The global nitrogen (N) cycle at the beginning of the 21st century has been shown to be strongly influenced by the inputs of reactive nitrogen (Nr) from human activities, including combustion-related ...NOx, industrial and agricultural N fixation, estimated to be 220 Tg N yr-1 in 2010, which is approximately equal to the sum of biological N fixation in unmanaged terrestrial and marine ecosystems. According to current projections, changes in climate and land use during the 21st century will increase both biological and anthropogenic fixation, bringing the total to approximately 600 Tg N yr-1 by around 2100. The fraction contributed directly by human activities is unlikely to increase substantially if increases in nitrogen use efficiency in agriculture are achieved and control measures on combustion-related emissions implemented. Some N-cycling processes emerge as particularly sensitive to climate change. One of the largest responses to climate in the processing of Nr is the emission to the atmosphere of NH3, which is estimated to increase from 65 Tg N yr-1 in 2008 to 93 Tg N yr-1 in 2100 assuming a change in global surface temperature of 5 degree C in the absence of increased anthropogenic activity. With changes in emissions in response to increased demand for animal products the combined effect would be to increase NH3 emissions to 135 Tg N yr-1. Another major change is the effect of climate changes on aerosol composition and specifically the increased sublimation of NH4NO3 close to the ground to form HNO3 and NH3 in a warmer climate, which deposit more rapidly to terrestrial surfaces than aerosols. Inorganic aerosols over the polluted regions especially in Europe and North America were dominated by (NH4)2SO4 in the 1970s to 1980s, and large reductions in emissions of SO2 have removed most of the SO42- from the atmosphere in these regions. Inorganic aerosols from anthropogenic emissions are now dominated by NH4NO3, a volatile aerosol which contributes substantially to PM10 and human health effects globally as well as eutrophication and climate effects. The volatility of NH4NO3 and rapid dry deposition of the vapour phase dissociation products, HNO3 and NH3, is estimated to be reducing the transport distances, deposition footprints and inter-country exchange of Nr in these regions. There have been important policy initiatives on components of the global N cycle. These have been regional or country-based and have delivered substantial reductions of inputs of Nr to sensitive soils, waters and the atmosphere. To date there have been no attempts to develop a global strategy to regulate human inputs to the nitrogen cycle. However, considering the magnitude of global Nr use, potential future increases, and the very large leakage of Nr in many forms to soils, waters and the atmosphere, international action is required. Current legislation will not deliver the scale of reductions globally for recovery from the effects of Nr deposition on sensitive ecosystems, or a decline in N2O emissions to the global atmosphere. Such changes would require substantial improvements in nitrogen use efficiency across the global economy combined with optimization of transport and food consumption patterns. This would allow reductions in Nr use, inputs to the atmosphere and deposition to sensitive ecosystems. Such changes would offer substantial economic and environmental co-benefits which could help motivate the necessary actions.
The ultimate step in the formation of thebaine, a pentacyclic opiate alkaloid readily converted to the narcotic analgesics codeine and morphine in the opium poppy, has long been presumed to be a ...spontaneous reaction. We have detected and purified a novel enzyme from opium poppy latex that is capable of the efficient formation of thebaine from (7S)-salutaridinol 7-O-acetate at the expense of labile hydroxylated byproducts, which are preferentially produced by spontaneous allylic elimination. Remarkably, thebaine synthase (THS), a member of the pathogenesis-related 10 protein (PR10) superfamily, is encoded within a novel gene cluster in the opium poppy genome that also includes genes encoding the four biosynthetic enzymes immediately upstream. THS is a missing component that is crucial to the development of fermentation-based opiate production and dramatically improves thebaine yield in engineered yeast.
Context.
The specific location from where molecules emit in a protoplanetary disk depends on the system properties. Therefore, directly constraining the emitting regions radially, azimuthally, and ...vertically is key to studying the environment of planet formation. Due to the difficulties and lack of high resolution observations, most of the current observational constraints for the vertical distribution of molecular emission rely on indirect methods.
Aims.
We aim to directly trace the vertical location of the emitting surface of multiple molecular tracers in protoplanetary disks. Our sample of disks includes Elias 2-27, WaOph 6, and the sources targeted by the MAPS ALMA Large Program. The set of molecules studied includes CO isotopologues in various transitions, HCN, CN, H
2
CO, HCO
+
, C
2
H, and c-C
3
H
2
.
