Enhancing the activity of oxygen-evolution and chlorine-evolution electrocatalysts by atomic layer deposition of TiO₂

We report that TiO₂ coatings formed via atomic layer deposition (ALD) may tune the activity of IrO₂, RuO₂, and FTO for the oxygen-evolution and chlorine-evolution reactions (OER and CER). Electrocatalysts exposed to ∼3–30 ALD cycles of TiO₂ exhibited overpotentials at 10 mA cm⁻² of geometric current density that were several hundred millivolts lower than uncoated catalysts, with correspondingly higher specific activities. For example, the deposition of TiO₂ onto IrO₂ yielded a 9-fold increase in the OER-specific activity in 1.0 M H₂SO₄ (0.1 to 0.9 mA cm_(ECSA)⁻² at 350 mV overpotential). The oxidation state of titanium and the potential of zero charge were also a function of the number of ALD cycles, indicating a correlation between oxidation state, potential of zero charge, and activity of the tuned electrocatalysts

Pyrochlore Photons: The U(1) Spin Liquid in a S=1/2 Three-Dimensional Frustrated Magnet

We study the S=1/2 Heisenberg antiferromagnet on the pyrochlore lattice in the limit of strong easy-axis exchange anisotropy. We find, using only standard techniques of degenerate perturbation theory, that the model has a U(1) gauge symmetry generated by certain local rotations about the z-axis in spin space. Upon addition of an extra local interaction in this and a related model with spins on a three-dimensional network of corner-sharing octahedra, we can write down the exact ground state wavefunction with no further approximations. Using the properties of the soluble point we show that these models enter the U(1) spin liquid phase, a novel fractionalized spin liquid with an emergent U(1) gauge structure. This phase supports gapped S^z = 1/2 spinons carrying the U(1) ``electric'' gauge charge, a gapped topological point defect or ``magnetic'' monopole, and a gapless ``photon,'' which in spin language is a gapless, linearly dispersing S^z = 0 collective mode. There are power-law spin correlations with a nontrivial angular dependence, as well as novel U(1) topological order. This state is stable to ALL zero-temperature perturbations and exists over a finite extent of the phase diagram. Using a convenient lattice version of electric-magnetic duality, we develop the effective description of the U(1) spin liquid and the adjacent soluble point in terms of Gaussian quantum electrodynamics and calculate a few of the universal properties. The resulting picture is confirmed by our numerical analysis of the soluble point wavefunction. Finally, we briefly discuss the prospects for understanding this physics in a wider range of models and for making contact with experiments.Comment: 22 pages, 14 figures. Further minor changes. To appear in Phys. Rev.

Social contact networks and mixing among students in K-12 schools in Pittsburgh, PA

Students attending schools play an important role in the transmission of influenza. In this study, we present a social network analysis of contacts among 1,828 students in eight different schools in urban and suburban areas in and near Pittsburgh, Pennsylvania, United States of America, including elementary, elementary-middle, middle, and high schools. We collected social contact information of students who wore wireless sensor devices that regularly recorded other devices if they are within a distance of 3 meters. We analyzed these networks to identify patterns of proximal student interactions in different classes and grades, to describe community structure within the schools, and to assess the impact of the physical environment of schools on proximal contacts. In the elementary and middle schools, we observed a high number of intra-grade and intra-classroom contacts and a relatively low number of inter-grade contacts. However, in high schools, contact networks were well connected and mixed across grades. High modularity of lower grades suggests that assumptions of homogeneous mixing in epidemic models may be inappropriate; whereas lower modularity in high schools suggests that homogenous mixing assumptions may be more acceptable in these settings. The results suggest that interventions targeting subsets of classrooms may work better in elementary schools than high schools. Our work presents quantitative measures of age-specific, school-based contacts that can be used as the basis for constructing models of the transmission of infections in schools

Application of DEN refinement and automated model building to a difficult case of molecular-replacement phasing: the structure of a putative succinyl-diaminopimelate desuccinylase from Corynebacterium glutamicum.

