Ambient pressure x-ray photoelectron spectroscopy setup for synchrotron-based in situ and operando atomic layer deposition research

An ambient pressure cell is described for conducting synchrotron-based x-ray photoelectron spectroscopy (XPS) measurements during atomic layer deposition (ALD) processes. The instrument is capable of true in situ and operando experiments in which it is possible to directly obtain elemental and chemical information from the sample surface using XPS as the deposition process is ongoing. The setup is based on the ambient pressure XPS technique, in which sample environments with high pressure (several mbar) can be created without compromising the ultrahigh vacuum requirements needed for the operation of the spectrometer and the synchrotron beamline. The setup is intended for chemical characterization of the surface intermediates during the initial stages of the deposition processes. The SPECIES beamline and the ALD cell provide a unique experimental platform for obtaining new information on the surface chemistry during ALD half-cycles at high temporal resolution. Such information is valuable for understanding the ALD reaction mechanisms and crucial in further developing and improving ALD processes. We demonstrate the capabilities of the setup by studying the deposition of TiO2 on a SiO2 surface by using titanium(IV) tetraisopropoxide and water as precursors. Multiple core levels and the valence band of the substrate surface were followed during the film deposition using ambient pressure XPS.Peer reviewe

Water and nitrogen processes along a typical water flowpath and streamwater exports from a forested catchment and changes after clear-cutting: a modelling study

International audienceA two dimensional model, FEMMA, to describe water and nitrogen (N) fluxes within and from a forested first-order catchment (Kangasvaara in Eastern Finland) was constructed by linking the most significant processes affecting the fluxes of water, ammonium, nitrate and dissolved organic nitrogen along a hillslope from the water divide to the stream. The hillslope represents the average flowpath of water in the catchment and the model was used to estimate the N fluxes for a catchment in eastern Finland before and after clear-cutting. The simulated results were in reasonable agreement with the nitrate, dissolved organic N and dissolved total N measurements from the study catchment and with other results in the literature. According to the simulations, the major sinks of N after clear-cutting were immobilisation by soil microbes, uptake by ground vegetation and sorption to soil. These sinks increased downslope from the clear-cut area, indicating the importance of an uncut buffer zone between the stream and the clear-cut area in reducing N exports. The buffer zone retained 76% of the N flux coming from the clear-cut area. Nitrification was a key process in controlling the N export after clear-cutting and N increases were mainly as nitrate. Most of the annual N export took place during the spring flood, when uptake of N by plants was minimal

Body and milk traits as indicators of dairy cow energy status in early lactation

The inclusion of feed intake and efficiency traits in dairy cow breeding goals can lead to increased risk of metabolic stress. An easy and inexpensive way to monitor postpartum energy status (ES) of cows is therefore needed. Cows' ES can be estimated by calculating the energy balance from energy intake and output and predicted by indicator traits such as change in body weight (Delta BW), change in body condition score (Delta BCS), milk fat:protein ratio (FPR), or milk fatty acid (FA) composition. In this study, we used blood plasma nonesterified fatty acids (NEFA) concentration as a biomarker for ES. We determined associations between NEFA concentration and ES indicators and evaluated the usefulness of body and milk traits alone, or together, in predicting ES of the cow. Data were collected from 2 research herds during 2013 to 2016 and included 137 Nordic Red dairy cows, all of which had a first lactation and 59 of which also had a second lactation. The data included daily body weight, milk yield, and feed intake and monthly BCS. Plasma samples for NEFA were collected twice in lactation wk 2 and 3 and once in wk 20. Milk samples for analysis of fat, protein, lactose, and FA concentrations were taken on the blood sampling days. Plasma NEFA concentration was higher in lactation wk 2 and 3 than in wk 20 (0.56 +/- 0.30, 0.43 +/- 0.22, and 0.13 +/- 0.06 mmol/L, respectively; all means +/- standard deviation). Among individual indicators, C18:1 cis-9 and the sum of C18:1 in milk had the highest correlations (r = 0.73) with NEFA. Seven multiple linear regression models for NEFA prediction were developed using stepwise selection. Of the models that included milk traits (other than milk FA) as well as body traits, the best fit was achieved by a model with milk yield, FPR, Delta BW, Delta BCS, FPR x Delta BW, and days in milk. The model resulted in a cross-validation coefficient of determination (R(2)cv) of 0.51 and a root mean squared error (RMSE) of 0.196 mmol/L. When only milk FA concentrations were considered in the model, NEFA prediction was more accurate using measurements from evening milk than from morning milk (R(2)cv = 0.61 vs. 0.53). The best model with milk traits contained FPR, C10:0, C14:0, C18:1 cis-9, C18:1 cis-9 x C14:0, and days in milk (R(2)cv = 0.62; RMSE = 0.177 mmol/L). The most advanced model using both milk and body traits gave a slightly better fit than the model with only milk traits (R(2)cv = 0.63; RMSE = 0.176 mmol/L). Our findings indicate that ES of cows in early lactation can be monitored with moderately high accuracy by routine milk measurements.Peer reviewe

From synchrotrons for XFELs : The soft x-ray near-edge spectrum of the ESCA molecule

