[C7H10N][In3Se5]: a layered selenide with two indium coordination environments

A new layered indium selenide, [C7H10N][In3Se5], was prepared under solvothermal conditions using 3,5-dimethylpyridine as a structure-directing agent. The crystal structure contains anionic layers of stoichiometry [In3Se5]− in which indium atoms with octahedral and tetrahedral coordination coexist. This material represents the first occurrence of octahedrally coordinated indium in a solvothermally-prepared indium selenide.

Synthesis, characterization and physical properties of the skutterudites YbxFe2Ni2Sb12 (0≤x≤0.4)

The skutterudites YbxFe2Ni2Sb12 (0≤x≤0.4) have been prepared by solid-state reaction and characterised by powder X-ray diffraction. The compounds crystallise in the cubic space group Im View the MathML source3¯ (a≈9.1 Å) with Yb atoms partially filling the voids in the skutterudite framework. A neutron time-of-flight diffraction experiment for Fe2Ni2Sb12 confirms the disorder of Fe and Ni atoms on the transition-metal site. Electrical resistivity, Seebeck coefficient and thermal conductivity measurements indicate that the thermoelectric performance of the skutterudites shows a marked dependence on the Yb content. Magnetic measurements over the temperature range 2≤T/K≤300 show paramagnetic behaviour for all compounds. Decomposition studies under an oxidising atmosphere at elevated temperatures have also been carried out by thermogravimetric analysis.

Synthesis and thermoelectric properties of the new skutterudites Yb x Fe2Ni2Sb12 (0 ≤ x ≤ 0.4)

The family of materials Yb x Fe2 Ni 2Sb12 (0 ≤ x ≤ 0.4) has been prepared by solid-state synthesis from the pure elements and characterized by powder X-ray diffraction. These materials crystallize in the skutterudite structure, with the framework voids partially filled with Yb atoms. Electrical resistivity, Seebeck coefficient and thermal conductivity measurements have been performed on hot-pressed samples, and indicate that the thermoelectric performance is significantly improved by increasing the Yb content. The decomposition of the compounds under oxidizing atmosphere at elevated temperatures has also been studied by thermogravimetric analysis. The physical properties and thermal stability of the new compounds are further discussed in comparison with those of the reported isostructural and isoelectronic Yb x Co4Sb12 (0 ≤ x ≤ 0.19).

Recent developments in nanostructured materials for high-performance thermoelectrics

This highlight discusses recent trends in the search for new high-efficiency thermoelectric materials. Thermoelectric materials offer considerable attractions in the pursuit of a more efficient use of existing energy resources, as they may be used to construct power-generation devices that allow useful electrical power to be extracted from otherwise waste heat. Here, we focus on the significant enhancements in thermoelectric performance that have been achieved through nanostructuring. The principal factor behind the improved performance appears to be increased phonon scattering at interfaces. This results in a substantial reduction in the lattice contribution to thermal conductivity, a low value of which is a key requirement for improved thermoelectric performance.

LEGO® bricks as building blocks for centimeter-scale biological environments

LEGO bricks are commercially available interlocking pieces of plastic that are conventionally used as toys. We describe their use to build engineered environments for cm-scale biological systems, in particular plant roots. Specifically, we take advantage of the unique modularity of these building blocks to create inexpensive, transparent, reconfigurable, and highly scalable environments for plant growth in which structural obstacles and chemical gradients can be precisely engineered to mimic soil.

Thermoelectric materials: a new rapid synthesis process for non-toxic and high-performance tetrahedrite compounds

The feasibility to synthesize, in large quantity, pure and non-toxic tetrahedrite compounds using high-energy mechanical-alloying from only elemental precursors is reported in the present paper for the first time. Our processing technique allows a better control of the final product composition and leads to high thermoelectric performances (ZT of 0.75 at 700 K), comparable to that reported on sealed tube synthesis samples. Combined with spark plasma sintering, the production of highly pure and dense samples is achieved in a very short time, at least 8 times shorter than in conventional liquid-solid-vapor synthesis process. The process described in this paper is a promising way to produce high performance tetrahedrite materials for cost-effective and large-scale thermoelectric applications.