Methods.
The vertical emitting region is determined directly from the channel maps by tracing the location of emission maxima along the upper surface. This method has been used in previous studies, but here we implement an accurate masking of the channel emission in order to recover the vertical location of the emission surface even at large radial distances from the star and for low-S/N lines. Parametric models are used to describe the emission surfaces and characterize any structure within the vertical profile.
Results.
The vertical location of the emitting layer is obtained for ten different molecules and transitions in HD 163296. In the rest of the sample it is possible to vertically locate between four and seven lines. Brightness temperature profiles are obtained for the entire sample and for all CO isotopologues. IM Lup, HD 163296, and MWC 480
12
CO and
13
CO show vertical modulations, which are characterized and found to be coincident with dust gaps and kinematical perturbations. We also present estimates of the gas pressure scale height in the disks from the MAPS sample. Compared to physical-chemical models, we find good agreement with the vertical location of CO isotopologues. In HD 163296, CN and HCN trace a similar intermediate layer, which is expected from physical-chemical models. For the other disks, we find that UV flux tracers and the vertical profiles of HCN and C
2
H are lower than predicted in theoretical models. HCN and H
2
CO show a highly structured vertical profile, possibly indicative of different formation pathways in the case of H
2
CO.
Conclusions.
It is possible to trace the vertical locations of multiple molecular species that in turn trace a wide variety of physical and chemical disk properties. The distribution of CO isotopologues is in agreement with theoretical predictions, and the emission is found at a wide range of vertical heights,
z
/
r
= 0.5–0.05. The vertical location of CO may be inversely related to the stellar mass. Other molecular lines are mostly found at
z
/
r
≤ 0.15. The vertical layering of molecules is in agreement with theoretical predictions in some systems, but not in all. Therefore, dedicated physical-chemical models are needed to further study and understand the diversity of the emission surfaces.
The structure–activity relationship was investigated in a series of synthetic TLR4 antagonists formed by a glucosamine core linked to two phosphate esters and two linear carbon chains. Molecular ...modeling showed that the compounds with 10, 12, and 14 carbons chains are associated with higher stabilization of the MD-2/TLR4 antagonist conformation than in the case of the C16 variant. Binding experiments with human MD-2 showed that the C12 and C14 variants have higher affinity than C10, while the C16 variant did not interact with the protein. The molecules, with the exception of the C16 variant, inhibited the LPS-stimulated TLR4 signal in human and murine cells, and the antagonist potency mirrored the MD-2 affinity calculated from in vitro binding experiments. Fourier-transform infrared, nuclear magnetic resonance, and small angle X-ray scattering measurements suggested that the aggregation state in aqueous solution depends on fatty acid chain lengths and that this property can influence TLR4 activity in this series of compounds.
The global nitrogen (N) cycle at the beginning of the 21st century has been shown to be strongly influenced by the inputs of reactive nitrogen (Nr) from human activities, including combustion-related ...NOx, industrial and agricultural N fixation, estimated to be 220 Tg N yr−1 in 2010, which is approximately equal to the sum of biological N fixation in unmanaged terrestrial and marine ecosystems. According to current projections, changes in climate and land use during the 21st century will increase both biological and anthropogenic fixation, bringing the total to approximately 600 Tg N yr−1 by around 2100. The fraction contributed directly by human activities is unlikely to increase substantially if increases in nitrogen use efficiency in agriculture are achieved and control measures on combustion-related emissions implemented. Some N-cycling processes emerge as particularly sensitive to climate change. One of the largest responses to climate in the processing of Nr is the emission to the atmosphere of NH3, which is estimated to increase from 65 Tg N yr−1 in 2008 to 93 Tg N yr−1 in 2100 assuming a change in global surface temperature of 5 °C in the absence of increased anthropogenic activity. With changes in emissions in response to increased demand for animal products the combined effect would be to increase NH3 emissions to 135 Tg N yr−1. Another major change is the effect of climate changes on aerosol composition and specifically the increased sublimation of NH4NO3 close to the ground to form HNO3 and NH3 in a warmer climate, which deposit more rapidly to terrestrial surfaces than aerosols. Inorganic aerosols over the polluted regions especially in Europe and North America were dominated by (NH4)2SO4 in the 1970s to 1980s, and large reductions