Unpacking the modeling process for energy policy making.

This article explores how the modeling of energy systems may lead to an undue closure of alternatives by generating an excess of certainty around some of the possible policy options. We retrospectively exemplify the problem with the case of the International Institute for Applied Systems Analysis (IIASA) global modeling in the 1980s. We discuss different methodologies for quality assessment that may help mitigate this issue, which include Numeral Unit Spread Assessment Pedigree (NUSAP), diagnostic diagrams, and sensitivity auditing (SAUD). We illustrate the potential of these reflexive modeling practices in energy policy-making with three additional cases: (i) the case of the energy system modeling environment (ESME) for the creation of UK energy policy; (ii) the negative emission technologies (NETs) uptake in integrated assessment models (IAMs); and (iii) the ecological footprint indicator. We encourage modelers to adopt these approaches to achieve more robust, defensible, and inclusive modeling activities in the field of energy research.

Equations of motion for weakly compressible point vortices.

Equations of motion for compressible point vortices in the plane are obtained in the limit of small Mach number, M, using a Rayleigh-Jansen expansion and the method of Matched Asymptotic Expansions. The solution in the region between vortices is matched to solutions around each vortex core. The motion of the vortices is modified over long time scales [Formula: see text] and [Formula: see text]. Examples are given for co-rotating and co-propagating vortex pairs. The former show a correction to the rotation rate and, in general, to the centre and radius of rotation, while the latter recover the known result that the steady propagation velocity is unchanged. For unsteady configurations, the vortex solution matches to a far field in which acoustic waves are radiated. This article is part of the theme issue 'Mathematical problems in physical fluid dynamics (part 2)'.

Underlying Polar and Nonpolar Modification MOF-Based Factors that Influence Permanent Porosity in Porous Liquids.

It is increasingly apparent that porous liquids (PLs) have unique use cases due to the combination of ready liquid handling and their inherently high adsorption capacity. Among the PL types, those with permanent porosity are the most promising. Although Type II and III PLs have economic synthetic methods and can be made from a huge variety of metal-organic frameworks (MOFs) and solvents, these nanocomposites still need to be stable to be useful. This work aims to systematically explore the possibilities of creating PLs using different MOF modification methods. This delivered underpinning insights into the molecular-level influence between solvent and MOF on the overall nanocomposite stability. Zirconium-based metal-organic frameworks were combined with two different solvents of varying chemistry to deliver CO2 sorption capacities as high as 2.9 mmol g-1 at 10 bar. The results of the study could have far-reaching ramifications for future investigations in the PL field.

Practical considerations in the design and use of porous liquids.

The possibility of creating well-controlled empty space within liquids is conceptually intriguing, and from an application perspective, full of potential. Since the concept of porous liquids (PLs) arose several years ago, research efforts in this field have intensified. This review highlights the design, synthesis, and applicability of PLs through a thorough examination of the current state-of-the-art. Following a detailed examination of the fundamentals of PLs, we examine the different synthetic approaches proposed to date, discuss the nature of PLs, and their pathway from the laboratory to practical application. Finally, possible challenges and opportunities are outlined.

Forage crops and cadmium: How changing farming systems might impact cadmium accumulation in animals.

Production advantages, environmental benefits and increasing parasite resistance are changing the composition of New Zealand pastures. Traditional ryegrass/clover pasture mixes are being replaced by forage herb crops such as lucerne, chicory and plantain that accumulate a higher concentration of contaminants such as cadmium (Cd). To explore the relationship between Cd in forage crops and the Cd concentration accumulated by animals, four-month-old lambs at four farms across the central North Island of New Zealand were grazed on different forage crops (ryegrass, chicory, lucerne and plantain) between weaning and slaughter. Soil and pasture samples, and sequential liver biopsies, were collected and analysed for total Cd. There were significant differences in Cd concentration between the forage crops (chicory > plantain > lucerne > ryegrass) and this ordering was repeated for Cd in liver. There was no exceedance of maximum limits (ML) for Cd in offal set by the EU and NZ/Australia food safety standards authorities for animals of this study, although the highest concentration of Cd in chicory (0.85 mg/kg DW) was considerably lower than has been recorded elsewhere in New Zealand (4.5 mg/kg DW). Provisional Soil Management Values (SMVs) were developed to explore compliance of liver with EU food standards as a function of grazing chicory. For a soil pH of 5, exceedance might occur at a soil cadmium concentration of 0.34 mg/kg. This concentration falls within Tier 0 of the New Zealand Tiered Fertiliser Management System which seeks to ensure soil Cd remains within acceptable limits over the next 100 years and beyond. Increased Cd uptake by fodder crops and its management in these Tier 0 pastoral soils is therefore an emerging issue for pastoral agriculture. The risk of ML exceedance for animals grazing forage crops such as chicory on low Cd soils should be further considered to ensure uninterrupted access to export markets.