Key bioactive reaction products of the NO/H2S interaction are S/N-hybrid species, polysulfides, and nitroxyl

Experimental evidence suggests that nitric oxide (NO) and hydrogen sulfide (H2S) signaling pathways are intimately intertwined, with mutual attenuation or potentiation of biological responses in the cardiovascular system and elsewhere. The chemical basis of this interaction is elusive. Moreover, polysulfides recently emerged as potential mediators of H2S/sulfide signaling, but their biosynthesis and relationship to NO remain enigmatic. We sought to characterize the nature, chemical biology, and bioactivity of key reaction products formed in the NO/sulfide system. At physiological pH, we find that NO and sulfide form a network of cascading chemical reactions that generate radical intermediates as well as anionic and uncharged solutes, with accumulation of three major products: nitrosopersulfide (SSNO−), polysulfides, and dinitrososulfite N-nitrosohydroxylamine-N-sulfonate (SULFI/NO), each with a distinct chemical biology and in vitro and in vivo bioactivity. SSNO− is resistant to thiols and cyanolysis, efficiently donates both sulfane sulfur and NO, and potently lowers blood pressure. Polysulfides are both intermediates and products of SSNO− synthesis/decomposition, and they also decrease blood pressure and enhance arterial compliance. SULFI/NO is a weak combined NO/nitroxyl donor that releases mainly N2O on decomposition; although it affects blood pressure only mildly, it markedly increases cardiac contractility, and formation of its precursor sulfite likely contributes to NO scavenging. Our results unveil an unexpectedly rich network of coupled chemical reactions between NO and H2S/sulfide, suggesting that the bioactivity of either transmitter is governed by concomitant formation of polysulfides and anionic S/N-hybrid species. This conceptual framework would seem to offer ample opportunities for the modulation of fundamental biological processes governed by redox switching and sulfur trafficking.

Hydrothermal synthesis of [C6H16N2][In2Se3(Se2)]: a new one-dimensional indium selenide

A new organically templated indium selenide, [C6H16N2][In2Se3(Se2)], has been prepared hydrothermally from the reaction of indium, selenium and trans-1,4-diaminocyclohexane in water at 170 °C. This material was characterised by single-crystal and powder X-ray diffraction, thermogravimetric analysis, UV–vis diffuse reflectance spectroscopy, FT-IR and elemental analysis. The compound crystallises in the monoclinic space group C2/c (a=12.0221(16) Å, b=11.2498(15) Å, c=12.8470(17) Å, β=110.514(6)°). The crystal structure of [C6H16N2][In2Se3(Se2)] contains anionic chains of stoichiometry [In2Se3(Se2)]2−, which are aligned parallel to the [1 0 1] direction, and separated by diprotonated trans-1,4-diaminocyclohexane cations. The [In2Se3(Se2)]2− chains, which consist of alternating four-membered [In2Se2] and five-membered [In2Se3] rings, contain perselenide (Se2)2− units. UV–vis diffuse reflectance spectroscopy indicates that [C6H16N2][In2Se3(Se2)] has a band gap of 2.23(1) eV

Joint data assimilation of satellite reflectance and net ecosystem exchange data constrains ecosystem carbon fluxes at a high-elevation subalpine forest

