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The solubilities of the rare earth chlorides REECl3, where REE = (La, Nd, Er), were measured in HCl bearing water vapor from 350 to 425 °C with water partial pressures ranging from 8 to 170 bar. Solubility data were fit to the Pitzer-Pabalan quasi-chemical model in order to extract thermodynamic parameters for the formation of the gaseous REE-chloride-water clusters REECl3(H2O)n. The data show that the solubility of the REE chlorides are orders of magnitude higher than salts such as NaCl or CuCl at low water fugacities, despite their sublimation energies being substantially higher. This enhanced solubility is likely due to the high enthalpy associated with binding a single water molecule to form the species REECl3(H2O), with derived enthalpies ranging from −378 to −465 kJ/mol. Addition of further water molecules to form higher order clusters (n > 1) involves enthalpy changes of ~−20 kJ/mol, and are in effect thermodynamically suppressed over the temperature range 350–425 °C. Despite the enhanced solubility of small REECl3 water clusters, simulations of boiling processes demonstrate that the REE show highly conservative behavior, partitioning strongly into the dense aqueous phase. Not surprisingly, the presence of phosphates in the system makes this effect even more pronounced, completely immobilizing the REE. This would reduce transport in both the vapor and aqueous phase to negligible levels. However, we suggest that vapor phase transport of the REE may play a significant role in systems having a relatively low partial pressure of water (below the saturation point), where the relatively high stability of the first hydrated REE chloride clusters (REECl3(H2O) and REECl3(H2O)2) will give a preference for gas transport of the REE relative to other elements. This can likely happen in systems involving a gas/melt exchange in fumarolic exhalations, where water vapor discharges at relatively low (close to atmospheric) pressures.

Thorium mineralization is frequently hosted in carbonate-bearing rocks, and thorium commonly substitutes into the structures of carbonate-bearing minerals that have precipitated from or been modified by hydrothermal fluids. Given this common association, it is reasonable to consider the hypothesis that the presence of carbonate ligands in hydrothermal solutions promotes the transport of Th through the formation of stable aqueous complexes. Our ability to evaluate this hypothesis, however, is hindered by the lack of experimental data for Th-carbonate species at conditions beyond ambient. The low-temperature data indicate that carbonate is a strong complexing agent for Th. In this contribution, we investigate the solubility of Th in carbonate-bearing fluids relevant to natural systems (0.05–0.5 m NaHCO3/Na2CO3; pHT ~ 7.8–9.8) at elevated temperature (175–250 °C). We demonstrate that, in contrast to the behavior of Th at low temperature, the stability of Th-carbonate complexes is not sufficient for them to predominate at these conditions. Instead, the solubility of Th is governed by hydrolysis reactions. Under the experimental conditions investigated, the predominant hydroxyl complexes are Th(OH)40 and Th(OH)5−. Thermodynamic formation constants were derived for these species at the temperatures considered in our experiments (log β4 = 43.34 and 44.31 at 175 and 200 °C, respectively, and log β5 = 46.15 and 47.9 at 225 and 250 °C, respectively) to permit forward modeling of Th mobility in natural systems. Our study indicates that carbonate ions are unlikely to play a role in transporting Th in hydrothermal fluids. Summarizing the results of this study and our previous studies of the solubility of Th in hydrothermal fluids, we conclude that SO42− is the primary ligand responsible for the hydrothermal transport of Th.

Elpasolite- and cryolite-type oxyfluorides can be regarded as superstructures of perovskite and exhibit structural diversity. While maintaining a similar structural topology with the prototype structures, changes in the size, electronegativity, and charge of cation and/or anion inevitably lead to structural evolution. Therefore, the nominal one-to-one relation suggested by a doubled formula of perovskite does not guarantee a simple 2-fold superstructure for many cases. Herein, the commensurately modulated perovskite-like K3TiOF5 was refined at 100 K from single-crystal X-ray diffraction data by using a pseudotetragonal subcell with lattice parameters of a = b = 6.066(2) A and c = 8.628(2) A. The length of the modulation vector was refined to 0.3a* + 0.1b* + 0.25c*. In the commensurate supercell of K3TiOF5, the B-site Ti4+ and K+ cations in [TiOF5]3- and [KOF5]6- octahedral units were found to be significantly displaced from the average atomic positions refined in the subcell. The displacements of the K+ cations are ±0.76 A, and those for the Ti4+ cations are approximately ±0.13 A. One- and two-dimensional solid-state 19F NMR measurements revealed two tightly clustered groups of resonances in a ratio of ca. 4:1, assigned to equatorial and axial fluorine, respectively, consistent with local [TiOF5]3- units. S/TEM results confirmed the average structure. Electronic structure calculations of the idealized I4mm subcell indicate the instability to a modulated structure arises from soft optical modes that is controlled by the octahedrally coordinated B-site potassium ions in the cryolite-type structure.

