Core level binding energy for nitrogen doped char: XPS deconvolution analysis from first principles

Amorphous carbon produced from lignocellulosic materials has received much attention in recent years because of its applications in environmental and agricultural management with potential to sequester carbon, serve as a soil amendment, and improve soil aggregation. Modern engineered amorphous carbons with promising properties, such as porous structure, surface functionalities (O, N, P, S) and layers with large number of defects, are used in the field of adsorption and catalysis. There is a growing interest in the production of nitrogen-doped carbonaceous materials because of their excellent properties in a variety of applications such carbon electrodes, heterogenous catalysis adsorption and batteries. However, quantifying the surface nitrogen and oxygen content in amorphous nitrogen doped carbons via deconvolution of C 1s x-ray photoelectron (XPS) spectra remains difficult due to limited information in the literature. No suitable method exists to accurately correlate both the nitrogen and oxygen content to the carbon (C 1s) XPS spectrum in the literature. To improve the interpretation of spectra, the C 1s, N 1s and O 1s core level energy shifts have been calculated for various nitrogenated carbon structures from first principles by performing density functional theory (DFT) based calculations. Furthermore, we propose a new method to improve the self-consistency of the XPS interpretation based on a seven-peak C 1s deconvolution (3 C-C peaks, 3 C-N/-O peaks, and π-π* transition peaks). With the DFT calculations, spectral components arising from surface-defect carbons could be distinguished from aromatic sp2 carbon. The deconvolution method proposed provides C/(N+O) ratios in very good agreement (error less than 5%) with those obtained from total C 1s, N 1s and O 1s peaks. Our deconvolution strategy provides a simple guideline for obtaining high-quality fits to experimental data on the basis of a careful evaluation of experimental conditions and resul

Synergistic effects between nitrogen functionalities and metals content on the removal of phosphate ions

The release of phosphate ions in the runoff is today a major threat to the environment and humans. Therefore, it is vital to develop effective technologies to remove phosphate ions from aqueous solutions before they are discharged into runoff and natural water bodies. This study aims to evaluate and proposed a mechanism of phosphate adsorption by using nitrogen and metals-functionalized chars. In order to isolate the contribution of individual components of lignocellulosic biomass, simple cellulose was used for the char production. Five samples of nitrogen-doped chars were produced via annealing cellulose under ammonia gas at different temperatures (500, 600, 700, 800, 850 and 900 ℃). Some of the analytical techniques used for the chars characterization were: Elemental and proximate analysis, gas physisorption analysis, Scanning Electron Microscopy and X-ray photoelectron spectroscopy analysis. These samples were subsequently used for phosphate adsorption. Characterization of the resulting chars shows an increase of the nitrogen content in the samples, where the greater percentage of it appears at a temperature of 800 ℃ (12.5 wt%) and the maximum surface area was for char produced at 900 ℃ (1314 m2/g). To evaluate the effect of nitrogen and metals in char to adsorb phosphate ions, three sets of chars were produced at 800 ℃; char with magnesium and nitrogen (Mg_N_char); char with nitrogen (N_char) and char with magnesium (Mg_N_char). The results show that Mg_N_char sample exhibits a maximum adsorption capacity of 340 mg/g, whereas the Mg_char and N_char samples give an adsorption capacity of 7.8 mg/g and 21.4 mg/g respectively. These results demonstrate that the presence of magnesium and nitrogen in chars is very effective in the retention of phosphate ions. Other metals such as Fe and Ca combined with nitrogen will also be tested, details of the results will be presented at the conference

The PHD Finger of Human UHRF1 Reveals a New Subgroup of Unmethylated Histone H3 Tail Readers

The human UHRF1 protein (ubiquitin-like containing PHD and RING finger domains 1) has emerged as a potential cancer target due to its implication in cell cycle regulation, maintenance of DNA methylation after replication and heterochromatin formation. UHRF1 functions as an adaptor protein that binds to histones and recruits histone modifying enzymes, like HDAC1 or G9a, which exert their action on chromatin. In this work, we show the binding specificity of the PHD finger of human UHRF1 (huUHRF1-PHD) towards unmodified histone H3 N-terminal tail using native gel electrophoresis and isothermal titration calorimetry. We report the molecular basis of this interaction by determining the crystal structure of huUHRF1-PHD in complex with the histone H3 N-terminal tail. The structure reveals a new mode of histone recognition involving an extra conserved zinc finger preceding the conventional PHD finger region. This additional zinc finger forms part of a large surface cavity that accommodates the side chain of the histone H3 lysine K4 (H3K4) regardless of its methylation state. Mutation of Q330, which specifically interacts with H3K4, to alanine has no effect on the binding, suggesting a loose interaction between huUHRF1-PHD and H3K4. On the other hand, the recognition appears to rely on histone H3R2, which fits snugly into a groove on the protein and makes tight interactions with the conserved aspartates D334 and D337. Indeed, a mutation of the former aspartate disrupts the formation of the complex, while mutating the latter decreases the binding affinity nine-fold

House-level risk factors associated with the colonization of broiler flocks with Campylobacter spp. in Iceland, 2001 – 2004

