In(OH)(3) and In2O3 nanorod bundles and spheres: Microemulsion-mediated hydrothermal synthesis and luminescence properties

Indium hydroxide, In(OH)(3), nano-microstructures with two kinds of morphology, nanorod bundles (around 500 nm in length and 200 nm in diameter) and caddice spherelike agglomerates (around 750 - 1000 nm in diameter), were successfully prepared by the cetyltrimethylammonium bromide (CTAB)/water/cyclohexane/n-pentanol microemulsion-mediated hydrothermal process. Calcination of the In(OH)(3) crystals with different morphologies (nanorod bundles and spheres) at 600 degrees C in air yielded In2O3 crystals with the same morphology. X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and photoluminescence (PL) spectra as well as kinetic decays were used to characterize the samples. The pH values of microemulsion play an important role in the morphological control of the as-formed In(OH)(3) nano-microstructures from the hydrothermal process. The formation mechanisms for the In( OH) 3 nano- microstructures have been proposed on an aggregation mechanism. In2O3 nanorod bundles and spheres show a similar blue emission peaking around 416 and 439 nm under the 383-nm UV excitation, which is mainly attributed to the oxygen vacancies in the In2O3 nano-microstructures.

Synthesis, structure, electrochemistry, photophysics and electroluminescence of 1,3,4-oxadiazole-based ortho-metalated iridium(III) complexes

Four new iridium(III) complexes 1-4, with 1,3,4-oxadiazole derivative as cyclometalated ligand for the first time, have been synthesized and structurally characterized by NMR, EA, MS and X-ray diffraction analysis (except 1). The stronger ligand field strength of the dithiolate ancillary ligands results in higher oxidation potentials and lower HOMO energy levels of complexes than acetylacetone. The absorption spectra of these complexes display low-energy metal-to-ligand charge transfer transition ranging from 350 to 500 nm. Complexes with dithiolate ancillary ligand emit at maximum wavelengths of ca. 500 nm, blue shifting 17 and 11 nm with respect to their counterpart with acetylacetone ligand. The electrophosphorescent devices with 2-4 as phosphorescent dopant in emitting layer have been fabricated. All devices have a low turn-on voltage in the range of 4.5 and 4.9 V. A high-efficiency green emission with maximum luminous efficiency of 5.28 cd/A at current density of 1.37 mA/cm(2) and a maximum brightness of 2592 cd/m(2) at 15.2 V has been achieved in device using 2 as emitter.

Patterning and luminescent properties of nanocrystallineY(2)O(3): Eu3+ phosphor films by sol-gel soft lithography

Nanocrystalline Y2O3:Eu3+ phosphor films and their patterning were fabricated by a Pechini sol-gel process combined with a soft lithography. X-ray diffraction (XRD), thermogravimetric and differential thermal analysis (TG-DTA), atomic force microscopy (AFM), optical microscopy, UV/vis transmission and photoluminescence (PL) spectra as well as lifetimes were used to characterize the resulting films. The results of XRD indicated that the films began to crystallize at 500 degreesC and the crystallinity increased with the elevation of annealing temperatures. Uniform and crack free non-patterned phosphor films were obtained, which mainly consisted of grains with an average size of 70 nm. Using micro-molding in capillaries technique, we obtained homogeneous and defects-free patterned gel and crystalline phosphor films with different stripe widths (5, 10, 20 and 50 mum). Significant shrinkage (50%) was observed in the patterned films during the heat treatment process. The doped Eu3+ showed its characteristic emission in crystalline Y2O3 phosphor films due to an efficient energy transfer from Y2O3 host to them. Both the lifetimes and PL intensity of the Eu3+ increased with increasing the annealing temperature from 500 to 900 degreesC, and the optimum concentrations for Eu3+ were determined to be 5 mol%.

H-1 NMR analysis for metabolites in serum and urine from rats administrated chronically with La(NO3)(3)

H-1 NMR spectroscopy has been used to assess long-term toxicological effects of a rare earth. Male Wistar rats were administrated orally with La(NO3)(3) at doses of 0.1, 0.2, 2.0, 10, and 20 mg/kg body wt, resp., for 3-6 months. Urine was collected at 1, 2, and 3 months and serum samples were taken after 6 months. Numerous low-M-r metabolites in rats serum and rats urine, including creatinine, citrate, glucose, ketone bodies, trimethylamine N-oxide (TMAO), and various amino acids, were identified on 400- and 500-MHz H-1 NMR spectra. La3+-induced renal and liver damage is characterized by an increase in the amounts of the excreted ketone bodies, amino acids, lactate, ethanol, succinate, TMAO, dimethylamine, and taurine and a decrease in citrate, glucose, urea, and allantoin. Information on the molecular basis of the long-term toxicity of La(NO3)(3) was derived from the abnormal patterns of metabolite excretions. An assay of some biochemical indexes and analysis of some enzymes in plasma supported NMR results.