We utilized an ecosystem process model (SIPNET, simplified photosynthesis and evapotranspiration model) to estimate carbon fluxes of gross primary productivity and total ecosystem respiration of a high-elevation coniferous forest. The data assimilation routine incorporated aggregated twice-daily measurements of the net ecosystem exchange of CO2 (NEE) and satellite-based reflectance measurements of the fraction of absorbed photosynthetically active radiation (fAPAR) on an eight-day timescale. From these data we conducted a data assimilation experiment with fifteen different combinations of available data using twice-daily NEE, aggregated annual NEE, eight-day f AP AR, and average annual fAPAR. Model parameters were conditioned on three years of NEE and fAPAR data and results were evaluated to determine the information content from the different combinations of data streams. Across the data assimilation experiments conducted, model selection metrics such as the Bayesian Information Criterion and Deviance Information Criterion obtained minimum values when assimilating average annual fAPAR and twice-daily NEE data. Application of wavelet coherence analyses showed higher correlations between measured and modeled fAPAR on longer timescales ranging from 9 to 12 months. There were strong correlations between measured and modeled NEE (R2, coefficient of determination, 0.86), but correlations between measured and modeled eight-day fAPAR were quite poor (R2 = −0.94). We conclude that this inability to determine fAPAR on eight-day timescale would improve with the considerations of the radiative transfer through the plant canopy. Modeled fluxes when assimilating average annual fAPAR and annual NEE were comparable to corresponding results when assimilating twice-daily NEE, albeit at a greater uncertainty. Our results support the conclusion that for this coniferous forest twice-daily NEE data are a critical measurement stream for the data assimilation. The results from this modeling exercise indicate that for this coniferous forest, average annuals for satellite-based fAPAR measurements paired with annual NEE estimates may provide spatial detail to components of ecosystem carbon fluxes in proximity of eddy covariance towers. Inclusion of other independent data streams in the assimilation will also reduce uncertainty on modeled values.

Nonlinearity of ocean heat uptake during warming and cooling in the FAMOUS climate model

Atmospheric CO2 concentration is expected to continue rising in the coming decades, but natural or artificial processes may eventually reduce it. We show that, in the FAMOUS atmosphere-ocean general circulation model, the reduction of ocean heat content as radiative forcing decreases is greater than would be expected from a linear model simulation of the response to the applied forcings. We relate this effect to the behavior of the Atlantic meridional overturning circulation (AMOC): the ocean cools more efficiently with a strong AMOC. The AMOC weakens as CO2 rises, then strengthens as CO2 declines, but temporarily overshoots its original strength. This nonlinearity comes mainly from the accumulated advection of salt into the North Atlantic, which gives the system a longer memory. This implies that changes observed in response to different CO2 scenarios or from different initial states, such as from past changes, may not be a reliable basis for making projections.

Distinct clinical and neuropathological features of G51D SNCA mutation cases compared with SNCA duplication and H50Q mutation

Background: We and others have described the neurodegenerative disorder caused by G51D SNCA mutation which shares characteristics of Parkinson’s disease (PD) and multiple system atrophy (MSA). The objective of this investigation was to extend the description of the clinical and neuropathological hallmarks of G51D mutant SNCA-associated disease by the study of two additional cases from a further G51D SNCA kindred and to compare the features of this group with a SNCA duplication case and a H50Q SNCA mutation case. Results: All three G51D patients were clinically characterised by parkinsonism, dementia, visual hallucinations, autonomic dysfunction and pyramidal signs with variable age at disease onset and levodopa response. The H50Q SNCA mutation case had a clinical picture that mimicked late-onset idiopathic PD with a good and sustained levodopa response. The SNCA duplication case presented with a clinical phenotype of frontotemporal dementia with marked behavioural changes, pyramidal signs, postural hypotension and transiently levodopa responsive parkinsonism. Detailed post-mortem neuropathological analysis was performed in all cases. All three G51D cases had abundant α-synuclein pathology with characteristics of both PD and MSA. These included widespread cortical and subcortical neuronal α-synuclein inclusions together with small numbers of inclusions resembling glial cytoplasmic inclusions (GCIs) in oligodendrocytes. In contrast the H50Q and SNCA duplication cases, had α-synuclein pathology resembling idiopathic PD without GCIs. Phosphorylated α-synuclein was present in all inclusions types in G51D cases but was more restricted in SNCA duplication and H50Q mutation. Inclusions were also immunoreactive for the 5G4 antibody indicating their highly aggregated and likely fibrillar state. Conclusions: Our characterisation of the clinical and neuropathological features of the present small series of G51D SNCA mutation cases should aid the recognition of this clinico-pathological entity. The neuropathological features of these cases consistently share characteristics of PD and MSA and are distinct from PD patients carrying the H50Q or SNCA duplication.

