Functionalized TiO2 nanoparticles for use for in situ anion immobilization

Anatase particles (40-60 nm) were coated with an organosilane monolayer terminated with an ethylenediamine (EDA) ligand. These functionalized nanoparticles (FNPs) were then treated with an aqueous solution of Cu(II) to create a cationic Cu-EDA complex bound to the nanoparticle surface. Cu(II) and EDA ligand incorporation were confirmed by X-ray photoelectron spectroscopy (XPS) analysis. The Cu(EDA)2 FNP was then studied for its binding affinity for pertechnetate anion from a Hanford groundwater matrix. The Cu(EDA)2 FNP was also evaluated for its injectability into a porous medium for possible application as a subsurface semipermeable reactive barrier. Injection was readily accomplished, and resulted in a highly uniform distribution of the FNP sorbent in the test column.     

Porous Carbon‐Hosted Atomically Dispersed Iron–Nitrogen Moiety as Enhanced Electrocatalysts for Oxygen Reduction Reaction in a Wide Range of pH

As one of the alternatives to replace precious metal catalysts, transition‐metal–nitrogen–carbon (M–N–C) electrocatalysts have attracted great research interest due to their low cost and good catalytic activities. Despite nanostructured M–N–C catalysts can achieve good electrochemical performances, they are vulnerable to aggregation and insufficient catalytic sites upon continuous catalytic reaction. In this work, metal–organic frameworks derived porous single‐atom electrocatalysts (SAEs) were successfully prepared by simple pyrolysis procedure without any further posttreatment. Combining the X‐ray absorption near‐edge spectroscopy and electrochemical measurements, the SAEs have been identified with superior oxygen reduction reaction (ORR) activity and stability compared with Pt/C catalysts in alkaline condition. More impressively, the SAEs also show excellent ORR electrocatalytic performance in both acid and neutral media. This study of nonprecious catalysts provides new insights on nanoengineering catalytically active sites and porous structures for nonprecious metal ORR catalysis in a wide range of pH.     

Joint Charge Storage for High‐Rate Aqueous Zinc–Manganese Dioxide Batteries

Aqueous rechargeable zinc–manganese dioxide batteries show great promise for large‐scale energy storage due to their use of environmentally friendly, abundant, and rechargeable Zn metal anodes and MnO₂ cathodes. In the literature various intercalation and conversion reaction mechanisms in MnO₂ have been reported, but it is not clear how these mechanisms can be simultaneously manipulated to improve the charge storage and transport properties. A systematical study to understand the charge storage mechanisms in a layered δ‐MnO₂ cathode is reported. An electrolyte‐dependent reaction mechanism in δ‐MnO₂ is identified. Nondiffusion controlled Zn²⁺ intercalation in bulky δ‐MnO₂ and control of H⁺ conversion reaction pathways over a wide C‐rate charge–discharge range facilitate high rate performance of the δ‐MnO₂ cathode without sacrificing the energy density in optimal electrolytes. The Zn‐δ‐MnO₂ system delivers a discharge capacity of 136.9 mAh g^?1 at 20 C and capacity retention of 93% over 4000 cycles with this joint charge storage mechanism. This study opens a new gateway for the design of high‐rate electrode materials by manipulating the effective redox reactions in electrode materials for rechargeable batteries.     

Molecular Storage of Mg Ions with Vanadium Oxide Nanoclusters

Mg batteries have potential advantages in terms of safety, cost, and reliability over existing battery technologies, but their practical implementations are hindered by the lack of amenable high‐voltage cathode materials. The development of cathode materials is complicated by limited understandings of the unique divalent Mg²⁺ ion electrochemistry and the interaction/transportation of Mg²⁺ ions with host materials. Here, it is shown that highly dispersed vanadium oxide (V₂O₅) nanoclusters supported on porous carbon frameworks are able to react with Mg²⁺ ions reversibly in electrolytes that are compatible with Mg metal, and exhibit high capacities and good reaction kinetics. They are able to deliver initial capacities exceeding 300 mAh g^?1 at 40 mA g^?1 in the voltage window of 0.5 to 2.8 V. The combined electron microscope, spectroscopy, and electrochemistry characterizations suggest a surface‐controlled pseudocapacitive electrochemical reaction, and may be best described as a molecular energy storage mechanism. This work can provide a new approach of using the molecular mechanism for pseudocapacitive storage of Mg²⁺ for Mg batteries cathode materials.     

Model based hydropower gate operation for mitigation of CSO impacts by means of river base flow increase.

In river stretches being subjected to flow regulation, usually for the purpose of energy production (e.g. Hydropower) or flood protection (river barrage), a special measure can be taken against the effect of combined sewer overflows (CSOs). The basic idea is the temporal increase of the river base flow (during storm weather) as an in-stream measure for mitigation of CSO spilling. The focus is the mitigation of the negative effect of acute pollution of substances. The measure developed can be seen as an application of the classic real time control (RTC) concept onto the river system. Upstream gate operation is to be based on real time monitoring and forecasting of precipitation. The main objective is the development of a model based predictive control system for the gate operation, by modelling of the overall wastewater system (incl. the receiving water). The main emphasis is put on the operational strategy and the appropriate short-term forecast of spilling events. The potential of the measure is tested for the application of the operational strategy and its ecological and economic feasibility. The implementation of such an in-stream measure into the hydropower's operational scheme is unique. Advantages are (a) the additional in-stream dilution of acute pollutants entering the receiving water and (b) the resulting minimization of the required CSO storage volume.     