Protein citrullination (deimination of arginine residue) is a well-known biomarker of inflammation. Elevated protein citrullination has been shown to colocalize with extracellular amyloid plaques in postmortem AD patient brains. Amyloid-β (Aβ) peptides which aggregate and accumulate in the plaques of Alzheimer's disease (AD) have sequential N-terminal truncations and multiple post-translational modifications (PTM) such as isomerization, pyroglutamate formation, phosphorylation, nitration, and dityrosine cross-linking. However, no conclusive biochemical evidence exists whether citrullinated Aβ is present in AD brains. In this study, using high-resolution mass spectrometry, we have identified citrullination of Aβ in sporadic and familial AD brains by characterizing the tandem mass spectra of endogenous N-truncated citrullinated Aβ peptides. Our quantitative estimations demonstrate that ∼ 35% of pyroglutamate3-Aβ pool was citrullinated in plaques in the sporadic AD temporal cortex and ∼ 22% in the detergent-insoluble frontal cortex fractions. Similarly, hypercitrullinated pyroglutamate3-Aβ (∼ 30%) was observed in both the detergent-soluble as well as insoluble Aβ pool in familial AD cases. Our results indicate that a common mechanism for citrullination of Aβ exists in both the sporadic and familial AD. We establish that citrullination of Aβ is a remarkably common PTM, closely associated with pyroglutamate3-Aβ formation and its accumulation in AD. This may have implications for Aβ toxicity, autoantigenicity of Aβ, and may be relevant for the design of diagnostic assays and therapeutic targeting.

The syntheses and crystal structures of two bimetallic molecular compounds, namely, bis[bis(6,6′-dimethyl-2,2′-bipyridine)copper(I)] hexafluoridozirconate(IV) 1.134-hydrate, [Cu(dmbpy)2]2[ZrF6]·1.134H2O (dmbpy = 6,6′-dimethyl-2,2′-bipyridyl, C12H12N2), (I), and bis[bis(6,6′-dimethyl-2,2′-bipyridine)copper(I)] hexafluoridohafnate(IV) 0.671-hydrate, [Cu(dmbpy)2]2[HfF6]·0.671H2O, (II), are reported. Apart from a slight site occupany difference for the water molecule of crystallization, compounds (I) and (II) are isostructural, featuring isolated tetrahedral cations of copper(I) ions coordinated by two dmbpy ligands and centrosymmetric, octahedral anions of fluorinated early transition metals. The tetrahedral environments of the copper complexes are distorted owing to the steric effects of the dmbpy ligands. The extended structures are built up through Coulombic interactions between cations and anions and π–π stacking interactions between heterochiral Δ- and Λ-[Cu(dmbpy)2]+ complexes. A comparison between the title compounds and other [Cu(dmbpy)2]+ compounds with monovalent and bivalent anions reveals a significant influence of the cation-to-anion ratio on the resulting crystal packing architectures, providing insights for future crystal design of distorted tetrahedral copper compounds.