in emissions of SO2 have removed most of the SO42− from the atmosphere in these regions. Inorganic aerosols from anthropogenic emissions are now dominated by NH4NO3, a volatile aerosol which contributes substantially to PM10 and human health effects globally as well as eutrophication and climate effects. The volatility of NH4NO3 and rapid dry deposition of the vapour phase dissociation products, HNO3 and NH3, is estimated to be reducing the transport distances, deposition footprints and inter-country exchange of Nr in these regions. There have been important policy initiatives on components of the global N cycle. These have been regional or country-based and have delivered substantial reductions of inputs of Nr to sensitive soils, waters and the atmosphere. To date there have been no attempts to develop a global strategy to regulate human inputs to the nitrogen cycle. However, considering the magnitude of global Nr use, potential future increases, and the very large leakage of Nr in many forms to soils, waters and the atmosphere, international action is required. Current legislation will not deliver the scale of reductions globally for recovery from the effects of Nr deposition on sensitive ecosystems, or a decline in N2O emissions to the global atmosphere. Such changes would require substantial improvements in nitrogen use efficiency across the global economy combined with optimization of transport and food consumption patterns. This would allow reductions in Nr use, inputs to the atmosphere and deposition to sensitive ecosystems. Such changes would offer substantial economic and environmental co-benefits which could help motivate the necessary actions.
This paper synthesizes data on aerosol (particulate matter, PM) physical characteristics, which were obtained in European aerosol research activities at free-troposphere, natural, rural, near-city, ...urban, and kerbside sites over the past decade. It covers only two sites in the semi-arid Mediterranean area, and lacks data from Eastern Europe. The data include PM10 and/or PM2.5 mass concentrations, and aerosol particle size distributions. Such data sets are more comprehensive than those currently provided by air quality monitoring networks (e.g. EMEP, EUROAIRNET). Data available from 31 sites in Europe (called “The Network”) were reviewed. They were processed and plotted to allow comparisons in spite of differences in the sampling and analytical techniques used in various studies. A number of conclusions are drawn as follows:
Background annual average PM10 and PM2.5 mass concentrations for continental Europe are 7.0±4.1 and 4.8±2.4
μg
m
−3, respectively.
The EU 2005 annual average PM10 standard of 40
μg
m
−3 is exceeded at a few sites in The Network. At all near city, urban and kerbside sites, the EU 2010 annual average PM10 standard of 20
μg
m
−3, as well as the US-EPA annual average PM2.5 standard of 15
μg
m
−3 are exceeded. In certain regions, PM10 and PM2.5 in cities are strongly affected by the regional aerosol background.
There is no “universal” (i.e. valid for all sites) ratio between PM2.5 and PM10 mass concentrations, although fairly constant ratios do exist at individual sites. There is no universal correlation between PM mass concentration on the one hand, and total particle number concentration on the other hand, although a ‘baseline’ ratio between number and mass is found for sites not affected by local emissions. This paper is the first part of two companion papers of which the second part describes chemical characteristics.
The non-canonical NF-κB activating kinase IKKα, encoded by CHUK (conserved-helix-loop-helix-ubiquitous-kinase), has been reported to modulate pro- or anti- inflammatory responses, cellular survival ...and cellular differentiation. Here, we have investigated the mechanism of action of IKKα as a novel effector of human and murine chondrocyte extracellular matrix (ECM) homeostasis and differentiation towards hypertrophy.
IKKα expression was ablated in primary human osteoarthritic (OA) chondrocytes and in immature murine articular chondrocytes (iMACs) derived from IKKα(f/f):CreERT2 mice by retroviral-mediated stable shRNA transduction and Cre recombinase-dependent Lox P site recombination, respectively. MMP-10 was identified as a major target of IKKα in chondrocytes by mRNA profiling, quantitative RT-PCR analysis, immunohistochemistry and immunoblotting. ECM integrity, as assessed by type II collagen (COL2) deposition and the lack of MMP-dependent COL2 degradation products, was enhanced by IKKα ablation in mice. MMP-13 and total collagenase activities were significantly reduced, while TIMP-3 (tissue inhibitor of metalloproteinase-3) protein levels were enhanced in IKKα-deficient chondrocytes. IKKα deficiency suppressed chondrocyte differentiation, as shown by the quantitative inhibition of.Alizarin red staining and the reduced expression of multiple chondrocyte differentiation effectors, including Runx2, Col10a1 and Vegfa,. Importantly, the differentiation of IKKα-deficient chondrocytes was rescued by a kinase-dead IKKα protein mutant.
