Gd加入Ce_xTb_(1-x)P_5O_(14)晶体中形成.Ce_xGd_yTb_(1-x-y)P_5O_(14)时阻碍了Ce~(3+)→Tb~(3+)的能量传递,导致Ce~(3+)的发射峰增强,Tb~(3+)的~5D_4—~F_J发射峰减弱、而~5D_3—~7F_J发射峰增强.

Cytoglobosins A-G, Cytochalasans from a Marine-Derived Endophytic Fungus, Chaetomium globosum QEN-14

Financial support from the Ministry of Science and Technology of China (2010CB833802 and 2007AA09Z446) and from the National Science Foundation of China (30910103914) is gratefully acknowledged.

Seasonal and spatial distribution of matrix-bound phosphine and its relationship with the environment in the Changjiang River Estuary, China

Sediment is commonly considered as a source of phosphine, which is a highly toxic and reactive atmospheric trace gas. This study aims to investigate the seasonal and spatial distribution of matrix-bound phosphine (MBP) and its relationship with the environment in the Changjiang River Estuary. A total of 43 surface sediments were collected in four seasons of 2006, and concentrations of MBP and relative environmental factors were analyzed. MBP ranged from 1.93 to 94.86 ng kg(-1) dry weight (dw) with an average concentration of 17.14 ng kg(-1) dw. The concentrations of MBP in the tipper estuary were, higher than those in the lower estuary, which could be attributed to greater pollutant inputs in the upper estuary. The concentrations of MBP also varied with season, with November > August > May > February. Significant correlations existed between MBP and total phosphorus (TP), organic phosphorus (OP), inorganic phosphorus (W), organic carbon (OC), total nitrogen (TN), the grain size, and redox potential (Eh), suggesting that these sedimentary environmental characteristics played an important role in controlling the MBP levels in the sediments. Notably, there were positive linear relationships between the concentrations of soluble reactive phosphorus (SRP), TP, and chlorophyll a (Chl a) in bottom water and MBP in sediments. These relationships might be very complicated and need further exploration. This work is the first comprehensive study of the seasonal and spatial distribution of MBP in sediments and its relationships with environmental factors in a typical estuary, and will lead to deeper understanding of the phosphorus (P) biogeochemical cycle. (C) 2008 Elsevier Ltd. All rights reserved.

The distribution, enrichment and source of potential harmful elements in surface sediments of Bohai Bay, North China

A geochemical study of Bohai Bay surface sediments was carried out to analyze the potential harmful element (PHE: Ge, Mo, In, Sn, Sb,Te, Tl, Bi and V) concentrations, transportation and deposition, enrichment factors and sources. Germanium, Mo, In, Sn, Sb, Te, Tl, Bi and V concentrations in the surface sediments were: 1.43-1.71, 0.52-1.43, 0.04-0.12, 2.77-4.14, 1.14-2.29, 0.027-0.085, 0.506-0.770, 0.27-0.63 and 70.35-115.90 mu g/g, respectively. The distributions of total PHE concentrations, together with sequential extraction analyses, showed that the PHEs were mainly due to natural inputs from the continental weathering delivered to the bay by rivers and atmospheric transportation and deposition. However, high Mo, Sb, Te, Bi and V occurred in non-residual fractions, suggesting some anthropogenic inputs in addition to the natural inputs. Besides sources, the distributions of PHEs were influenced by the coupling of physical, chemical and biological processes. Enrichment factor (EF) was computed for each site for each element in order to assess the polluting elements and the degree of pollution at each site. Results revealed that the EFs were generally lower than 1.0, particularly for Ge, Mo, In, Sn, Tl and V; however, the EFs were higher (>1.5), particularly for Sb, Te and Bi, revealing moderate contamination. (C) 2010 Elsevier B.V. All rights reserved.

Effect of H2S on stress corrosion cracking and hydrogen permeation behaviour of X56 grade steel in atmospheric environment

Susceptibility to stress corrosion cracking of X56 steel and its relationship with hydrogen permeation behaviour in atmospheric environment containing H2S was investigated by hydrogen permeation tests at a slow strain rate. The results show that: the fracture strain decreases with the decrease of strain rate under the same experimental conditions; the fracture strain also decreases with the increase of H2S concentration under the same strain rate, and the increased concentration of H2S has no significant effect on the hydrogen permeation in the first wet, etc. dry cycle, however has lead to increased hydrogen permeation in the later cycles. The SEM images of the fractured surfaces show clear evidences of enhanced stress corrosion cracking susceptibility by H2S.