Synthetic materials designed for improved biomimicry of the extracellular matrix must contain fibrous, bioactive, and mechanical cues. Self-assembly of low molecular weight gelator (LMWG) peptides Fmoc-DIKVAV (Fmoc-aspartic acid-isoleucine-lysine-valine-alanine-valine) and Fmoc-FRGDF (Fmoc-phenylalanine-arginine-glycine-aspartic acid-phenylalanine) creates fibrous and bioactive hydrogels. Polysaccharides such as agarose are biocompatible, degradable, and non-toxic. Agarose and these Fmoc-peptides have both demonstrated efficacy in vitro and in vivo. These materials have complementary properties; agarose has known mechanics in the physiological range but is inert and would benefit from bioactive and topographical cues found in the fibrous, protein-rich extracellular matrix. Fmoc-DIKVAV and Fmoc-FRGDF are synthetic self-assembling peptides that present bioactive cues "IKVAV" and "RGD" designed from the ECM proteins laminin and fibronectin. The work presented here demonstrates that the addition of agarose to Fmoc-DIKVAV and Fmoc-FRGDF results in physical characteristics that are dependent on agarose concentration. The networks are peptide-dominated at low agarose concentrations, and agarose-dominated at high agarose concentrations, resulting in distinct changes in structural morphology. Interestingly, at mid-range agarose concentration, a hybrid network is formed with structural similarities to both peptide and agarose systems, demonstrating reinforced mechanical properties. Bioactive-LMWG polysaccharide hydrogels demonstrate controllable microenvironmental properties, providing the ability for tissue-specific biomaterial design for tissue engineering and 3D cell culture.

Actinium-225 is used in nuclear medicine for the treatment of malignant tumours. It can be applied to produce Bi-213 in a reusable generator or can be used alone as an agent for radiation therapy, in particular for targeted alpha therapy. However, the availability of Ac-225 for worldwide use, particularly in low- and middle-income countries, is limited. We present a feasibility study employing GATE, an open-source Monte Carlo simulation toolkit, on the production of Ac-225 from a neutron generator. This work suggests that a design consisting of three concentric cylinders, the innermost a Cf-252 neutron source, the middle nickel cylinder acting as a proton-producing target and the outer cylinder a RaCl2 target may provide a feasible design outline for an Ac-225 generator.

The causes of methane's renewed rise since 2007, accelerated growth from 2014 and record rise in 2020, concurrent with an isotopic shift to values more depleted in 13 C, remain poorly understood. This rise is the dominant departure from greenhouse gas scenarios that limit global heating to less than 2°C. Thus a comprehensive understanding of methane sources and sinks, their trends and inter-annual variations are becoming more urgent. Efforts to quantify both sources and sinks and understand latitudinal and seasonal variations will improve our understanding of the methane cycle and its anthropogenic component. Nationally declared emissions inventories under the UN Framework Convention on Climate Change (UNFCCC) and promised contributions to emissions reductions under the UNFCCC Paris Agreement need to be verified independently by top-down observation. Furthermore, indirect effects on natural emissions, such as changes in aquatic ecosystems, also need to be quantified. Nitrous oxide is even more poorly understood. Despite this, options for mitigating methane and nitrous oxide emissions are improving rapidly, both in cutting emissions from gas, oil and coal extraction and use, and also from agricultural and waste sources. Reductions in methane and nitrous oxide emission are arguably among the most attractive immediate options for climate action. This article is part of a discussion meeting issue 'Rising methane: is warming feeding warming? (part 1)'.

Crystal structures of three compounds with the formula [Cu(phen)(H2O)3(MF6)]·H2O (M = Ti, Zr, Hf) based on bimetallic Λ-shaped mol­ecules and a related salt with the formula [Cu(phen)(H2O)2F]2[HfF6]·H2O are reported., The crystal structures of three bridged bimetallic mol­ecular compounds, namely, tri­aqua-2κ3 O-μ-fluorido-penta­fluorido-1κ5 F-(1,10-phenanthroline-2κ2 N,N′)copper(II)titanium(IV) monohydrate, [Cu(TiF6)(phen)(H2O)3]·H2O (phen is 1,10-phenanthroline, C12H8N2), (I), tri­aqua-2κ3 O-μ-fluorido-penta­fluorido-1κ5 F-(1,10-phenanthroline-2κ2 N,N′)copper(II)zirconium(IV) monohydrate, [Cu(ZrF6)(phen)(H2O)3]·H2O, (II), and tri­aqua-2κ3 O-μ-fluorido-penta­fluorido-1κ5 F-(1,10-phenanthroline-2κ2 N,N′)copper(II)hafnium(IV) monohydrate, [Cu(HfF6)(phen)(H2O)3]·H2O, (III), and one mol­ecular salt, bis­[diaqua­fluorido­(1,10-phenanthroline-κ2 N,N′)copper(II)] hexa­fluorido­hafnate(IV) dihydrate, [CuF(phen)(H2O)2]2[HfF6]·2H2O, (IV), are reported. The bridged bimetallic compounds adopt Λ-shaped configurations, with the octa­hedrally coordinated copper(II) center linked to the fluorinated early transition metal via a fluoride linkage. The extended structures of these Λ-shaped compounds are organized through both intra- and inter­molecular hydrogen bonds and inter­molecular π–π stacking. The salt compound [Cu(phen)(H2O)2F]2[HfF6]·H2O displays an isolated square-pyramidal Cu(phen)(H2O)2F+ complex linked to other cationic complexes and isolated HfF6 2− anions through inter­molecular hydrogen-bonding inter­actions.

