On the role of specific interactions in the diffusion of nanoparticles in aqueous polymer solutions

Understanding nanoparticle diffusion within non-Newtonian biological and synthetic fluids is essential in designing novel formulations (e.g., nanomedicines for drug delivery, shampoos, lotions, coatings, paints, etc.), but is presently poorly defined. This study reports the diffusion of thiolated and PEGylated silica nanoparticles, characterized by small-angle neutron scattering, in solutions of various water-soluble polymers such as poly(acrylic acid) (PAA), poly(Nvinylpyrrolidone) (PVP), poly(ethylene oxide) (PEO), and hydroxyethylcellulose (HEC) probed using NanoSight nanoparticle tracking analysis. Results show that the diffusivity of nanoparticles is affected by their dimensions, medium viscosity, and, in particular, the specific interactions between nanoparticles and the macromolecules in solution; strong attractive interactions such as hydrogen bonding hamper diffusion. The water-soluble polymers retarded the diffusion of thiolated particles in the order PEO > PVP > PAA > HEC whereas for PEGylated silica particles retardation followed the order PAA > PVP = HEC > PEO. In the absence of specific interactions with the medium, PEGylated nanoparticles exhibit enhanced mobility compared to their thiolated counterparts despite some increase in their dimensions.

Formulation and implementation of a residual-mean ocean circulation model

A parameterization of mesoscale eddies in coarse-resolution ocean general circulation models (GCM) is formulated and implemented using a residual-mean formalism. In that framework, mean buoyancy is advected by the residual velocity (the sum of the Eulerian and eddy-induced velocities) and modified by a residual flux which accounts for the diabatic effects of mesoscale eddies. The residual velocity is obtained by stepping forward a residual-mean momentum equation in which eddy stresses appear as forcing terms. Study of the spatial distribution of eddy stresses, derived by using them as control parameters to ‘‘fit’’ the residual-mean model to observations, supports the idea that eddy stresses can be likened to a vertical down-gradient flux of momentum with a coefficient which is constant in the vertical. The residual eddy flux is set to zero in the ocean interior, where mesoscale eddies are assumed to be quasi-adiabatic, but is parameterized by a horizontal down-gradient diffusivity near the surface where eddies develop a diabatic component as they stir properties horizontally across steep isopycnals. The residual-mean model is implemented and tested in the MIT general circulation model. It is shown that the resulting model (1) has a climatology that is superior to that obtained using the Gent and McWilliams parameterization scheme with a spatially uniform diffusivity and (2) allows one to significantly reduce the (spurious) horizontal viscosity used in coarse resolution GCMs.

Mixed layer lateral eddy fluxes mediated by air-sea interaction

The modulation of air–sea heat fluxes by geostrophic eddies due to the stirring of temperature at the sea surface is discussed and quantified. It is argued that the damping of eddy temperature variance by such air–sea fluxes enhances the dissipation of surface temperature fields. Depending on the time scale of damping relative to that of the eddying motions, surface eddy diffusivities can be significantly enhanced over interior values. The issues are explored and quantified in a controlled setting by driving a tracer field, a proxy for sea surface temperature, with surface altimetric observations in the Antarctic Circumpolar Current (ACC) of the Southern Ocean. A new, tracer-based diagnostic of eddy diffusivity is introduced, which is related to the Nakamura effective diffusivity. Using this, the mixed layer lateral eddy diffusivities associated with (i) eddy stirring and small-scale mixing and (ii) surface damping by air–sea interaction is quantified. In the ACC, a diffusivity associated with surface damping of a comparable magnitude to that associated with eddy stirring (;500 m2 s21) is found. In frontal regions prevalent in the ACC, an augmentation of surface lateral eddy diffusivities of this magnitude is equivalent to an air–sea flux of 100 W m22 acting over a mixed layer depth of 100 m, a very significant effect. Finally, the implications for other tracer fields such as salinity, dissolved gases, and chlorophyll are discussed. Different tracers are found to have surface eddy diffusivities that differ significantly in magnitude.

A traceable physical calibration of the vertical advection-diffusion equation for modelling ocean heat uptake

The classic vertical advection-diffusion (VAD) balance is a central concept in studying the ocean heat budget, in particular in simple climate models (SCMs). Here we present a new framework to calibrate the parameters of the VAD equation to the vertical ocean heat balance of two fully-coupled climate models that is traceable to the models’ circulation as well as to vertical mixing and diffusion processes. Based on temperature diagnostics, we derive an effective vertical velocity w∗ and turbulent diffusivity k∗ for each individual physical process. In steady-state, we find that the residual vertical velocity and diffusivity change sign in mid-depth, highlighting the different regional contributions of isopycnal and diapycnal diffusion in balancing the models’ residual advection and vertical mixing. We quantify the impacts of the time-evolution of the effective quantities under a transient 1%CO2 simulation and make the link to the parameters of currently employed SCMs.

Frontal networks in adults with autism spectrum disorder

It has been postulated that autism spectrum disorder is underpinned by an ‘atypical connectivity’ involving higher-order association brain regions. To test this hypothesis in a large cohort of adults with autism spectrum disorder we compared the white matter networks of 61 adult males with autism spectrum disorder and 61 neurotypical controls, using two complementary approaches to diffusion tensor magnetic resonance imaging. First, we applied tract-based spatial statistics, a ‘whole brain’ non-hypothesis driven method, to identify differences in white matter networks in adults with autism spectrum disorder. Following this we used a tract-specific analysis, based on tractography, to carry out a more detailed analysis of individual tracts identified by tract-based spatial statistics. Finally, within the autism spectrum disorder group, we studied the relationship between diffusion measures and autistic symptom severity. Tract-based spatial statistics revealed that autism spectrum disorder was associated with significantly reduced fractional anisotropy in regions that included frontal lobe pathways. Tractography analysis of these specific pathways showed increased mean and perpendicular diffusivity, and reduced number of streamlines in the anterior and long segments of the arcuate fasciculus, cingulum and uncinate—predominantly in the left hemisphere. Abnormalities were also evident in the anterior portions of the corpus callosum connecting left and right frontal lobes. The degree of microstructural alteration of the arcuate and uncinate fasciculi was associated with severity of symptoms in language and social reciprocity in childhood. Our results indicated that autism spectrum disorder is a developmental condition associated with abnormal connectivity of the frontal lobes. Furthermore our findings showed that male adults with autism spectrum disorder have regional differences in brain anatomy, which correlate with specific aspects of autistic symptoms. Overall these results suggest that autism spectrum disorder is a condition linked to aberrant developmental trajectories of the frontal networks that persist in adult life.

First-order turbulence closure for modelling complex canopy flows

Simple first-order closure remains an attractive way of formulating equations for complex canopy flows when the aim is to find analytic or simple numerical solutions to illustrate fundamental physical processes. Nevertheless, the limitations of such closures must be understood if the resulting models are to illuminate rather than mislead. We propose five conditions that first-order closures must satisfy then test two widely used closures against them. The first is the eddy diffusivity based on a mixing length. We discuss the origins of this approach, its use in simple canopy flows and extensions to more complex flows. We find that it satisfies most of the conditions and, because the reasons for its failures are well understood, it is a reliable methodology. The second is the velocity-squared closure that relates shear stress to the square of mean velocity. Again we discuss the origins of this closure and show that it is based on incorrect physical principles and fails to satisfy any of the five conditions in complex canopy flows; consequently its use can lead to actively misleading conclusions.