Purification of histidine tagged bacteriorhodopsin, pharaonis halorhodopsin and pharaonis sensory rhodopsin II functionally expressed in Escherichia coli

Bacteriorhodopsin (BR) from Halobacterium salinarum as well as halorhodopsin (pHR) and sensory rhodopsin II (pSRII) from Natronobacterium pharaonis were functionally expressed in E. coli using the method of Shimono et al. IFEBS Lett. (1997) 420, 54-56]. The histidine tagged proteins were purified with yields up to 1.0 mg/l cell culture and characterized by ESI mass spectrometry and their photocycle. The pSRII and pHR photocycles were indistinguishable from the wild type proteins. The BR photocycle was considerably prolonged. pSOII is located in the cytoplasmic membrane and the C-terminus is oriented towards the cytoplasm as determined by immunogold labelling.     

Application of NMR-Spectroscopy to Retinal Proteins

The application of NMR spectroscopy to the retinal proteins bacteriorhodopsin (BR) and rhodopsin is reviewed. ²H-, ¹⁵N-, and ¹³C-solid-state NMR spectroscopy have contributed considerably to understanding the conformation and chemical environment of the protonated retinylidene Schiff base in BR as well as in rhodospin. The data from both pigments clarified the mechanism of the opsin shift which is quite different for rhodopsin and BR. An analysis of the chemical shifts of isotopically labeled aspartic acid, tyrosine, and proline incorporated into BR-provided evidence for the protonation state of Asp and Tyr, and the isomerization state of the Xaa—Pro peptide bond, respectively. Solid-state NMR spectroscopy was also applied to the investigation of the photocycle intermediates of BR, as well as bathorhodopsin and metarhodopsin II, which are formed after light-activation of rhodopsin. Solution NMR spectroscopy of BR solubilized in detergents or organic solvents, as well as of opsin-derived peptide segments, was also applied to the investigation of the two- and three-dimensional structure of BR.     

Combined sewer system versus separate system--a comparison of ecological and economical performance indicators.

This paper aims at comparing the cost-effectiveness of the two main types of urban drainage systems, that is, the combined sewer system and the separate sewer system, based on the analysis of simulations. The problem of which of the two systems is better was heavily discussed over the years and the answer given to the question was usually: 'it depends'. In this work, specific impacts are investigated in terms of a cause-effect analysis. The results are subsequently summarized and can help in the choice of the system to be implemented. Despite earlier reasoning, studies on river water quality strongly indicate that the separate system is not always the preferable solution because the polluted runoff from the street, containing e.g. different heavy metals, is discharged directly into the river. This analysis aims to compare the two different sewer systems on the basis of literature data and simulation of specific cases. The results are evaluated, as suggested in the EU-Water Framework Directive, on the basis of different assessment criteria: river water quality and morphology impacts, emissions and costs.     

Shared epitopes for HLA-A3-restricted melanoma-reactive human CTL include a naturally processed epitope from Pmel-17/gp100

Human CD8+ CTL recognize peptides bound to class I MHC molecules on the surface of melanoma cells. Several peptides derived from melanocyte lineage-specific proteins have been identified as epitopes for HLA-A2 restricted melanoma-reactive CTL. Because less than half of melanoma patients express HLA-A2, it is important to identify CTL epitopes restricted by other common MHC molecules including HLA-A1 and -A3. We have generated HLA-A3-restricted human CTL that recognize one or more shared melanoma Ags. All of the melanomas recognized by one of these CTL lines express Pmel-17/gp100, and those that fail to express this Ag are not lysed. This CTL line also specifically recognizes the lymphoblastoid line C1R-A3 following infection with a recombinant vaccinia encoding the melanocyte lineage-specific protein Pmel-17/gp100. Thus, at least one Pmel-17/ gp100 peptide is an epitope for this CTL line. We have identified ALLAVGATK (Pmel-17/gp100 residues 17-25) as an epitope for this CTL line and have shown that it is naturally processed and presented by HLA-A3 on melanoma cells. A second HLA-A3-restricted melanoma-reactive CTL line recognizes at least one additional shared epitope. These findings suggest that cellular immune responses directed against multiple shared melanoma epitopes exist in the 20 to 25% of melanoma patients who express HLA-A3. In addition, immunotherapy directed against Pmel-17/gp100 and other shared melanoma Ags may be useful in a large subset of these patients.     

Nitrogen-incorporation induced changes in the microstructure of nanocrystalline WO3 thin films

Nitrogen incorporated tungsten oxide (WO₃) films were grown by reactive magnetron sputter-deposition by varying the nitrogen content in the reactive gas mixture keeping the deposition temperature fixed at 400 °C. The crystal structure, surface morphology, chemical composition, and electrical resistivity of nitrogen doped WO₃ films were evaluated using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and electrical conductivity measurements. The results indicate that the nitrogen-incorporation induced changes in the microstructure and electrical properties of WO₃ films are significant. XRD measurements coupled with SEM analysis indicate that the increasing nitrogen content decreases the grain size and crystal quality. The nitrogen concentration increases from 0 at.% to 1.35 at.% with increasing nitrogen flow rate from 0 to 20 sccm. The corresponding dc electrical conductivity of the films had shown a decreasing trend with increasing nitrogen content.