Foodborne illness is an ongoing problem worldwide and is caused by bacteria that invade the food chain from the farm, slaughter house, restaurant or grocery, or in the home and can be controlled by strategies using biocides (antiseptics and disinfectants). Susceptibility profiles were determined for 96 Campylobacter jejuni strains obtained in 2011-2012 from broiler chicken house environments to antimicrobials and disinfectants as per the methods of the Clinical and Laboratory Standards Institute and TREK Diagnostics using CAMPY AST Campylobacter plates. Low prevalence of antimicrobial resistance was observed in C. jejuni strains to tetracycline (TET; 21.9%), ciprofloxacin (CIP; 13.5%), and nalidixic acid (NAL; 12.5%). The resistance profiles had a maximum of 3 antimicrobials, CIP-NAL-TET, with TET being the main profile observed. No cross-resistance was observed between antimicrobials and disinfectants. The C. jejuni strains (99%) were resistant to triclosan, 32% were resistant to chlorhexidine, and they all were susceptible to benzalkonium chloride. The strains had low-level minimum inhibitory concentrations (MICs) to the disinfectants P-128, Food Service Sanitizer, F-25 Sanitizer, Final Step 512 Sanitizer, OdoBan, dioctyldimethylammmonium chloride, didecyldimethylammonium chloride (C10AC), benzyldimethyldodecylammonium chloride (C12BAC), and benzyldimethyltetradecylammonium chloride (C14BAC). Intermediate MICs against DC&R, cetylpyridinium bromide hydrate, hexadecylpyridinium chloride, ethylhexadecyldimethylammonium bromide, and hexadecyltrimethylammonium bromide with elevated intermediate MICs against Tek-Trol, benzyldimethylhexadecylammonium chloride, tris(hydroxylmethyl)nitromethane (THN), and formaldehyde. The highest MIC were obtained for povidone-iodine. The components THN and the benzylammonium chlorides C12BAC and C14BAC were responsible for the inhibition by DC&R. The components C10AC and C12BAC may act synergistically causing inhibition of C. jejuni by the disinfectant P-128. The formaldehyde component in DC&R was not effective against C. jejuni compared with the ammonium chloride components. Its use in disinfectants may result in additional unnecessary chemicals in the environment. Didecyldimethylammonium chloride is the most effective ammonium chloride component against C. jejuni.

Tropospheric ozone (O3) negatively impacts human health and is also a greenhouse gas. It is formed photochemically by reactions of nitrogen oxides (NOx) and volatile organic compounds (VOCs), of which wildfires are an important source. This study presents data from research flights sampling wildfires in West and Central African savannah regions, both close to the fires and after the emissions had been transported several days over the tropical North Atlantic Ocean. Emission factors (EFs) in g kg−1 for NOx (as NO), six VOCs and formaldehyde were calculated from enhancement to mole fractions in data taken close to the fires. For NOx, the emission factor was calculated as 2.05 ± 0.43 g kg−1 for Senegal and 1.20 ± 0.28 g kg−1 for Uganda, both higher than the average value of 1.13 ± 0.6 g kg−1 for previous studies of African savannah regions. For most VOCs (except acetylene), EFs in Uganda were lower by factors of 20–50% compared to Senegal, with almost all the values below those in the literature. O3 enhancement in the fire plumes was investigated by examining the ΔO3/ΔCO enhancement ratio, with values ranging from 0.07–0.14 close to the fires up to 0.25 for measurements taken over the Atlantic Ocean up to 200 hours downwind. In addition, measurements of O3 and its precursors were compared to the output of a global chemistry transport model (GEOS-CF) for the flights over the Atlantic Ocean. Normalised mean bias (NMB) comparison between the measured and modelled data was good outside of the fire plumes, with CO showing a model under-prediction of 4.6% and O3 a slight over-prediction of 0.7% (both within the standard deviation of the data). For NOx the agreement was poorer, with an under-prediction of 9.9% across all flights. Inside the fire plumes the agreement between modelled and measured values is worse, with the model being biased significantly lower for all three species. In total across all flights, there was an under-prediction of 29.4%, 16.5% and 37.5% for CO, O3 and NOx respectively. Finally, the measured ΔO3/ΔCO enhancement ratios were compared to those in the model for the equivalent flight data, with the model showing a lower value of 0.17 ± 0.03 compared to an observed value of 0.29 ± 0.05. The results detailed here show that the O3 burden to the North Atlantic Ocean from African wildfires may be underestimated and that further study is required to better study the O3 precursor emissions and chemistry.

