pH-, thermo- and electrolyte-responsive polymer gels derived from a well-defined, RAFT-synthesized, poly(2-vinyl-4,4-dimethylazlactone) homopolymer via one-pot post-polymerization modification

Well-defined stimulus-responsive polymer gels were prepared from poly(2-vinyl-4,4-dimethylazlatone) (PVDMA) via one-pot post-polymerization modification. VDMA homopolymers were reacted with diamine crosslinking agents and functional 1° or 2° amines to form polymer gels that swelled in organic solvents and, in many cases, aqueous solutions. A series of functional amine reagents, including N,N-dimethylethylenediamine (DMEDA), N,N-diethylethylenediamine (DEEDA), morpholine, 3-morpholinopropylamine (MPPA) and tetrahydrofurfurylamine (THFA), were chosen as functional amines to produce polymer gels containing environmentally sensitive species. 13C solid-state NMR and FTIR spectroscopic measurements confirmed complete conversion of the reactive scaffolds. pH-dependent swelling behavior at ambient temperature was observed in DMEDA-, DEEDA- and MPPA-modified hydrogels. Kinetic studies showed the swelling behaviors of DMEDA-modified hydrogels were regulated by cross-linker type and concentration in acidic water (pH = 4) at ambient temperature. The swelling ratio of hydrogels modified by DEEDA, MPPA and THFA also depended strongly on temperature, indicating successful synthesis of thermoresponsive gels. Furthermore, the concentration of added sodium sulfate played a significant role with respect to the swelling properties of MPPA-modified hydrogels. These smart materials may be of interest in the biomedical field as well as in other applications

A Scale-Explicit Framework for Conceptualizing the Environmental Impacts of Agricultural Land Use Changes

Demand for locally-produced food is growing in areas outside traditionally dominant agricultural regions due to concerns over food safety, quality, and sovereignty; rural livelihoods; and environmental integrity. Strategies for meeting this demand rely upon agricultural land use change, in various forms of either intensification or extensification (converting non-agricultural land, including native landforms, to agricultural use). The nature and extent of the impacts of these changes on non-food-provisioning ecosystem services are determined by a complex suite of scale-dependent interactions among farming practices, site-specific characteristics, and the ecosystem services under consideration. Ecosystem modeling strategies which honor such complexity are often impenetrable by non-experts, resulting in a prevalent conceptual gap between ecosystem sciences and the field of sustainable agriculture. Referencing heavily forested New England as an example, we present a conceptual framework designed to synthesize and convey understanding of the scale- and landscape-dependent nature of the relationship between agriculture and various ecosystem services. By accounting for the total impact of multiple disturbances across a landscape while considering the effects of scale, the framework is intended to stimulate and support the collaborative efforts of land managers, scientists, citizen stakeholders, and policy makers as they address the challenges of expanding local agriculture

High-Risk Contexts for Violence Against Women: Using Latent Class Analysis to Understand Structural and Contextual Drivers of Intimate Partner Violence at the National Level

Introduction: Intimate partner violence (IPV) affects 1 in 3 women and poses a major human rights threat and public health burden, yet there is great variation in risk globally. Whilst individual risk factors are well-studied, less research has focussed on the structural and contextual drivers of IPV and how these co-occur to create contexts of high risk. Methods: We compiled IPV drivers from freely-accessible global country-level data sources and combined gender inequality, natural disasters, conflict, colonialism, socioeconomic development and inequality, homicide and social discrimination in a latent class analysis, and identified underlying 'risk contexts' based on fit statistics and theoretical plausibility (N=5,732 country-years; 190 countries). We used multinomial regression to compare risk contexts according to: proportion of population with disability, HIV/AIDS, refugee status, and mental health disorders; proportion of men with drug use disorders; men's alcohol consumption; and population median age (N=1,654-5,725 country-years). Finally, we compared prevalence of physical and/or sexual IPV experienced by women in the past 12 months across risk contexts (N=3,175 country-years). Results: Three distinct risk contexts were identified: 1) non-patriarchal egalitarian, low rates of homicide; 2) patriarchal post-colonial, high rates of homicide; 3) patriarchal post-colonial conflict and disaster-affected. Compared to non-patriarchal egalitarian contexts, patriarchal post-colonial contexts had a younger age distribution and a higher prevalence of drug use disorders, but a lower prevalence of mental health disorders and a smaller refugee population. IPV risk was highest in the two patriarchal post-colonial contexts and associated with country income classification. Conclusions: Whilst our findings support the importance of gender norms in shaping women's risk of experiencing IPV, they also point towards an association with a history of colonialism. To effectively address IPV for women in high prevalence contexts, structural interventions and policies are needed that address not only gender norms, but also broader structural inequalities arising from colonialism

