Transport and transformation of hexavalent chromium through soils and into ground water

A detailed characterization of the underlying and adjacent soils of a chrome‐plating shop was performed to provide information on the extent of soil and aquifer contamination at the site and on the potential for off‐site migration and environmental impact. Intact, moist cores were obtained from more than 40 different locations, resulting in more than 200 discrete samples for total metal analysis, selective extraction tests, and adsorption‐reduction experiments, to assess the chemical speciation and distribution of chromium on the contaminated soils and its leaching potential. Surface analytical techniques were also used to determine chemical speciation and to further elucidate mineral fractions responsible for retention of the chromium on the soils and sediments. Adsorption and reduction capacities of the saturated aquifer sediments were variable and low, while the unsaturated soils’ reduction capacities were much greater and were correlated with depth (decreasing capacity with increasing depth). The soils’ adsorption and reduction capacities were eventually overwhelmed, however, and permitted the passage of Cr(VI) into the underlying ground water. Adsorption capacity differences were primarily related to clay content and pH, and less so to the presence of amorphous iron oxide coatings on matrix minerals as operationally defined by the selective extraction methods used in the study. Reduction of Cr(VI) to Cr(III) and subsequent precipitation as (Fe, Cr)(OH)₃ is proposed as the primary attenuation mechanism in the unsaturated soils immediately beneath the shop, based on extraction and surface analyses results.     

Resource and hardware options for microarray-based experimentation.

DNA microarray technology permits the study of biological systems and processes on a genome-wide scale. Arrays based on cDNA clones, oligonucleotides and genomic clones have been developed for investigations of gene expression, genetic analysis and genomic changes associated with disease. Over the past 3-4 years, microarrays have become more widely available to the research community. This has occurred through increased commercial availability of custom and generic arrays and the development of robotic equipment that has enabled array printing and analysis facilities to be established in academic research institutions. This brief review examines the public and commercial resources, the microarray fabrication and data capture and analysis equipment currently available to the user.     

Acceleration Workspace of Cooperating Multi-Finger Robot Systems

We present a mathematical method for acceleration workspace analysis of cooperating multi-finger robot systems using a model of point-contact with friction. A new unified formulation from dynamic equations of cooperating multi-finger robots is derived considering the force and acceleration relationships between the fingers and the object to be handled. From the dynamic equation, maximum translational and rotational acceleration bounds of an object are calculated under given constraints of contact conditions, configurations of fingers, and bounds on the torques of joint actuators for each finger. Here, the rotational acceleration bounds can be applied as an important manipulability index when the multi-finger robot grasps an object. To verify the proposed method, we used a set of case studies with a simple multi-finger mechanism system. The achievable acceleration boundary in task space can be obtained successfully with the proposed method and the acceleration boundary depends on the configurations of fingers.     

Intracellular and Extracellular Biomineralization Induced by Klebsiella pneumoniae LH1 Isolated from Dolomites

Abstract

The interaction between bacteria and minerals is very complicated and has been intensively studied in the laboratory and the field in the last few decades, but the processes and mechanisms of biomineralization and mineral precipitation are still not fully understood and need to be explored further. In the present work, biomineralization experiments were undertaken using Klebsiella pneumoniae LH1, collected from a natural surface environment in an area of outcrops of Cambrian dolomite, in a culture medium with various Mg/Ca molar ratios (0, 3, 6 and 12). The mineral precipitates obtained were analyzed by X-ray diffraction (XRD), scanning electron microscope (SEM), energy dispersive spectrometer (EDS), Fourier transform infrared spectrometer (FTIR), laser scanning confocal microscopy (LSCM) and X-ray photoelectron spectroscopy (XPS). Cells were analyzed with a scanning transmission electron microscope (STEM), high resolution transmission electron microscope (HRTEM) and selected area electron diffraction (SAED). The composition of amino acids in extracellular polymeric substances (EPS) was also determined. In the experiments it was found that the production of ammonia and the presence of carbonate anhydrase promoted the increase of the medium pH and that minerals are nucleated on the EPS, which consist chiefly of amino acids and negatively-charged organic functional groups. With increasing Mg/Ca ratios, the mineral phases changed, including calcite (100%) at Mg/Ca molar ratio of 0, monohydrocalcite (36.05%) + dypingite (63.95%) at Mg/Ca molar ratio of 3, monohydrocalcite (29.72%) + dypingite (15.48%) + nesquehonite (54.80%) at Mg/Ca molar ratio of 6, and monohydrocalcite (14.2%) + dypingite (1.0%) + nesquehonite (84.80%) at Mg/Ca molar ratio of 12. Some intracellular amorphous calcium- and magnesium-rich inclusions were also detected in K. pneumoniae LH1, suggesting intracellular biomineralization accompanying the extracellular mineral precipitation. This study provides further understanding of the biomineralization processes of microorganisms.     