Tailoring molecular interactions between microporous polymers in high performance mixed matrix membranes for gas separations.

Membranes are crucial to lowering the huge energy costs of chemical separations. Whilst some promising polymers demonstrate excellent transport properties, problems of plasticisation and physical aging due to mobile polymer chains, amongst others, prevent their exploitation in membranes for industrial separations. Here we reveal that molecular interactions between a polymer of intrinsic microporosity (PIM) matrix and a porous aromatic framework additive (PAF-1) can simultaneously address plasticisation and physical aging whilst also increasing gas transport selectivity. Extensive spectroscopic characterisation and control experiments involving two near-identical PIMs, one with methyl groups (PIM-EA(Me2)-TB) and one without (PIM-EA(H2)-TB), directly confirm the key molecular interaction as the adsoprtion of methyl groups from the PIM matrix into the nanopores of the PAF. This interaction reduced physical aging by 50%, suppressed polymer chain mobilities at high pressure and increased H2 selectivity over larger gases such as CH4 and N2.

Control of Physical Aging in Super-Glassy Polymer Mixed Matrix Membranes.

ConspectusSince the discovery of polymers of intrinsic microporosity (PIMs) in 2004, the fast size-selective interconnected pore cavities of the polymers have caused the upper bound of membrane performance to be revised, twice. Simultaneously, porous materials have meant that mixed matrix membranes (MMMs) are now a relatively simple method of enhancing transport properties. While there are now reliable routes with mixed matrices to improve the fundamental transport properties of membrane materials, many of the other properties crucial for separation applications remain largely unaddressed. Physical aging severely affects membrane performance over time, especially for those prepared from high fractional free volume polymers. Gradual densification of the glassy polymer chains causes the connected pore channels present in these materials to constrict. Studies now suggest that aging of superglassy polymer materials is a two-step process; a rapid densification occurs within the first few days, followed by a gradual rearrangement of packed chains over longer time frames toward a theoretical equilibrium state. Although advantageous in terms of size selectivity, the considerable drop in permeation over the days and weeks after manufacture greatly impacts material applicability. While often still permeating faster than traditional membrane materials, the continuous gradual collapse of cavities in these polymers are a significant challenge in the application of high free volume polymer membranes. In 2014, we discovered that the porous aromatic framework PAF-1 not only greatly improved the membrane's void space and speed of gas transport but also seemingly froze several glassy polymers in a low-density state, holding the polymer's pore channels open, a process termed as Porosity Induced Side chain Adsorption (PISA).This discovery of PISA fundamentally challenged the conventional wisdom at the time that the aging rate could only be addressed by densification of the polymer. Unlike other high-performance glassy polymers, membranes containing PAF-1 can retain their high permeability for more than a year. Several other examples of antiaging behavior have been subsequently reported by the team, where control of aging rate as a function of gas penetrant, selectivity increases, and stability at higher pressures was reported. These works also demonstrate that these mixed matrix systems had applicability for several other separations, including pervaporation, solvent nanofiltration, and as separators for energy applications. In our subsequent studies, the antiaging mechanism has been elucidated as an effect of the interaction between the polymer's accessible pendant methyl group and the aromatic pore surface of PAF-1 or other antiaging additives. In otherwise identical MMMs, where this hypothesized methyl-π interaction is either absent or interrupted, we find that the antiaging behavior expected by the fixation of the polymer chains to the pore surface and PAF-1 does not occur. As a design approach for mixed matrix membranes, targeted interfacial interactions are a promising pathway for developing other stable membranes, enabling the exciting class of PIM materials to improve industrial separation efficiency.

Stability Analysis of a Bulk-Surface Reaction Model for Membrane Protein Clustering.

