Reduced texaphyrin: A ratiometric optical sensor for heavy metals in aqueous solution

We report here a water-soluble metal cation sensor system based on the as-prepared or reduced form of an expanded porphyrin, texaphyrin. Upon metal complexation, a change in the redox state of the ligand occurs that is accompanied by a color change from red to green. Although long employed for synthesis in organic media, we have now found that this complexation-driven redox behavior may be used to achieve the naked eye detectable colorimetric sensing of several number of less-common metal ions in aqueous media. Exposure to In(III), Hg(II), Cd(II), Mn(II), Bi(III), Co(II), and Pb(II) cations leads to a colorimetric response within 10 min. This process is selective for Hg(II) under conditions of competitive analysis. Furthermore, among the subset of response-producing cations, In(III) proved unique in giving rise to a ratiometric change in the ligand-based fluorescence features, including an overall increase in intensity. The cation selectivity observed in aqueous media stands in contrast to what is seen in organic solvents, where a wide range of texaphyrin metal complexes may be prepared. The formation of metal cation complexes under the present aqueous conditions was confirmed by reversed phase high-performance liquid chromatography, ultra-violet-visible absorption and fluorescence spectroscopies, and high-resolution mass spectrometry.     

A boronic acid-based fluorescent hydrogel for monosaccharide detection

A boronic acid-based anthracene fluorescent probe was functionalised with an acrylamide unit to incorporate into a hydrogel system for monosaccharide detection. In solution, the fluorescent probe displayed a strong fluorescence turn-on response upon exposure to fructose, and an expected trend in apparent binding constants, as judged by a fluorescence response where D-fructose>D-galactose>D-mannose>D-glucose. The hydrogel incorporating the boronic acid monomer demonstrated the ability to detect monosaccharides by fluorescence with the same overall trend as the monomer in solution with the addition of D-fructose resulting in a 10-fold enhancement (≤0.25 mol/L).     

AA7075高强铝合金热冲压流变行为本构模型对比研究

在热冲压过程中,AA7075高强铝合金板料经充分固溶后移入室温模具进行冲压成形并淬火。为表征AA7075铝合金在热冲压工艺中的变形行为,在温度200~480℃、应变速率0.01~10s-1范围内进行了高温拉伸试验。基于Arrhenius类型本构模型、Johnson-Cook模型以及Zerilli-Armstrong模型提出了多种修正本构模型,并应用实验所获流变曲线进行了拟合。提出的修正模型通过将模型参数表示为应变、应变速率及温度相关的多项式函数耦合了应变、应变速率及温度对流变应力的影响,并通过均方误差(MSE)以及相关系数R值对模型流变应力预测准确性进行了评价。结果表明,修正的Johnson-Cook模型能够更加准确的预测AA7075高温流变行为。     

Behavior of ZrO2-C Refractories in Thin-strip Casting of Steel

Zirconia graphite refractory is used as a core-nozzle in the thin-strip casting of steel. Post-mortem analysis of used refractory was performed in an effort to establish the failure mechanism. Corrosion behavior was studied against molten steel with Mn O- SiO 2based liquid inclusions. Corrosion of these materials involves dissolution and oxidation of graphite in the matrix followed by penetration of liquid slag leading to degradation of ZrO 2particles. Thermodynamic equilibrium calculations were performed to study this corrosion mechanism.     

Revealing the relationships between alloy structure,composition and plastic deformation in a ternary alloy system by a combinatorial approach

A high-throughput approach based on magnetron co-sputtering of alloy libraries is employed to inves-tigate mechanical properties of crystalline and amorphous alloys in a ternary palladium(Pd)-tungsten(W)-silicon(Si)system with the aim to reveal the difference in plastic deformation response and extract the relevant structure-property relationships of the alloys in the system.It was found that in contrast to crystalline alloys,the amorphous ones,i.e.,metallic glasses,exhibited a much smaller fluctuation range in the plasticity parameters(Er2/H and Wp/Wt),indicating a significant difference in the plastic deformation mechanism controlling the mechanical properties for the respective alloys.We propose that the inho-mogeneous deformation of amorphous alloys localized in thin shear bands is responsible for the weaker compositional dependence of both plasticity parameters,while dislocation gliding in crystalline materials is significantly more dependent on the exact structure,thus resulting in a larger scattering range.Based on the representative efficient cluster packing model,a set of composition-dependent atomic structural models is proposed to figure out the structure-property relationships of amorphous alloys in Pd-W-Si alloy system.     

ICP-AES法测定7种高原野生蜂蜜的矿质元素含量

为探明不同种类高原野生蜂蜜的矿质元素组成,促进高原蜂蜜资源开发利用及品质评价,本研究采用湿法消解、电感耦合等离子体原子发射光谱法(ICP-AES)对包括野花蜜、野生枸杞蜂蜜、野生香草蜜、野生油菜花蜜、野党参蜜、野藿香蜜、珍品雪山花蜜等7个品种高原野生蜂蜜的20种元素——Ca、K、Mg、Na、P、S、Ba、Cu、Fe、Li、Mn、Mo、Ni、Sr、Ti、Zn、Al、As、Cr和P进行测定,并应用聚类分析方法对测定结果进行分析。结果表明:在选定的条件下,各元素间相互干扰小,对测定结果无明显影响;该方法回收率在94.9%～101.3%之间,具有较好的准确度与精密度;不同品种高原蜂蜜中各种元素含量存在一定的差异,其中元素K、P、Ca、Fe、Mg、Na、Mn、Zn含量较高。从聚类树状图上可知,7种蜂蜜可聚类为2类。野党参蜜和野藿香蜜表现出较高的相似性,都可聚为一类,这显示其品质的稳定性。     

