Poly(2-oxazoline) hydrogels : state-of-the-art and emerging applications

The synthesis of poly(2-oxazoline)s has been known since the 1960s. In the last two decades, they have risen in popularity thanks to improvements in their synthesis and the realization of their potential in the biomedical field due to their stealth properties, stimuli responsiveness, and tailorable properties. Even though the bulk of the research to date has been on linear forms of the polymer, they are also of interest for creating network structures due to the relatively easy introduction of reactive functional groups during synthesis that can be cross-linked under a variety of conditions. This opinion article briefly reviews the history of poly(2-oxazoline)s and examines the in vivo data on soluble poly(2-oxazoline)s to date in an effort to predict how hydrogels may perform as implantable materials. This is followed by an overview of the most recent hydrogel synthesis methods and emerging applications, and is concluded with a section on the future directions predicted for these fascinating yet underutilized polymers

AIR multigrid with GMRES polynomials (AIRG) and additive preconditioners for Boltzmann transport

We develop a reduction multigrid based on approximate ideal restriction (AIR) for use with asymmetric linear systems. We use fixed-order GMRES polynomials to approximate $A_\textrm{ff}^{-1}$ and we use these polynomials to build grid transfer operators and perform F-point smoothing. We can also apply a fixed sparsity to these polynomials to prevent fill-in. When applied in the streaming limit of the Boltzmann Transport Equation (BTE), with a P$^0$ angular discretisation and a low-memory spatial discretisation on unstructured grids, this "AIRG" multigrid used as a preconditioner to an outer GMRES iteration outperforms the lAIR implementation in hypre, with two to three times less work. AIRG is very close to scalable; we find either fixed work in the solve with slight growth in the setup, or slight growth in the solve with fixed work in the setup when using fixed sparsity. Using fixed sparsity we see less than 20% growth in the work of the solve with either 6 levels of spatial refinement or 3 levels of angular refinement. In problems with scattering AIRG performs as well as lAIR, but using the full matrix with scattering is not scalable. We then present an iterative method designed for use with scattering which uses the additive combination of two fixed-sparsity preconditioners applied to the angular flux; a single AIRG V-cycle on the streaming/removal operator and a DSA method with a CG FEM. We find with space or angle refinement our iterative method is very close to scalable with fixed memory use

Evolution of Antarctic ozone in September-December predicted by CCMVal-2 model simulations for the 21st century

Chemistry-Climate Model Validation phase 2 (CCMVal-2) model simulations are used to analyze Antarctic ozone increases in 2000–2100 during local spring and early summer, both vertically integrated and at several pressure levels in the lower stratosphere. Multi-model median trends of monthly zonal mean total ozone column (TOC), ozone volume mixing ratio (VMR), wind speed and temperature poleward of 60° S are investigated. Median values are used to account for large variability in models, and the associated uncertainty is calculated using a bootstrapping technique. According to the trend derived from the twelve CCMVal-2 models selected, Antarctic TOC will not return to a 1965 baseline, an average of 1960–1969 values, by the end of the 21st century in September–November, but will return in ~2080 in December. The speed of December ozone depletion before 2000 was slower compared to spring months, and thus the decadal rate of December TOC increase after 2000 is also slower. Projected trends in December ozone VMR at 20–100 hPa show a much slower rate of ozone recovery, particularly at 50–70 hPa, than for spring months. Trends in temperature and winds at 20–150 hPa are also analyzed in order to attribute the projected slow increase of December ozone and to investigate future changes in the Antarctic atmosphere in general, including some aspects of the polar vortex breakup.J. M. Siddaway, S. V. Petelina, D. J. Karoly, A. R. Klekociuk, and R. J. Dargavill

Suppression of Phase Separation in LiFePO4 Nanoparticles During Battery Discharge

Using a novel electrochemical phase-field model, we question the common belief that LixFePO4 nanoparticles separate into Li-rich and Li-poor phases during battery discharge. For small currents, spinodal decomposition or nucleation leads to moving phase boundaries. Above a critical current density (in the Tafel regime), the spinodal disappears, and particles fill homogeneously, which may explain the superior rate capability and long cycle life of nano-LiFePO4 cathodes.Comment: 27 pages, 8 figure