Circular Dichroism Spectroscopy Study of Crystalline‐to‐Amorphous Transformation in Chiral Platinum(II) Complexes

Two couples of enantiomeric platinum(II) complexes: Pt(L_1a)Cl ( 1a ), Pt(L_1b)Cl ( 1b ) and Pt(L_1a)(C ≡ C ? Ph) ( 2a ), Pt(L_1b)(C ≡ C ? Ph) ( 2b ) (L_1a = (+)‐1,3‐di‐(2‐(4,5‐pinene)pyridyl)benzene, L_1b = (?)‐1,3‐di‐(2‐(4,5‐pinene)pyridyl)benzene) were synthesized and characterized. Their absolute configurations were determined by single crystal X‐ray diffraction and further verified by circular dichroism (CD) spectra (including electronic circular dichroism [ECD] and vibrational circular dichroism [VCD]). These complexes show interesting mechanoluminescence and/or vapoluminescence due to crystalline‐to‐amorphous transformation. The crystalline solids, grinding‐induced amorphous powders, and vapor‐induced amorphous powders of complexes 2a and 2b were comparatively investigated by solid‐state ECD and VCD spectra. The transformation from crystalline solids to amorphous powders was accompanied by significant variances of the spectral feature in both ECD and VCD spectra. Chirality 25:384–392, 2013. © 2013 Wiley Periodicals, Inc.     

Challenges and Strategies in Thermal Processing of Amorphous Solid Dispersions: A Review

Thermal processing of amorphous solid dispersions continues to gain interest in the pharmaceutical industry, as evident by several recently approved commercial products. Still, a number of pharmaceutical polymer carriers exhibit thermal or viscoelastic limitations in thermal processing, especially at smaller scales. Additionally, active pharmaceutical ingredients with high melting points and/or that are thermally labile present their own specific challenges. This review will outline a number of formulation and process-driven strategies to enable thermal processing of challenging compositions. These include the use of traditional plasticizers and surfactants, temporary plasticizers utilizing sub- or supercritical carbon dioxide, designer polymers tailored for hot-melt extrusion processing, and KinetiSol® Dispersing technology. Recent case studies of each strategy will be described along with potential benefits and limitations.     

Silk‐ and volatile‐based male mate choice in the genital plug‐producing spider

Female mating history can have a strong effect on male fertilization success. Although males often prefer to mate with virgin females, they often also engage with mated females. As the intensity of sperm competition can differ among mated females, males are expected to evolve means to identify their status. In spiders, males often use female silk to gather information about female quality. Males of many spider species deposit mating plugs into female genitalia to hinder further copulations. We tested whether males of the foliage‐dwelling, plug‐producing spider Philodromus cespitum, which is an important natural enemy of pests, discriminate between females of different mating status and whether they can determine the extent of genital plugging in mated females solely on the basis of cues gained from deposited female silk. We presented males with draglines of females that varied in either mating status (virgin vs. mated), the extent of plugging (small vs. big plug), or the age of the plug (fresh vs. old plug) and examined their mate preferences. Additionally, we tested whether males were attracted to volatile cues produced by female bodies. Our experiments revealed that males preferred draglines of virgin females to those of mated females, and mated females with small plugs to those with large plugs. They were also attracted to female volatile cues. This study suggests that males are able to extract fine‐scale information on mating status from female draglines.     

Low‐Temperature Micro‐Solid Oxide Fuel Cells with Partially Amorphous La0.6Sr0.4CoO3‐δ Cathodes

Partially amorphous La_0.6Sr_0.4CoO_3‐δ (LSC) thin‐film cathodes are fabricated using pulsed laser deposition and are integrated in free‐standing micro‐solid oxide fuel cells (micro‐SOFC) with a 3YSZ electrolyte and a Pt anode. A low degree of crystallinity of the LSC layers is achieved by taking advantage of the miniaturization of the cells, which permits low‐temperature operation (300–450 °C). Thermomechanically stable micro‐SOFC are obtained with strongly buckled electrolyte membranes. The nanoporous columnar microstructure of the LSC layers provides a large surface area for oxygen incorporation and is also believed to reduce the amount of stress at the cathode/electrolyte interface. With a high rate of failure‐free micro‐SOFC membranes, it is possible to avoid gas cross‐over and open‐circuit voltages of 1.06 V are attained. First power densities as high as 200–262 mW cm^?2 at 400–450 °C are achieved. The area‐specific resistance of the oxygen reduction reaction is lower than 0.3 Ω cm² at 400 °C around the peak power density. These outstanding findings demonstrate that partially amorphous oxides are promising electrode candidates for the next‐generation of solid oxide fuel cells working at low‐temperatures.     

A Simple Electrochemical Route to Access Amorphous Mixed‐Metal Hydroxides for Supercapacitor Electrode Materials

Supercapacitors or electrochemical capacitors, as energy storage devices, require very stable positive electrode materials for useful applications. Although most positive electrodes are based on crystalline mixed‐metal hydroxides, their pseudocapacitors usually perform poorly or have a short cycle life. High activities can be achieved with amorphous phases. Methods to produce amorphous materials are also not typically amenable towards mixed‐metal compositions. It is demonstrated that electrochemistry in an ambient environment can be used to produce a series of amorphous mixed‐metal hydroxides with a homogeneous distribution of metals for use as positive electrode materials in a supercapacitor. The integrated performance of the amorphous ternary mixed‐metal hydroxide pseudocapacitor is superior to that of crystalline materials. The amorphous Ni‐Co‐Fe hydroxide supercapacitor is characterized by a long‐term cycling stability that retained 94% of its capacity after 20 000 cycles. This is much higher than the cycle life of crystalline devices. These results show the broad applicability of this methodology towards new electrode materials for high‐performance supercapacitors, especially amorphous mixed‐metal hydroxides, as advanced electrode materials.