Ball milling as an effective route for the preparation of doped bornite: synthesis, stability and thermoelectric properties

Bornite, Cu5FeS4, is a naturally-occuring mineral with an ultralow thermal conductivity and potential for thermoelectric power generation. We describe here a new, easy and scalable route to synthesise bornite, together with the thermoelectric behaviour of manganese-substituted derivatives, Cu5Fe1-xMnxS4 (0 ≤ x ≤ 0.10). The electrical and thermal transport properties of Cu5Fe1-xMnxS4 (0 ≤ x ≤ 0.10), which are p-type semiconductors, were measured from room temperature to 573 K. The stability of bornite was investigated by thermogravimetric analysis under inert and oxidising atmospheres. Repeated measurements of the electrical transport properties confirm that bornite is stable up to 580 K under an inert atmosphere, while heating to 890 K results in rapid degradation. Ball milling leads to a substantial improvement in the thermoelectric figure of merit of unsusbtituted bornite (ZT = 0.55 at 543 K), when compared to bornite prepared by conventional high-temperature synthesis (ZT < 0.3 at 543 K). Manganese-substituted samples have a ZT comparable to that of unsubstituted bornite.

Effect of maternal protein restriction during pregnancy and postweaning high-fat feeding of diet-induced thermogenesis in adult mouse offspring

Purpose Prenatal undernutrition followed by postweaning feeding of a high-fat diet results in obesity in the adult offspring. In this study, we investigated whether diet-induced thermogenesis is altered as a result of such nutritional mismatch. Methods Female MF-1 mice were fed a normal protein (NP, 18 % casein) or a protein-restricted (PR, 9 % casein) diet throughout pregnancy and lactation. After weaning, male offspring of both groups were fed either a high-fat diet (HF; 45 % kcal fat) or standard chow (C, 7 % kcal fat) to generate the NP/C, NP/HF, PR/C and PR/HF adult offspring groups (n = 7–11 per group). Results PR/C and NP/C offspring have similar body weights at 30 weeks of age. Postweaning HF feeding resulted in significantly heavier NP/HF offspring (P < 0.01), but not in PR/HF offspring, compared with their chow-fed counterparts. However, the PR/HF offspring exhibited greater adiposity (P < 0.01) v the NP/HF group. The NP/HF offspring had increased energy expenditure and increased mRNA expression of uncoupling protein-1 and β-3 adrenergic receptor in the interscapular brown adipose tissue (iBAT) compared with the NP/C mice (both at P < 0.01). No such differences in energy expenditure and iBAT gene expression were observed between the PR/HF and PR/C offspring. Conclusions These data suggest that a mismatch between maternal diet during pregnancy and lactation, and the postweaning diet of the offspring, can attenuate diet-induced thermogenesis in the iBAT, resulting in the development of obesity in adulthood.

Nitrosopersulfide (SSNO-) targets soluble guanylyl cyclase and induces vasodilation in vivo

Background Recent experimental evidence suggests that nitric oxide (NO) and hydrogen sulfide signaling pathways are intimately intertwined particularly in the vasculature, with mutual attenuation or potentiation of biological responses under control of the soluble guanylyl cyclase (sGC) / phopshodiesterase (PDE) pathway. There is now compelling evidence that part of the NO/sulfide cross talk has a chemical foundation via the formation of S/N-hybrid molecules including thionitrous acid (HSNO) and nitrosopersulfde (SSNO-). The aim of this study was to characterize the bioactive products of the interaction between sulfide and NO metabolites targeting sGC that may potentially regulate vasodilation. Results We found that the chemical interaction of sulfide with NO or nitrosothiols leads to formation of S/N-hybrid metabolites including SSNO- via intermediate formation of HSNO. Contrary to a recent report in the literature but consistent with the transient nature of HSNO, its formation was not detectable by high-resolution mass spectrometry under physiologically relevant conditions. SSNO- is also formed in non-aqueous media by the reaction of nitrite with oxidized sulfur species including colloidal sulfur and polysulfides. SSNO- is stable in the presence of high concentrations of thiols, release NO, and activates sGC in RFL-6 cells in an NO-dependent fashion. Moreover, SSNO- is a potent vasodilator in aortic rings in vitro and lowers blood pressure in rats in vivo. The presence of high concentrations of SOD or thiols does not affect SSNO- mediated sGC activation, while it potentiates and inhibits the effects of the nitroxyl (HNO) donor Angeli's salt, suggesting that HNO release from SSNO- is not involved in sGC activation. Conclusion The reaction between NO and sulfide leads to fomation of S/N-hybrid molecules including SSNO-, releasing NO, activating sGC and inducing vasodilation. SSNO- is considerably more stable than HSNO at pH 7.4 and thus a more likely biological mediator that can account for the chemical cross-talk between NO and sulfide.