Protein aggregation on the plasma membrane (PM) is of critical importance to many cellular processes such as cell adhesion, endocytosis, fibrillar conformation, and vesicle transport. Lateral diffusion of protein aggregates or clusters on the surface of the PM plays an important role in governing their heterogeneous surface distribution. However, the stability behavior of the surface distribution of protein aggregates remains poorly understood. Therefore, understanding the spatial patterns that can emerge on the PM solely through protein-protein interaction, lateral diffusion, and feedback is an important step toward a complete description of the mechanisms behind protein clustering on the cell surface. In this work, we investigate the pattern formation of a reaction-diffusion model that describes the dynamics of a system of ligand-receptor complexes. The purely diffusive ligand in the cytosol can bind receptors in the PM and the resultant ligand-receptor complexes not only diffuse laterally but can also form clusters resulting in different oligomers. Finally, the largest oligomers recruit ligands from the cytosol using positive feedback. From a methodological viewpoint, we provide theoretical estimates for diffusion-driven instabilities of the protein aggregates based on the Turing mechanism. Our main result is a threshold phenomenon, in which a sufficiently high recruitment of ligands promotes the input of new monomeric components and consequently drives the formation of a single-patch spatially heterogeneous steady state.

Numerical solution of scattering problems using a Riemann-Hilbert formulation.

A fast and accurate numerical method for the solution of scalar and matrix Wiener-Hopf (WH) problems is presented. The WH problems are formulated as Riemann-Hilbert problems on the real line, and a numerical approach developed for these problems is used. It is shown that the known far-field behaviour of the solutions can be exploited to construct numerical schemes providing spectrally accurate results. A number of scalar and matrix WH problems that generalize the classical Sommerfeld problem of diffraction of plane waves by a semi-infinite plane are solved using the approach.

Solvation Effects on the Permeation and Aging Performance of PIM-1-Based MMMs for Gas Separation.

Membranes are particularly attractive for lowering the energy intensity of separations as they eliminate phase changes. While many tantalizing polymers are known, limitations in selectivity and stability slightly preclude further development. Mixed-matrix membranes may address these shortcomings. Key to their realization is the intimate mixing between the polymer and the additive to eliminate nonselective transport, improve selectivity, and resist physical aging. Polymers of intrinsic microporosity (PIMs) have inherently promising gas transport properties. Here, we show that porous additives can improve transport and resist aging in PIM-1. We develop a simple, low-cost, and scalable hyper-cross-linked polymer (poly-dichloroxylene, pDCX), which was hydroxylated to form an intimate mixture with the polar PIM-1. Solvent variation allowed control of physical aging rates and improved selectivity for smaller gases. This detailed study has allowed many interactions within mixed matrix membranes to be directly elucidated and presents a practical means to stabilize porous polymers for separation applications.

Building Additional Passageways in Polyamide Membranes with Hydrostable Metal Organic Frameworks To Recycle and Remove Organic Solutes from Various Solvents.

Membrane separation is a promising technology for extracting temperature-sensitive organic molecules from solvents. However, a lack of membrane materials that are permeable toward organic solvents yet highly selective curtails large-scale membrane applications. To overcome the trade-off between flux and selectivity, additional molecular transportation pathways are constructed in ultrathin polyamide membranes using highly hydrostable metal organic frameworks with diverse functional surface architectures. Additional passageways enhance water permeance by 84% (15.4 L m-2 h-1 bar-1) with nearly 100% rose bengal rejection and 97.6% azithromycin rejection, while showing excellent separation performance in ethyl acetate, ketones, and alcohols. These unique composite membranes remain stable in both aqueous and organic solvent environments. This immediately finds application in the purification of aqueous mixtures containing organic soluble compounds, such as antibiotics, during pharmaceutical manufacturing.

Effect of choline chloride premedication on xylazine-induced hypoxaemia in sheep.

OBJECTIVE: To determine the anti-inflammatory efficacy of choline in vivo and in vitro and to investigate the anti-inflammatory mechanisms of choline. STUDY DESIGN: Randomized, controlled studies. ANIMALS: In vivo trials used 16 Romney sheep. In vitro experiments utilized RAW 264.7 mouse macrophage cells. METHODS: Hypoxaemia induced in 16 sheep by intravenous (IV) injection of 50 µg kg-1 xylazine, an α-2 agonist, was measured in sheep at 0, 1 and 4 minutes using arterial blood gas analysis with and without 50 mg kg-1 IV choline chloride premedication. Cell culture studies used enzyme-linked immunosorbent assay to measure the release of tumour necrosis factor (TNF-α) from lipopolysaccharide (LPS) stimulated macrophages with and without choline chloride premedication. TNF-α release was compared to thalidomide suppressed and untreated cells. RESULTS: Choline premedication in sheep mitigated a reduction in arterial partial pressure of oxygen (PaO2) but did not prevent development of clinically significant hypoxaemia. Decrease in mean PaO2 of choline treated sheep was 6.36 kPa (47.7 mmHg) compared to 9.81 kPa (73.6 mmHg) in control sheep. In vitro studies demonstrate that choline administered concurrent with LPS activation did not significantly suppress TNF-α expression but that treatment of cells with choline 10 minutes prior to LPS activation did significantly suppress TNF-α expression. Choline pretreated cells expressed 23.99 ± 4.52 ng mg-1 TNF-α while LPS only control cells expressed 33.83 ± 3.20 ng mg-1. CONCLUSIONS: Choline is able to prevent macrophage activation in vitro when administered prior to LPS activation and may reduce hypoxaemia in sheep developing pulmonary oedema after xylazine administration. This effect requires premedication with choline. CLINICAL RELEVANCE: Pharmacological manipulation of autonomic inflammatory responses holds promise for the treatment of inflammation. However, the complex cellular mechanisms involved in this reflex means that an adequate therapy should approach multiple pathways and mechanisms of the inflammatory response.