A predictive understanding of soft x-ray near-edge absorption spectra of small molecules is an enduring theoretical challenge and of current interest for x-ray probes of molecular dynamics. We report the experimental absorption spectrum for the electron spectroscopy for chemical analysis (ESCA) molecule (ethyl trifluoroacetate) near the carbon 1s absorption edge between 285-300 eV. The ESCA molecule with four chemically distinct carbon sites has previously served as a theoretical benchmark for photoelectron spectra and now for photoabsorption spectra. We report a simple edge-specific approach for systematically expanding standard basis sets to properly describe diffuse Rydberg orbitals and the importance of triple excitations in equation-of-motion coupled-cluster calculations of the energy interval between valence and Rydberg excitations

The effect of partial substitution of rapeseed meal and faba beans by Spirulina platensis microalgae on milk production, nitrogen utilization, and amino acid metabolism of lactating dairy cows

Alternative protein sources such as microalgae and faba beans may have environmental benefits over rapeseed. We studied the effects of rapeseed meal (RSM) or faba beans (FB) as a sole protein feed or as protein feeds partially substituted with Spirulina platensis (spirulina) microalgae on milk production, N utilization, and AA metabolism of dairy cows. Eight multiparous Finnish Ayrshire cows (113 +/- 36.3 d in milk; mean +/- SD) were used in a balanced, replicated 4 x 4 Latin square with 2 x 2 factorial arrangement of treatments and 21-d periods. Four cows in one Latin square were rumen cannulated. Treatments were 2 isonitrogenously fed protein sources, RSM or rolled FB, or one of these sources with half of its crude protein substituted by spirulina (RSM-SPI and FB-SPI). Cows had ad libitum access to total mixed rations consisting of grass silage, barley, sugar beet pulp, minerals, and experimental protein feed. The substitution of RSM with FB did not affect dry matter intake (DMI) but decreased neutral detergent fiber intake and increased the digestibility of other nutrients. Spirulina in the diet decreased DMI and His intake. Spirulina had no effect on Met intake in cows on RSM diets but increased it in those on FB diets. Energy-corrected milk (ECM) and protein yields were decreased when RSM was substituted by FB. Milk and lactose yields were decreased in cows on the RSM-SPI diet compared with the RSM diet but increased in those on FB-SPI compared with FB. The opposite was true for milk fat and protein concentrations; thus, spirulina in the diet did not affect ECM. Feed conversion efficiency (ECM: DMI) increased in cows on FB diets with spirulina, whereas little effect was observed for those on RSM diets. The substitution of RSM by FB decreased arterial concentration of Met and essential AA. Spirulina in the diet increased milk urea N and ruminal NH4-N and decreased the efficiency of N utilization in cows on RSM diets, whereas those on FB diets showed opposite results. Met likely limited milk production in cows on the FB diet as evidenced by the decrease in arterial Met concentration and milk protein yield when RSM was substituted by FB. The results suggest the potential to improve milk production response to faba beans with supplementation of Met-rich feeds such as spirulina. This study also confirmed spirulina had poorer palatability than RSM and FB despite total mixed ration feeding and lower milk production when spirulina partially replaced RSM.Peer reviewe

Identification of a cytokine network sustaining neutrophil and Th17 activation in untreated early rheumatoid arthritis

© 2010 Cascão et al.; licensee BioMed Central Ltd. This is an open access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/2.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.Introduction: Rheumatoid arthritis (RA) is a chronic inflammatory autoimmune disease characterized by sustained synovitis. Recently, several studies have proposed neutrophils and Th17 cells as key players in the onset and perpetuation of this disease. The main goal of this work was to determine whether cytokines driving neutrophil and Th17 activation are dysregulated in very early rheumatoid arthritis patients with less than 6 weeks of disease duration and before treatment (VERA). Methods: Cytokines related to neutrophil and Th17 activation were quantified in the serum of VERA and established RA patients and compared with other very early arthritis (VEA) and healthy controls. Synovial fluid (SF) from RA and osteoarthritis (OA) patients was also analyzed. Results: VERA patients had increased serum levels of cytokines promoting Th17 polarization (IL-1b and IL-6), as well as IL-8 and Th17-derived cytokines (IL-17A and IL-22) known to induce neutrophil-mediated inflammation. In established RA this pattern is more evident within the SF. Early treatment with methotrexate or corticosteroids led to clinical improvement but without an impact on the cytokine pattern. Conclusions: VERA patients already display increased levels of cytokines related with Th17 polarization and neutrophil recruitment and activation, a dysregulation also found in SF of established RA. 0 Thus, our data suggest that a cytokine-milieu favoring Th17 and neutrophil activity is an early event in RA pathogenesis.This work was supported by a grant from Sociedade Portuguesa de Reumatologia/Schering-Plough 2005. RAM and RC were funded by Fundação para a Ciência e a Tecnologia (FCT) SFRH/BD/30247/2006 and SFRH/BD/40513/2007, respectively. MMS-C was funded by Marie Curie Intra-European Fellowship PERG-2008-239422 and a EULAR Young Investigator Award