IKKα acts independent of its kinase activity to help drive chondrocyte differentiation towards a hypertrophic-like state. IKKα positively modulates ECM remodeling via multiple downstream targets (including MMP-10 and TIMP-3 at the mRNA and post-transcriptional levels, respectively) to maintain maximal MMP-13 activity, which is required for ECM remodeling leading to chondrocyte differentiation. Chondrocytes are the unique cell component in articular cartilage, which are quiescent and maintain ECM integrity during tissue homeostasis. In OA, chondrocytes reacquire the capacity to proliferate and differentiate and their activation results in pronounced cartilage degeneration. Τηυσ, our findings are also of potential relevance for defining the onset and/or progression of OA disease.
Bursting bubbles at the ocean-surface produce airborne salt-water spray-droplets, in turn, forming climate-cooling marine haze and cloud layers. The reflectance and ultimate cooling effect of these ...layers is determined by the spray's water-uptake properties that are modified through entrainment of ocean-surface organic matter (OM) into the airborne droplets. We present new results illustrating a clear dependence of OM mass-fraction enrichment in sea spray (OMss) on both phytoplankton-biomass, determined from Chlorophyll-a (Chl-a) and Net Primary Productivity (NPP). The correlation coefficient for OMss as a function of Chl-a increased form 0.67 on a daily timescale to 0.85 on a monthly timescale. An even stronger correlation was found as a function of NPP, increasing to 0.93 on a monthly timescale. We suggest the observed dependence is through the demise of the bloom, driven by nanoscale biological processes (such as viral infections), releasing large quantities of transferable OM comprising cell debris, exudates and other colloidal materials. This OM, through aggregation processes, leads to enrichment in sea-spray, thus demonstrating an important coupling between biologically-driven plankton bloom termination, marine productivity and sea-spray modification with potentially significant climate impacts.
We performed a comprehensive demographic study of the CO extent relative to dust of the disk population in the Lupus clouds in order to find indications of dust evolution and possible correlations ...with other disk properties. We increased the number of disks of the region with measured
R
CO
and
R
dust
from observations with the Atacama Large Millimeter/submillimeter Array to 42, based on the gas emission in the
12
CO
J
= 2−1 rotational transition and large dust grains emission at ~0.89 mm. The CO integrated emission map is modeled with an elliptical Gaussian or Nuker function, depending on the quantified residuals; the continuum is fit to a Nuker profile from interferometric modeling. The CO and dust sizes, namely the radii enclosing a certain fraction of the respective total flux (e.g.,
R
68%
), are inferred from the modeling. The CO emission is more extended than the dust continuum, with a
R
68%
CO
/
R
68%
dust
median value of 2.5, for the entire population and for a subsample with high completeness. Six disks, around 15% of the Lupus disk population, have a size ratio above 4. Based on thermo-chemical modeling, this value can only be explained if the disk has undergone grain growth and radial drift. These disks do not have unusual properties, and their properties spread across the population’s ranges of stellar mass (
M
⋆
), disk mass (
M
disk
), CO and dust sizes (
R
CO
,
R
dust
), and mass accretion of the entire population. We searched for correlations between the size ratio and
M
⋆
,
M
disk
,
R
CO
, and
R
dust
: only a weak monotonic anticorrelation with the
R
dust
is found, which would imply that dust evolution is more prominent in more compact dusty disks. The lack of strong correlations is remarkable: the sample covers a wide range of stellar and disk properties, and the majority of the disks have very similar size ratios. This result suggests that the bulk of the disk population may behave alike and be in a similar evolutionary stage, independent of the stellar and disk properties. These results should be further investigated, since the optical depth difference between CO and dust continuum might play a major role in the observed size ratios of the population. Lastly, we find a monotonic correlation between the CO flux and the CO size. The results for the majority of the disks are consistent with optically thick emission and an average CO temperature of around 30 K; however, the exact value of the temperature is difficult to constrain.
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