Phasing by molecular replacement remains difficult for targets that are far from the search model or in situations where the crystal diffracts only weakly or to low resolution. Here, the process of determining and refining the structure of Cgl1109, a putative succinyl-diaminopimelate desuccinylase from Corynebacterium glutamicum, at ∼3 Å resolution is described using a combination of homology modeling with MODELLER, molecular-replacement phasing with Phaser, deformable elastic network (DEN) refinement and automated model building using AutoBuild in a semi-automated fashion, followed by final refinement cycles with phenix.refine and Coot. This difficult molecular-replacement case illustrates the power of including DEN restraints derived from a starting model to guide the movements of the model during refinement. The resulting improved model phases provide better starting points for automated model building and produce more significant difference peaks in anomalous difference Fourier maps to locate anomalous scatterers than does standard refinement. This example also illustrates a current limitation of automated procedures that require manual adjustment of local sequence misalignments between the homology model and the target sequence

Enhancing the activity of oxygen-evolution and chlorine-evolution electrocatalysts by atomic layer deposition of TiO₂

We report that TiO₂ coatings formed via atomic layer deposition (ALD) may tune the activity of IrO₂, RuO₂, and FTO for the oxygen-evolution and chlorine-evolution reactions (OER and CER). Electrocatalysts exposed to ∼3–30 ALD cycles of TiO₂ exhibited overpotentials at 10 mA cm⁻² of geometric current density that were several hundred millivolts lower than uncoated catalysts, with correspondingly higher specific activities. For example, the deposition of TiO₂ onto IrO₂ yielded a 9-fold increase in the OER-specific activity in 1.0 M H₂SO₄ (0.1 to 0.9 mA cm_(ECSA)⁻² at 350 mV overpotential). The oxidation state of titanium and the potential of zero charge were also a function of the number of ALD cycles, indicating a correlation between oxidation state, potential of zero charge, and activity of the tuned electrocatalysts

Mars analysis correction data assimilation: a multi-annual reanalysis of atmospheric observations for the red planet

Ever-increasing numbers of atmospheric observations from orbiting spacecraft, and increasingly sophisticated numerical atmospheric models, have recently permitted data assimilation techniques to be applied to planets beyond the Earth. Mars is the first extra-terrestrial planet for which reanalyses of the atmospheric state are now available. The Thermal Emission Spectrometer (TES) on board NASA’s Mars Global Surveyor (MGS) has produced an extensive atmospheric data set during its scientific mapping phase between 1999 and 2004. Nadir thermal profiles for the atmosphere below about 40 km altitude, and total dust and water ice opacities, have been retrieved from TES spectra, covering almost three complete Martian seasonal cycles (each seasonal cycle on Mars corresponds to 668.6 mean solar days, and the Martian mean solar day is about 24 hours and 40 minutes). Note that dust on Mars plays a key role in the weather and climate, mainly through its strong absorption of short wave radiation with a short radiative relaxation timescale of 1-2 days. Assimilating dust opacities correctly is, therefore, particularly important for atmospheric data assimilation on the Red Planet. TES retrieved observations have been analysed by assimilation into a Mars general circulation model (MGCM), making use of a sequential procedure known as the Analysis Correction scheme, a form of successive corrections method which has proved simple and robust under Martian conditions, even during the less-than-ideal MGS aerobraking period. The MGCM used at the University of Oxford and at The Open University consists of a spectral dynamical solver and a tracer transport scheme developed in the UK. Its package of state-of-the-art physical parameterization routines is shared with the LMD-MarsGCM, developed by the Laboratoire de Météorologie Dynamique in Paris (France). One limitation of TES is that relatively few limb profiles are available, compared to nadir soundings. Our MGS/TES reanalysis, therefore, does not include observations of temperature above about 40 km altitude, nor 3D information on dust opacity (the vertical distribution of dust opacity is prescribed assuming a well mixed dust layer with a rapid transition to a clear upper atmosphere at a height which depends on latitude and season. In September 2006 NASA’s Mars Reconnaissance Orbiter (MRO) started its mapping phase. The Mars Climate Sounder (MCS) on board MRO is a radiometer with eight mid- and far-infrared channels and one visible channel, which takes measurements in limb and off-nadir geometries. Retrieved vertical profiles of temperature, dust and water ice opacities from MCS observations can now be assimilated using the same scheme we used for TES, with the advantage of the extension in altitude (thermal profiles can extend to above 80 km altitude, although errors become larger at greater altitudes), the increased vertical resolution (~ 5km compared to > 10km for TES nadir retrievals), and the direct information on the vertical distribution of dust and water ice. Overall, the application of our data assimilation scheme to retrieved observations from TES and MCS spans almost six complete Martian seasonal cycles. This represents a multi-annual climatology for Mars, which has the advantage of being a complete, dynamically-balanced, four-dimensional best-fit to observations for all the atmospheric variables, including those for which no direct measurements are available (e.g. wind and surface pressure) and with regions of no observations filled-in in a physically-consistent way. The reanalysis represents, therefore, a unique opportunity to study the inter-annual variability of the Martian weather and climate with respect to all its components, such as the dust cycle, the water cycle, the CO2 cycle, the atmospheric tides and other prominent waves, such as high latitude baroclinic waves. In this contribution we present the first results of a complete assimilation of both datasets, using a consistent model and data assimilation scheme, and highlight the challenges of combining TES and MCS data assimilation to produce a multi-annual climatology. Particular attention will be devoted to the inter-annual variability of the atmospheric thermal field in response to dust storm activity. We will also provide an insight into the dynamics, looking in particular at the high latitude winds, waves and polar vortices. Our data assimilation products are freely available to the community for both science- and engineering-oriented purposes. The British Atmospheric Data Centre (BADC, http://badc.nerc.ac.uk) hosts our datasets, which, for the time being, are limited to the MGS/TES reanalysis. People may contact the corresponding author in order to register their interest and be updated about the status of the project. New versions of the MGS/TES reanalysis as well as the MRO/MCS reanalysis will be made available through the BADC in future. Interested people can download the current TES reanalysis dataset by registering at the BADC and searching for the MACDA (“Mars Analysis Correction Data Assimilation”) project. The direct link to the project is provided by the following URL: http://badc.nerc.ac.uk/view/badc.nerc.ac.uk__ATOM__DE_095e8da2-cf02-11e0-8b7a-00e08147026