Magic angle spinning (MAS) NMR linewidths in the presence of solid-state dynamics

In solid-state NMR, the magic angle spinning (MAS) technique fails to suppress anisotropic spin interactions fully if reorientational dynamics are present, resulting in a decay of the rotational-echo train in the time-domain signal. We show that a simple analytical model can be used to quantify this linebroadening effect as a function of the MAS frequency, reorientational rate constant, and magnitude of the inhomogeneous anisotropic broadening. We compare this model with other theoretical approaches and with exact computer simulations, and show how it may be used to estimate rate constants from experimental NMR data

Geniculo-Cortical Projection Diversity Revealed within the Mouse Visual Thalamus.

The mouse dorsal lateral geniculate nucleus (dLGN) is an intermediary between retina and primary visual cortex (V1). Recent investigations are beginning to reveal regional complexity in mouse dLGN. Using local injections of retrograde tracers into V1 of adult and neonatal mice, we examined the developing organisation of geniculate projection columns: the population of dLGN-V1 projection neurons that converge in cortex. Serial sectioning of the dLGN enabled the distribution of labelled projection neurons to be reconstructed and collated within a common standardised space. This enabled us to determine: the organisation of cells within the dLGN-V1 projection columns; their internal organisation (topology); and their order relative to V1 (topography). Here, we report parameters of projection columns that are highly variable in young animals and refined in the adult, exhibiting profiles consistent with shell and core zones of the dLGN. Additionally, such profiles are disrupted in adult animals with reduced correlated spontaneous activity during development. Assessing the variability between groups with partial least squares regression suggests that 4-6 cryptic lamina may exist along the length of the projection column. Our findings further spotlight the diversity of the mouse dLGN--an increasingly important model system for understanding the pre-cortical organisation and processing of visual information. Furthermore, our approach of using standardised spaces and pooling information across many animals will enhance future functional studies of the dLGN.Funding was provided by a Wellcome Trust grant jointly awarded to IDT and SJE (083205, www.wellcome.ac.uk), and by MRC PhD Studentships awarded to MNL and ACH (http://www.mrc.ac.uk/).This is the final version of the article. It was first available from PLOS via http://dx.doi.org/10.1371/journal.pone.014484

Universality and Scaling at the Onset of Quantum Black Hole Formation

In certain two-dimensional models, collapsing matter forms a black hole if and only if the incoming energy flux exceeds the Hawking radiation rate. Near the critical threshold, the black hole mass is given by a universal formula in terms of the distance from criticality, and there exists a scaling solution describing the formation and evaporation of an arbitrarily small black hole.Comment: 9 pages, 3 figures (uuencoded

The global and regional impacts of climate change under Representative Concentration Pathway forcings and Shared Socioeconomic Pathway socioeconomic scenarios

This paper presents an evaluation of the global and regional consequences of climate change for heat extremes, water resources, river and coastal flooding, droughts, agriculture and energy use. It presents change in hazard and resource base under different rates of climate change (Representative Concentration Pathways: RCP), and socio-economic impacts are estimated for each combination of RCP and Shared Socioeconomic Pathway. Uncertainty in the regional pattern of climate change is characterised by CMIP5 climate model projections. The analysis adopts a novel approach using relationships between level of warming and impact to rapidly estimate impacts under any climate forcing. The projections provided here can be used to inform assessments of the implications of climate change. At the global scale all the consequences of climate change considered here are adverse, with large increases under the highest rates of warming. Under the highest forcing the global average annual chance of a major heatwave increases from 5% now to 97% in 2100, the average proportion of time in drought increases from 7% to 27%, and the average chance of the current 50-year flood increases from 2% to 7%. The socio-economic impacts of these climate changes are determined by socio-economic scenario. There is variability in impact across regions, reflecting variability in projected changes in precipitation and temperature. The range in the estimated impacts can be large, due to uncertainty in future emissions and future socio-economic conditions and scientific uncertainty in how climate changes in response to future emissions. For the temperature-based indicators, the largest source of scientific uncertainty is in the estimated magnitude of equilibrium climate sensitivity, but for the indicators determined by precipitation the largest source is in the estimated spatial and seasonal pattern of changes in precipitation. By 2100 the range across socio-economic scenario is often greater than the range across the forcing levels

High-sensitivity cardiac troponin concentrations at presentation in patients with ST-segment elevation myocardial infarction

No abstract available