<p>Abstract</p> <p>Background</p> <p>The concurrent rise in consumption of fresh chicken meat and human campylobacteriosis in the late 1990's in Iceland led to a longitudinal study of the poultry industry to identify the means to decrease the frequency of broiler flock colonization with <it>Campylobacter</it>. Because horizontal transmission from the environment is thought to be the most likely source of <it>Campylobacter </it>to broilers, we aimed to identify broiler house characteristics and management practices associated with flock colonization. Between May 2001 and September 2004, pooled caecal samples were obtained from 1,425 flocks at slaughter and cultured for <it>Campylobacter</it>. Due to the strong seasonal variation in flock prevalence, analyses were restricted to a subset of 792 flocks raised during the four summer seasons. Logistic regression models with a farm random effect were used to analyse the association between flock <it>Campylobacter </it>status and house-level risk factors. A two-stage process was carried out. Variables were initially screened within major subsets: ventilation; roof and floor drainage; building quality, materials and repair; house structure; pest proofing; biosecurity; sanitation; and house size. Variables with p ≤ 0.15 were then offered to a comprehensive model. Multivariable analyses were used in both the screening stage (i.e. within each subset) and in the comprehensive model.</p> <p>Results</p> <p>217 out of 792 flocks (27.4%) tested positive. Four significant risk factors were identified. <it>Campylobacter </it>colonization was predicted to increase when the flock was raised in a house with vertical (OR = 2.7), or vertical and horizontal (OR = 3.2) ventilation shafts, when the producer's boots were cleaned and disinfected prior to entering the broiler house (OR = 2.2), and when the house was cleaned with geothermal water (OR = 3.3).</p> <p>Conclusion</p> <p>The increased risk associated with vertical ventilation shafts might be related to the height of the vents and the potential for vectors such as flies to gain access to the house, or, increased difficulty in accessing the vents for proper cleaning and disinfection. For newly constructed houses, horizontal ventilation systems could be considered. Boot dipping procedures should be examined on farms experiencing a high prevalence of <it>Campylobacter</it>. Although it remains unclear how geothermal water increases risk, further research is warranted to determine if it is a surrogate for environmental pressures or the microclimate of the farm and surrounding region.</p

A new perspective on turbulent Galactic magnetic fields through comparison of linear polarisation decomposition techniques

We compare two rotationally invariant decomposition techniques on linear polarization data: the spin-2 spherical harmonic decomposition in two opposite parities, the E- and B-mode, and the multiscale analysis of the gradient of linear polarization, |∇ P|. We demonstrate that both decompositions have similar properties in the image domain and the spatial frequency domain. They can be used as complementary tools for turbulence analysis of interstellar magnetic fields in order to develop a better understanding of the origin of energy sources for the turbulence, the origin of peculiar magnetic field structures and their underlying physics. We also introduce a new quantity |∇EB| based on the E- and B-modes and we show that in the intermediate- and small-scale limit |∇EB| |∇ P|. Analysis of the 2.3 GHz S-band Polarization All Sky Survey shows many extended coherent filament-like features appearing as ‘double jumps’ in the |∇ P| map that are correlated with negative and positive filaments of B-type polarization. These local asymmetries between the two polarization types, E and B, of the non-thermal Galactic synchrotron emission have an influence on the E- and B-mode power spectra analyses. The wavelet-based formalism of the polarization gradient analysis allows us to locate the position of E- or B-mode features responsible for the local asymmetries between the two polarization types. In analysed subregions, the perturbations of the magnetic field are trigged by star clusters associated with H II regions, the Orion–Eridanus superbubble and the North Polar Spur at low Galactic latitude

Chemisorption Induced Formation of Biphenylene Dimer on Surfaces

We report an example that demonstrates the clear interdependence between surface-supported reactions and molecular adsorption configurations. Two biphenyl-based molecules with two and four bromine substituents, i.e. 2,2-dibromo-biphenyl (DBBP) and 2,2,6,6-tetrabromo-1,1-biphenyl (TBBP), show completely different reaction pathways on a Ag(111) surface, leading to the selective formation of dibenzo[e,l]pyrene and biphenylene dimer, respectively. By combining low-temperature scanning tunneling microscopy, synchrotron radiation photoemission spectroscopy, and density functional theory calculations, we unravel the underlying reaction mechanism. After debromination, a bi-radical biphenyl can be stabilized by surface Ag adatoms, while a four-radical biphenyl undergoes spontaneous intramolecular annulation due to its extreme instability on Ag(111). Such different chemisorption-induced precursor states between DBBP and TBBP consequently lead to different reaction pathways after further annealing. In addition, using bond-resolving scanning tunneling microscopy and scanning tunneling spectroscopy, we determine the bond length alternation of biphenylene dimer product with atomic precision, which contains four-, six-, and eight-membered rings. The four-membered ring units turn out to be radialene structures