Impacts of phosphorus concentration and light intensity on river periphyton biomass and community structure

Periphyton growth rate has been identified as the key process that leads to river eutrophication. Effort has focused on reducing phosphorus concentrations to control periphyton biomass, but other factors, such as light, are also important. Within-stream flume mesocosms were deployed in the River Lambourn, UK, to investigate how light intensity and phosphorus concentrations affect periphyton biomass and community structure. Soluble reactive phosphorus (SRP) concentrations were tripled in some flumes, and decreased in others by dosing of FeCl3. Increasing SRP concentrations from the ambient concentration of 49 µg L-1 to 155 µg L-1 had no effect on biomass, but community composition (by flow cytometry) shifted from diatom to cyanobacterial dominance. Reducing light levels (equivalent to riparian tree shading) decreased biomass by 40 %, showing that the biofilms were light limited at SRP concentration ≥ 49 µg L-1. Periphyton were phosphorus / light co-limited when SRP concentrations were reduced to 33 µg L-1. Further reductions in SRP concentration (23 µg L-1) resulted in phosphorus limitation of periphyton biomass and increased dominance of diatoms and chlorophytes within the biofilm. Reducing light intensity through providing riparian tree shading could be an important management tool to reduce periphyton biomass and improve ecological status

Interface Controlled Thermal Resistances of Ultra-Thin Chalcogenide-Based Phase Change Memory Devices

Phase change memory (PCM) is a rapidly growing technology that not only offers advancements in storage-class memories but also enables in-memory data processing to overcome the von Neumann bottleneck. In PCMs, data storage is driven by thermal excitation. However, there is limited research regarding PCM thermal properties at length scales close to the memory cell dimensions. Our work presents a new paradigm to manage thermal transport in memory cells by manipulating the interfacial thermal resistance between the phase change unit and the electrodes without incorporating additional insulating layers. Experimental measurements show a substantial change in interfacial thermal resistance as GST transitions from cubic to hexagonal crystal structure, resulting in a factor of 4 reduction in the effective thermal conductivity. Simulations reveal that interfacial resistance between PCM and its adjacent layer can reduce the reset current for 20 and 120 nm diameter devices by up to ~ 40% and ~ 50%, respectively. These thermal insights present a new opportunity to reduce power and operating currents in PCMs

Two-photon Lithography for 3D Magnetic Nanostructure Fabrication

Ferromagnetic materials have been utilised as recording media within data storage devices for many decades. Confinement of the material to a two dimensional plane is a significant bottleneck in achieving ultra-high recording densities and this has led to the proposition of three dimensional (3D) racetrack memories that utilise domain wall propagation along nanowires. However, the fabrication of 3D magnetic nanostructures of complex geometry is highly challenging and not easily achievable with standard lithography techniques. Here, by using a combination of two-photon lithography and electrochemical deposition, we show a new approach to construct 3D magnetic nanostructures of complex geometry. The magnetic properties are found to be intimately related to the 3D geometry of the structure and magnetic imaging experiments provide evidence of domain wall pinning at a 3D nanostructured junction