Hydrogen entry into steel during atmospheric corrosion process

Hydrogen entry and permeation into iron were measured by an electrochemical method during atmospheric corrosion reaction. The hydrogen permeation was enhanced on passive films because the hydrogen adsorption increased by the hydrogen evolution mechanism which is different from that on a bear iron surface. The permeation rate during a wet and dry corrosion cycle showed a maximum in the drying process depending upon the surface pH and the corrosion potential. The pollutant such as Na2SO3 which decreases the pH and the corrosion potential causes an increase in the permeation rate. The mechanism of the change in the permeation rate during the wet and dry cycles is explained by the polarization diagram of the electrode covered by thin water layer. (c) 2005 Elsevier Ltd. All rights reserved.

Hydrogen permeation behavior and corrosion monitoring atmospheric of steel in cyclic wet-dry environment

Hydrogen permeation of 16Mn steel under a cyclic wet-dry condition was investigated by Devanathan-Stachurski's electrolytic cell with a membrane covered on the exit side by a nickel layer and the weight loss was measured for each wet-dry cycle. The results show that hydrogen permeation current change with different atmospheric environment: distilled water, seawater, and seawater containing 100 ppm H2S. The results show that seawater can induce an increase in the hydrogen permeation current due to the hydrolyzation reaction. And after the increase, equilibrium is reached due to the equilibrium of hydrolyzation reaction effect and the block of the rust layer. On the other hand, H2S contamination also can induce an increase in the maximum hydrogen permeation current due to the hydrolyzation reaction. And H2S contamination delays the time that hydrogen permeation is detected because of the formation of the FeS(1-x) film. The FeS(1-x) film can block the absorption of hydrogen onto the specimen surface. The surface potential change and the pH change of the metal surface control the hydrogen permeation current. And a clear linear correlation exists between the quantities of hydrogen permeated through the 16Mn steel and the weight loss. Based on the linear correlation, we monitored the corrosion rate by monitoring the hydrogen permeation current by a sensor outside. Good coherences were shown between results in laboratory and outside.

Enhancement of atmospheric pressure chemical ionization for the determination of free and glycine-conjugated bile acids in human serum

A highly sensitive and accurate method based on the precolumn derivatization of bile acids (BA) with a high ionization efficiency labeling reagent 1,2-benzo-3,4-dihydrocarbazole-9-ethyl-benzenesulfonate (BDEBS) coupled with LC/MS has been developed. After derivatization, BA molecules introduced a weak basic nitrogen atom into the molecular core structure that was readily ionized in commonly used acidic HPLC mobile phases. Derivatives were sufficiently stable to be efficiently analyzed by atmospheric pressure chemical ionization (APCI)-MS/MS in positive-ion mode. The MS/MS spectra of BA derivatives showed an intense protonated molecular ion at m/z [M + H](+). The collision-induced dissociation of the molecular ion produced fragment ions at [MH - H2O](+), [MH - 2H(2)O](+), [MH - 3H(2)O](+). The characteristic fragment ions were at m/z 320.8, 262.8, and 243.7 corresponding to a cleavage of N - CO, O - CO, and C - OCC, respectively, and bonds of derivatized molecules. The selected reaction monitoring, based on the m/z [M + H]+ -> [MH - H2O](+), [MH - H2O](+), [MH - 2H(2)O](+), [MH-3H(2)O](+), 320.8, 262.8, and 243.7 transitions, was highly specific for the BA derivatives. The LODs for APCI in a positive-ion mode, at an S/N of 5, were 44.36-153.6 fmol. The validation results showed high accuracy in the range of 93-107% and the mean interday precision for all standards was < 15% at broad linear dynamic ranges (0.0244-25nmol/mL). Good linear responses were observed with coefficients of > 0.9935 in APCI/MS detection. Therefore, the facile BDEBS derivatization coupled with mass spectrometric analysis allowed the development of a highly sensitive and specific method for the quantitation of trace levels of the free and glycine-conjugated BA from human serum samples.