Dynamics and transport properties of three surface quasigeostrophic point vortices.

The surface quasi-geostrophic (SQG) equations are a model for low-Rossby number geophysical flows in which the dynamics are governed by potential temperature dynamics on the boundary. We examine point vortex solutions to this model as well as the chaotic flows induced by three point vortices. The chaotic transport induced by these flows is investigated using techniques of Poincaré maps and the Finite Time Braiding Exponent (FTBE). This chaotic transport is representative of the mixing in the flow, and these terms are used interchangeably in this work. Compared with point vortices in two-dimensional flow, the SQG vortices are found to produce flows with higher FTBE, indicating more mixing. Select results are presented for analyzing mixing for arbitrary vortex strengths.

Post-synthetic Ti exchanged UiO-66 metal-organic frameworks that deliver exceptional gas permeability in mixed matrix membranes.

Gas separation membranes are one of the lowest energy technologies available for the separation of carbon dioxide from flue gas. Key to handling the immense scale of this separation is maximised membrane permeability at sufficient selectivity for CO2 over N2. For the first time it is revealed that metals can be post-synthetically exchanged in MOFs to drastically enhance gas transport performance in membranes. Ti-exchanged UiO-66 MOFs have been found to triple the gas permeability without a loss in selectivity due to several effects that include increased affinity for CO2 and stronger interactions between the polymer matrix and the Ti-MOFs. As a result, it is also shown that MOFs optimized in previous works for batch-wise adsorption applications can be applied to membranes, which have lower demands on material quantities. These membranes exhibit exceptional CO2 permeability enhancement of as much as 153% when compared to the non-exchanged UiO-66 mixed-matrix controls, which places them well above the Robeson upper bound at just a 5 wt.% loading. The fact that maximum permeability enhancement occurs at such low loadings, significantly less than the optimum for other MMMs, is a major advantage in large-scale application due to the more attainable quantities of MOF needed.

In the shadow of a pepper-centric historiography: Understanding the global diffusion of capsicums in the sixteenth and seventeenth centuries.

Historians of the Eurasian spice trade focus on the fortunes of black pepper (Piper Nigrum L.), largely because the trading companies of the Dutch and English which they study also did. Capsicum peppers are, however, the world׳s most consumed spice, and their story needs to be told in parallel. The five species of capsicum peppers spread across the world in less than two hundred years following their discovery by Europeans in South and Central America and proved both hardier than Piper nigrum and able to reproduce spontaneously. While the taste was similar but more pungent than black pepper, capsicums provided an important vitamin C and bioflavanoid supplement to poorer people in southern and eastern Europe far from the precepts of good taste as dictated from Paris, and rapidly became a mainstay of tropical cuisine across the world. This contribution seeks both to trace and to understand that diffusion and its principal vectors from historical research amongst a plethora of primary source materials in European and Asian languages. Medical and dietetic reaction is presented from a wide range of contemporary texts. The work proceeds according to deductive reasoning and in comparison to the diffusion of black pepper consumption. It reveals the very different strategies of import substitution and commercial embargo undertaken by Portuguese and Spanish authorities, a somewhat later date of arrival in China than previously thought, and three different, competing lines of entry into an important area of later cultivation, namely Central Europe.

An Arabidopsis rhomboid protease has roles in the chloroplast and in flower development.

Increasing numbers of cellular pathways are now recognized to be regulated via proteolytic processing events. The rhomboid family of serine proteases plays a pivotal role in a diverse range of pathways, activating and releasing proteins via regulated intramembrane proteolysis. The prototype rhomboid protease, rhomboid-1 in Drosophila, is the key activator of epidermal growth factor (EGF) receptor pathway signalling in the fly and thus affects multiple aspects of development. The role of the rhomboid family in plants is explored and another developmental phenotype, this time in a mutant of an Arabidopsis chloroplast-localized rhomboid, is reported here. It is confirmed by GFP-protein fusion that this protease is located in the envelope of chloroplasts and of chlorophyll-free plastids elsewhere in the plant. Mutant plants lacking this organellar rhomboid demonstrate reduced fertility, as documented previously with KOM-the one other Arabidopsis rhomboid mutant that has been reported in the literature-along with aberrant floral morphology.