Recent progress in understanding and projecting regional and global mean sea-level change

Considerable progress has been made in understanding the present and future regional and global sea level in the 2 years since the publication of the Fifth Assessment Report (AR5) of the Intergovernmental Panel on Climate Change. Here, we evaluate how the new results affect the AR5’s assessment of (i) historical sea level rise, including attribution of that rise and implications for the sea level budget, (ii) projections of the components and of total global mean sea level (GMSL), and (iii) projections of regional variability and emergence of the anthropogenic signal. In each of these cases, new work largely provides additional evidence in support of the AR5 assessment, providing greater confidence in those findings. Recent analyses confirm the twentieth century sea level rise, with some analyses showing a slightly smaller rate before 1990 and some a slightly larger value than reported in the AR5. There is now more evidence of an acceleration in the rate of rise. Ongoing ocean heat uptake and associated thermal expansion have continued since 2000, and are consistent with ocean thermal expansion reported in the AR5. A significant amount of heat is being stored deeper in the water column, with a larger rate of heat uptake since 2000 compared to the previous decades and with the largest storage in the Southern Ocean. The first formal detection studies for ocean thermal expansion and glacier mass loss since the AR5 have confirmed the AR5 finding of a significant anthropogenic contribution to sea level rise over the last 50 years. New projections of glacier loss from two regions suggest smaller contributions to GMSL rise from these regions than in studies assessed by the AR5; additional regional studies are required to further assess whether there are broader implications of these results. Mass loss from the Greenland Ice Sheet, primarily as a result of increased surface melting, and from the Antarctic Ice Sheet, primarily as a result of increased ice discharge, has accelerated. The largest estimates of acceleration in mass loss from the two ice sheets for 2003–2013 equal or exceed the acceleration of GMSL rise calculated from the satellite altimeter sea level record over the longer period of 1993–2014. However, when increased mass gain in land water storage and parts of East Antarctica, and decreased mass loss from glaciers in Alaska and some other regions are taken into account, the net acceleration in the ocean mass gain is consistent with the satellite altimeter record. New studies suggest that a marine ice sheet instability (MISI) may have been initiated in parts of the West Antarctic Ice Sheet (WAIS), but that it will affect only a limited number of ice streams in the twenty-first century. New projections of mass loss from the Greenland and Antarctic Ice Sheets by 2100, including a contribution from parts of WAIS undergoing unstable retreat, suggest a contribution that falls largely within the likely range (i.e., two thirds probability) of the AR5. These new results increase confidence in the AR5 likely range, indicating that there is a greater probability that sea level rise by 2100 will lie in this range with a corresponding decrease in the likelihood of an additional contribution of several tens of centimeters above the likely range. In view of the comparatively limited state of knowledge and understanding of rapid ice sheet dynamics, we continue to think that it is not yet possible to make reliable quantitative estimates of future GMSL rise outside the likely range. Projections of twenty-first century GMSL rise published since the AR5 depend on results from expert elicitation, but we have low confidence in conclusions based on these approaches. New work on regional projections and emergence of the anthropogenic signal suggests that the two commonly predicted features of future regional sea level change (the increasing tilt across the Antarctic Circumpolar Current and the dipole in the North Atlantic) are related to regional changes in wind stress and surface heat flux. Moreover, it is expected that sea level change in response to anthropogenic forcing, particularly in regions of relatively low unforced variability such as the low-latitude Atlantic, will be detectable over most of the ocean by 2040. The east-west contrast of sea level trends in the Pacific observed since the early 1990s cannot be satisfactorily accounted for by climate models, nor yet definitively attributed either to unforced variability or forced climate change.