Fast Calculation of the Weak Lensing Aperture Mass Statistic

The aperture mass statistic is a common tool used in weak lensing studies. By convolving lensing maps with a filter function of a specific scale, chosen to be larger than the scale on which the noise is dominant, the lensing signal may be boosted with respect to the noise. This allows for detection of structures at increased fidelity. Furthermore, higher-order statistics of the aperture mass (such as its skewness or kurtosis), or counting of the peaks seen in the resulting aperture mass maps, provide a convenient and effective method to constrain the cosmological parameters. In this paper, we more fully explore the formalism underlying the aperture mass statistic. We demonstrate that the aperture mass statistic is formally identical to a wavelet transform at a specific scale. Further, we show that the filter functions most frequently used in aperture mass studies are not ideal, being non-local in both real and Fourier space. In contrast, the wavelet formalism offers a number of wavelet functions that are localized both in real and Fourier space, yet similar to the 'optimal' aperture mass filters commonly adopted. Additionally, for a number of wavelet functions, such as the starlet wavelet, very fast algorithms exist to compute the wavelet transform. This offers significant advantages over the usual aperture mass algorithm when it comes to image processing time, demonstrating speed-up factors of ~ 5 - 1200 for aperture radii in the range 2 to 64 pixels on an image of 1024 x 1024 pixels.Comment: 9 pages, 5 figures, Accepted for publication in MNRAS (18 April 2012

The epigenomic landscape of African rainforest hunter-gatherers and farmers

International audienceThe genetic history of African populations is increasingly well documented, yet their patterns of epigenomic variation remain uncharacterized. Moreover, the relative impacts of DNA sequence variation and temporal changes in lifestyle and habitat on the human epigenome remain unknown. Here we generate genome-wide genotype and DNA methylation profiles for 362 rainforest hunter-gatherers and sedentary farmers. We find that the current habitat and historical lifestyle of a population have similarly critical impacts on the methylome, but the biological functions affected strongly differ. Specifically, methylation variation associated with recent changes in habitat mostly concerns immune and cellular functions, whereas that associated with historical lifestyle affects developmental processes. Furthermore, methylation variation—particularly that correlated with historical lifestyle—shows strong associations with nearby genetic variants that, moreover, are enriched in signals of natural selection. Our work provides new insight into the genetic and environmental factors affecting the epigenomic landscape of human populations over time

A synthesis of Martian aqueous mineralogy after 1 Mars year of observations from the Mars Reconnaissance Orbiter

Martian aqueous mineral deposits have been examined and characterized using data acquired during Mars Reconnaissance Orbiter's (MRO) primary science phase, including Compact Reconnaissance Imaging Spectrometer for Mars hyperspectral images covering the 0.4–3.9 μm wavelength range, coordinated with higher–spatial resolution HiRISE and Context Imager images. MRO's new high-resolution measurements, combined with earlier data from Thermal Emission Spectrometer; Thermal Emission Imaging System; and Observatoire pour la Minéralogie, L'Eau, les Glaces et l'Activitié on Mars Express, indicate that aqueous minerals are both diverse and widespread on the Martian surface. The aqueous minerals occur in 9–10 classes of deposits characterized by distinct mineral assemblages, morphologies, and geologic settings. Phyllosilicates occur in several settings: in compositionally layered blankets hundreds of meters thick, superposed on eroded Noachian terrains; in lower layers of intracrater depositional fans; in layers with potential chlorides in sediments on intercrater plains; and as thousands of deep exposures in craters and escarpments. Carbonate-bearing rocks form a thin unit surrounding the Isidis basin. Hydrated silica occurs with hydrated sulfates in thin stratified deposits surrounding Valles Marineris. Hydrated sulfates also occur together with crystalline ferric minerals in thick, layered deposits in Terra Meridiani and in Valles Marineris and together with kaolinite in deposits that partially infill some highland craters. In this paper we describe each of the classes of deposits, review hypotheses for their origins, identify new questions posed by existing measurements, and consider their implications for ancient habitable environments. On the basis of current data, two to five classes of Noachian-aged deposits containing phyllosilicates and carbonates may have formed in aqueous environments with pH and water activities suitable for life

The Science Case for a Return to Enceladus

The plume of Enceladus is unique in the solar system in providing direct access to fresh material from an extraterrestrial subsurface ocean. The Cassini Mission, though not specifically designed for it, was able to take advantage of the plume to conduct the best characterization to date of an extraterrestrial ocean. Evidence gathered from multiple instruments points to a global, subsurface liquid water ocean rich in salts and organic compounds, with water-rock interactions occurring presumably in hydrothermal systems at or below the moon’s sea floor. Meeting the criteria of “extended regions of liquid water, conditions favorable for the assembly of complex organic molecules, and energy source(s) to sustain metabolism,” the ocean of Enceladus can therefore be considered habitable. It is also the only confirmed place beyond the Earth where we can easily sample fresh material from a demonstrably habitable environment without the complications of digging or drilling. The next step is to investigate whether Enceladus’ ocean is actually inhabited. Here, we summarize the evidence for Enceladus’ ocean and its habitability, identify constraints and outstanding questions on the detectability of life within its ocean, and recommend a return to Enceladus with a dedicated search-for-life mission (or missions)