Y_2O_3∶Eu~(3+)发光薄膜的溶胶凝胶法制备、表征及图案化

采用Pechini溶胶 凝胶法制备了纳米级Y2O3∶Eu3+发光薄膜,同时,通过软石印技术得到了条纹宽度为5～60μm的Y2O3∶Eu3+图案化发光薄膜。通过X射线衍射(XRD)、付里叶变换 红外光谱(FT IR)、原子力显微镜(AFM),光致发光(PL)光谱及寿命等方法对得到的发光薄膜进行了表征。XRD结果表明500℃时薄膜开始结晶,900℃已结晶完全,得到了立方相的产物。图案化的条纹在烧结的过程中发生了明显的收缩(50%)。Y2O3基质向掺杂的稀土离子Eu3+发生了有效的能量传递,使得Eu3+显示出5D0 7FJ(J=0,1,2,3,4)特征发射。寿命和光致发光光谱的研究表明,发光强度随着温度的升高而增强。

Synthesis and properties of aromatic polyimides derived from 2,2,' 3,3 '-biphenyltetracarboxylic dianhydride

2,2,'3,3' -Biphenyltetracarboxylic dianhydride (2,2,'3,3'-BPDA) was prepared by a coupling reaction of dimethyl 3-iodophthalate. The X-ray single-crystal structure determination showed that this dianhydride had a bent and noncopolanar structure, presenting a striking contrast to its isomer, 3,3,'4,4'-BPDA. This dianhydride was reacted with aromatic diamines in a polar aprotic solvent such as N,N-dimethylacetamide (DMAc) to form polyamic acid intermediates, which imidized chemically to polyimides with inherent viscosities of 0.34-0.55 dL/g, depending on the diamine used. The polyimides from 2,2,'3,3'-BPDA exhibited a good solubility and were dissolved in polar aprotic solvents and polychlorocarbons. These polyimides have high glass transition temperatures above 283 degrees C. Thermogravimetric analyses indicated that these polyimides were fairly stable up to 500 degrees C, and the 5% weight loss temperatures were recorded in the range of 534-583 degrees C in nitrogen atmosphere and 537-561 degrees C in air atmosphere. All polyimides were amorphous according to X-ray determination. (C) 1999 John Wiley & Sons, Inc.

Cold event at 5 500 a BP recorded in mud sediments on the inner shelf of the East China Sea

A 700-year record (1.0-1.5 a resolution) of the East Asian winter monsoon (EAWM), based on grain-size analysis and AMS(14)C dating of Core EC2005 from the inner-shelf mud wedge of the East China Sea (ECS), was compared with the Dongge stalagmite delta O-18 record during the mid-Holocene. The upper muddy section of Core EC2005 has been formed mainly by suspended sediments derived from the Changjiang (Yangtze) River mouth since 7.3 ka BP. High precipitation and a strengthened EAWM might have played key roles in the high sedimentation rate (1 324-1 986 cm/ka) between 5.9-5.2 ka BP. The EAWM strengthened when the Asian summer monsoon weakened, especially around 5 500 a BP, which corresponded to a worldwide cold event. The EAWM during the mid-Holocene shows statistically significant solar periodicities at 62 and 11 a. The 5 500 a BP cold event might be resulted from orbital forcing and changes in solar activity.

甘肃西峰黄土剖面500 ka以来的蜗牛化石记录及其古气候、古环境变化研究

The loess-paleosol sequences in China are among the best continental records of paleoclimate changes. Although numerous sedimentological and geochemical studies have contributed greatly to the understanding of past climate changes during this period, it is still necessary to decipher more details through investigating these sequences using various approaches including biological analyses. In this study, we analyze the mollusk fossil assemblages preserved in the upper part of the Xifeng section, from the fifth loess layer (L5) to the Holocene soil (S0), with the sampling interval of 10 cm. The main results and conclusions obtained are as follows: 1. A continuous terrestrial mollusk fossil record, covering the past 500 ka, has been obtained from the Xifeng loess-paleosol sequence, which provides important biological data for the study of paleoenvironmental changes in the Loess Plateau and its comparison with marine record during this period. A total of 475 mollusk assemblages were studied, and twenty-one species have been identified among the 210,000 mollusk individuals counted. Among these species, most have modern representatives and are found in previous terrestrial mollusk studies of Chinese loess-paleosol sequences. Thus, they can be grouped into cold-aridiphilous, thermo-humidiphilous, oriental, and cool-humidiphilous ecological groups, as defined by previous studies. 2. Comparison of mollusk assemblages between the last five glacials and four interglacials and Holocene shows very different climate conditions. The warmest period occurred at MIS 11, MIS 5e, and Holocene, respectively. The coldest period is the Last Glacial Maximam, rather than the MIS 12. 3. Our mollusk record provides insight into the climate conditions in the Loess Plateau during the MIS 11, interpreted as the closest analog to the present interglacial. S4 paleosol, equivalent of MIS 11, developed under two major different climate regimes: ranging from the very warm–humid early phase to the mild-cool late interval. Furthermore, a cooling spell has been documented at the interglacial optimum, reflecting unstable climate conditions. The early warm–humid conditions lasted over 30 ka, supporting that MIS 11 is a unique long interglacial in the Quaternary climate history. 4. Comparison of MIS 11 and Holocene climates based on the mollusk species compositions indicates major differences. The climate at the early part of MIS 11 was warmer and more humid than during the Holocene optimum period, but the conditions during the late part of MIS 11 were similar to or cooler than late Holocene. Our study indicates that the extent of warming during the Holocene might be significantly less than the conditions that prevailed during the early part of MIS 11 interglacial period. 5. Two strong summer monsoon events were observed during the MIS 12 and MIS 10. They correspond to the maximam values of insolation gradient between low and high latitudes, suggesting a causal linkage. 6. Our study, combined with the previously investigated Luochuan land snail record, reveals that the climate in the Loess Plateau during MIS 3 experienced three stages: relatively warm, humid climate prevailed during MIS 3c, relatively cold, dry climate during MIS 3b, and relatively warm-humid period during MIS 3a. Climate at this time fluctuated frequently in Luochuan, and changed from warm-cool to cold-dry in Xifeng. Our results reveal that the relatively warm-humid climate during MIS 3c may be resulted from an increasing insolation gradient controlled by obliquity. Our result also reveals that obvious regional difference existed in the Loess Plateau during MIS 3. A greater climate gradient occurred during this time compared with today’s climate pattern in the Loess Plateau.