Wind gusts and plant aeroelasticity effects on the aerodynamics of pollen shedding: a hypothetical turbulence-initiated wind-pollination mechanism.

Plant reproduction depends on pollen dispersal. For anemophilous (wind-pollinated) species, such as grasses and many trees, shedding pollen from the anther must be accomplished by physical mechanisms. The unknown nature of this process has led to its description as the 'paradox of pollen liberation'. A simple scaling analysis, supported by experimental measurements on typical wind-pollinated plant species, is used to estimate the suitability of previous resolutions of this paradox based on wind-gust aerodynamic models of fungal-spore liberation. According to this scaling analysis, the steady Stokes drag force is found to be large enough to liberate anemophilous pollen grains, and unsteady boundary-layer forces produced by wind gusts are found to be mostly ineffective since the ratio of the characteristic viscous time scale to the inertial time scale of acceleration of the wind stream is a small parameter for typical anemophilous species. A hypothetical model of a stochastic aeroelastic mechanism, initiated by the atmospheric turbulence typical of the micrometeorological conditions in the vicinity of the plant, is proposed to contribute to wind pollination.

[N-methyl-11C]Mirtazapine for positron emission tomography neuroimaging of antidepressant actions in humans.

RATIONALE: Many actions of antidepressant drugs cannot yet be studied using positron emission tomography (PET) neuroimaging due to lack of suitable radioligands. We believe that mirtazapine, radiolabeled with C-11, might be suitable for PET neuroimaging of alpha2-adrenoceptors in selected regions of the living human brain. OBJECTIVE: To determine the regional central biodistribution and pharmacokinetics of [N-methyl-11C]mirtazapine in humans. METHODS: Five healthy volunteers received an intravenous injection of [N-methyl-11C]mirtazapine for evaluating its metabolism, biodistribution and pharmacokinetics. RESULTS: [N-methyl-11C]Mirtazapine entered the brain readily, with initial clearance from blood to tissue (K1) ranging from 0.31 ml/ml/min in amygdala to 0.54 ml/ml/min in thalamus. The rate of metabolism of [N-methyl-11C]mirtazapine in the bloodstream was relatively slow, with 20-40% of [11C]-derived radioactivity still present as parent compound at 60 min post-injection. The clearance of [N-methyl-11C]mirtazapine from the tissue compartment (k2') ranged from a low of 0.03 min(-1) in amygdala to a high of 0.06-0.07 min(-1) in thalamus and cerebellum. The volume of distribution (Ve') of [N-methyl-11C]mirtazapine was markedly greater in hippocampus and amygdala (11.3-12.0) than in cerebellum (6.7), with intermediate levels in the thalamus (9.4). CONCLUSIONS: [N-methyl-11C]Mirtazapine has suitable properties for PET neuroimaging. We envision [N-methyl-11C]mirtazapine as a molecular probe for PET imaging of antidepressant actions at sites such as alpha2-adrenoceptors in the living human brain.

Biodistribution and radiation dosimetry of [N-methyl-11C]mirtazapine, an antidepressant affecting adrenoceptors.

Central adrenoceptors cannot currently be studied by PET neuroimaging due to a lack of appropriate radioligands. The fast-acting antidepressant drug mirtazapine, radiolabelled for PET, may be of value for assessing central adrenoceptors, provided that the radiation dosimetry of the radioligand is acceptable. To obtain that information, serial whole-body images were made for up to 70 min following intravenous injection of 326 and 185 MBq [N-methyl-11C]mirtazapine (specific activities E.O.S. of 119 and 39G Bq/micromol, respectively) in a healthy volunteer. Ten source organs plus remaining body were considered in estimating absorbed radiation doses calculated using MIRD 3.1. The highest absorbed organ doses were found to the lungs (3.4 x 10(-2) mGy/MBq), adrenals (1.2 x 10(-2) mGy/MBq), spleen (1.2 x 10(-2) mGy/MBq), and gallbladder wall (1.1 x 10(-2) mGy/MBq). The effective dose was estimated to be 6.8 x 10(-3) mSv/MBq, which is similar to that produced by several radioligands used routinely for neuroimaging.