Atmospheric deposition of carbon and nutrients across an arid metropolitan area

Urbanization is increasing rapidly in semi-arid environments and is predicted to alter atmospheric deposition of nutrients and pollutants to cities as well as to ecosystems downwind. We examined patterns of wet and coarse dry deposition chemistry over a five-year period at 7 sites across the Central Arizona-Phoenix (CAP) study area, one of two urban sites within the National Science Foundation's Long-Term Ecological Research (LTER) program. Wet and dry deposition of organic carbon (oC) were significantly elevated in the urban core; in contrast, mean annual wet and dry fluxes of nitrogen (N) were low (<6 kg ha(-1) yr(-1)) compared to previous estimates and did not differ significantly among sites. Wet deposition of sulfate (SO(4)2-) was high across CAP (mean 1.39 kg ha(-1) yr(-1) as S) and represented the dominant anion in rainfall. Dry deposition rates did not show strong seasonal trends with the exception of oC, which was 3-fold higher in winter than in summer; ammonium (NH4+) deposition was high but more variable. Dry deposition of NO3- and oC was strongly correlated with particulate base cations and dust-derived soluble reactive phosphorus (SRP), suggesting that urban-derived dust is scrubbing the atmosphere of acidic gases and entrained particles and increasing local deposition. Differences between measured and predicted rates of dry N deposition to the urban core may be explained by incomplete collection of gas phase N on surrogate deposition surfaces in this hot and arid environment. The extent of urban enhancement of cations and oC inputs to desert ecosystems appears to be restricted to the urbanized metropolitan area rather than extending far downwind, although a low number of sites make it difficult to resolve this spatial pattern. Nevertheless, wet and dry inputs may be important for biogeochemical cycles in nutrient and carbon-poor desert ecosystems within and near arid cities.     

Hydrogen and methane production from household solid waste in the two-stage fermentation process

A two-stage process combined hydrogen and methane production from household solid waste was demonstrated working successfully. The yield of 43 mL H(2)/g volatile solid (VS) added was generated in the first hydrogen production stage and the methane production in the second stage was 500 mL CH(4)/g VS added. This figure was 21% higher than the methane yield from the one-stage process, which was run as control. Sparging of the hydrogen reactor with methane gas resulted in doubling of the hydrogen production. pH was observed as a key factor affecting fermentation pathway in hydrogen production stage. The optimum pH range for hydrogen production in this system was in the range from 5 to 5.5. The short hydraulic retention time (2 days) applied in the first stage was enough to separate acidogenesis from methanogenesis. No additional control for preventing methanogenesis in the first stage was necessary. Furthermore, this study also provided direct evidence in the dynamic fermentation process that, hydrogen production increase was reflected by acetate to butyrate ratio increase in liquid phase.     

A model approach to assess the long-term trends of indirect photochemistry in lake water. The case of Lake Maggiore (NW Italy)

A model-based approach is here developed and applied to predict the long-term trends of indirect photochemical processes in the surface layer (5 m water depth) of Lake Maggiore, NW Italy. For this lake, time series of the main parameters of photochemical importance that cover almost two decades are available. As a way to assess the relevant photochemical reactions, the modelled steady-state concentrations of important photogenerated transients (^•OH, ³CDOM* and CO₃^-•) were taken into account. A multivariate analysis approach was adopted to have an overview of the system, to emphasise relationships among chemical, photochemical and seasonal variables, and to highlight annual and long-term trends. Over the considered time period, because of the decrease of the dissolved organic carbon (DOC) content of water and of the increase of alkalinity, a significant increase is predicted for the steady-state concentrations of the radicals ^•OH and CO₃^−•. Therefore, the photochemical degradation processes that involve the two radical species would be enhanced. Another issue of potential photochemical importance is related to the winter maxima of nitrate (a photochemical ^•OH source) and the summer maxima of DOC (^•OH sink and ³CDOM* source) in the lake water under consideration. From the combination of sunlight irradiance and chemical composition data, one predicts that the processes involving ^•OH and CO₃^−• would be most important in spring, while the reactions involving ³CDOM* would be most important in summer.     

Use of in-stream reservoirs to reduce bacterial contamination of rural watersheds

An investigation into bacterial water quality problems was conducted on an interconnected stream and irrigation system within the Oldman River Basin of southern Alberta, Canada. Levels of indicator bacteria, including fecal coliforms, generic Escherichia coli and fecal streptococci, were repeatedly measured in streams and irrigation return canals of this river basin during the summer of 2001. Bacterial-loading segments of the irrigation/stream system were identified through a comparison of indicator bacteria levels in pairs of upstream and downstream sites. Mann-Whitney U-tests indicated that reservoirs significantly reduced bacterial counts. A temporal comparison of E. coli counts and river discharges suggested that these indicator bacteria do not originate from within in-stream sediments. Site-specific as well as cumulative inputs from a variety of non-point sources are likely to be responsible for the high downstream levels of indicator bacteria in this water system. The use of management practices such as in-stream reservoirs may significantly reduce contamination, and increase the quality of limited rural water supplies to allow their reuse and safe discharge into downstream water sources. The identification of bacteria-loading river/canal segments could also be used to prioritize restoration projects.