Contribution of ocean, fossil fuel, land biosphere, and biomass burning carbon fluxes to seasonal and interannual variability in atmospheric CO2

Author Posting. © American Geophysical Union, 2008. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Journal of Geophysical Research 113 (2008): G01010, doi:10.1029/2007JG000408.Seasonal and interannual variability in atmospheric carbon dioxide (CO2) concentrations was simulated using fluxes from fossil fuel, ocean and terrestrial biogeochemical models, and a tracer transport model with time-varying winds. The atmospheric CO2 variability resulting from these surface fluxes was compared to observations from 89 GLOBALVIEW monitoring stations. At northern hemisphere stations, the model simulations captured most of the observed seasonal cycle in atmospheric CO2, with the land tracer accounting for the majority of the signal. The ocean tracer was 3–6 months out of phase with the observed cycle at these stations and had a seasonal amplitude only ∼10% on average of observed. Model and observed interannual CO2 growth anomalies were only moderately well correlated in the northern hemisphere (R ∼ 0.4–0.8), and more poorly correlated in the southern hemisphere (R < 0.6). Land dominated the interannual variability (IAV) in the northern hemisphere, and biomass burning in particular accounted for much of the strong positive CO2 growth anomaly observed during the 1997–1998 El Niño event. The signals in atmospheric CO2 from the terrestrial biosphere extended throughout the southern hemisphere, but oceanic fluxes also exerted a strong influence there, accounting for roughly half of the IAV at many extratropical stations. However, the modeled ocean tracer was generally uncorrelated with observations in either hemisphere from 1979–2004, except during the weak El Niño/post-Pinatubo period of the early 1990s. During that time, model results suggested that the ocean may have accounted for 20–25% of the observed slowdown in the atmospheric CO2 growth rate.We acknowledge the support of NASA grant NNG05GG30G and NSF grant ATM0628472

The effects of CO2, climate and land-use on terrestrial carbon balance, 1920-1992: An analysis with four process-based ecosystem models

The concurrent effects of increasing atmospheric CO2 concentration, climate variability, and cropland establishment and abandonment on terrestrial carbon storage between 1920 and 1992 were assessed using a standard simulation protocol with four process-based terrestrial biosphere models. Over the long-term(1920–1992), the simulations yielded a time history of terrestrial uptake that is consistent (within the uncertainty) with a long-term analysis based on ice core and atmospheric CO2 data. Up to 1958, three of four analyses indicated a net release of carbon from terrestrial ecosystems to the atmosphere caused by cropland establishment. After 1958, all analyses indicate a net uptake of carbon by terrestrial ecosystems, primarily because of the physiological effects of rapidly rising atmospheric CO2. During the 1980s the simulations indicate that terrestrial ecosystems stored between 0.3 and 1.5 Pg C yr−1, which is within the uncertainty of analysis based on CO2 and O2 budgets. Three of the four models indicated (in accordance with O2 evidence) that the tropics were approximately neutral while a net sink existed in ecosystems north of the tropics. Although all of the models agree that the long-term effect of climate on carbon storage has been small relative to the effects of increasing atmospheric CO2 and land use, the models disagree as to whether climate variability and change in the twentieth century has promoted carbon storage or release. Simulated interannual variability from 1958 generally reproduced the El Niño/Southern Oscillation (ENSO)-scale variability in the atmospheric CO2 increase, but there were substantial differences in the magnitude of interannual variability simulated by the models. The analysis of the ability of the models to simulate the changing amplitude of the seasonal cycle of atmospheric CO2 suggested that the observed trend may be a consequence of CO2 effects, climate variability, land use changes, or a combination of these effects. The next steps for improving the process-based simulation of historical terrestrial carbon include (1) the transfer of insight gained from stand-level process studies to improve the sensitivity of simulated carbon storage responses to changes in CO2 and climate, (2) improvements in the data sets used to drive the models so that they incorporate the timing, extent, and types of major disturbances, (3) the enhancement of the models so that they consider major crop types and management schemes, (4) development of data sets that identify the spatial extent of major crop types and management schemes through time, and (5) the consideration of the effects of anthropogenic nitrogen deposition. The evaluation of the performance of the models in the context of a more complete consideration of the factors influencing historical terrestrial carbon dynamics is important for reducing uncertainties in representing the role of terrestrial ecosystems in future projections of the Earth system