Developing highly selective chemiresistive gas sensors is of great importance for non-invasive health diagnosis and environmental monitoring. There is a need for new materials and robust techniques to selectively detect specific gases in different environments. Here, we present a new approach for fabricating metal–organic framework (MOF) encapsulated metal oxide nanoparticle fractal networks for selective gas sensing applications. SnO2 chemiresistors were fabricated using a flame spray pyrolysis technique. ZnO was then conformally deposited over the ultra-porous nanoparticle network (UNN) of SnO2 using atomic layer deposition (ALD), which was subsequently converted to ZIF-8 using a chemical vapour conversion technique. The SnO2 UNN helps in providing a large surface area for enhancing the reaction of the film with the analyte, while the ZIF-8 hinders the interaction with large gas molecules, increasing the selectivity towards smaller analytes such as NO2. The compact sensor layer showed a higher response of 0.3 (Ra/Rg − 1) at 1 ppm for NO2 as compared to ethanol (0.08 at 1 ppm). The increased selectivity towards NO2 (3.2 A) can be attributed to the selective diffusion of smaller gas molecules through the ZIF-8 pores (3.4 A) compared to molecules with a larger kinetic diameter such as ethanol (4.53 A) and acetone (4.6 A).

The challenge with engineering soft materials is to find a chemically functionalized material that can be easily fabricated into complex structures while providing a supportive cellular milieu. The current gold standard is gelatin methacryloyl (GelMA), a semi-synthetic collagen-derived biomaterial that has found widespread utility as a bioink for 3D bioprinting. Although a fundamental understanding of controlling the mechanical properties of GelMA exists, the nano- and cell-scale network topology needs to be investigated to produce controlled structures. Here, for the first time, small-angle X-ray scattering (SAXS) is used to elucidate how structural changes on the network level dictate the final properties within a GelMA hydrogel. Scaffold nanostructure was observed pre- and post-crosslinking, with emphasis on assessing structural changes in response to changes in Degree of Functionalization (DoF) and polymer concentration. Samples were modelled regarding local-polymer conformation (mass fractal dimension), distance between entanglements (correlation length), and mesh size. Importantly, DoF is observed to alter crosslinked polymer conformation and nanoscale mesh size. These results inform future design of GelMA-based bioinks, allowing researchers to further leverage the young and evolving bioprinting technology for broad-spectrum applications such as cell/stem cell printing, organoid-based tissue structure, building cell/organ-on-a-chip, through to the hierarchical engineering of multicellular living systems.

The aim of this study was to evaluate the antibacterial properties of methylsulfonylmethane (MSM) on vancomycin-resistant Enterococcus faecium (VRE). Bacterial proliferation was measured spectropho...

Electrochemical biosensors allow the rapid, selective, and sensitive transduction of critical biological parameters into measurable signals. However, current electrochemical biosensors often fail to selectively and sensitively detect small molecules due to their small size and low molecular complexity. We have developed an electrochemical biosensing platform that harnesses the analyte-dependent conformational change of highly selective solute-binding proteins to amplify the signal generated by analyte binding. Using this platform, we constructed and characterized two biosensors that can sense leucine and glycine, respectively. We show that these biosensors can selectively and sensitively detect their targets over a wide range of concentrations – up to seven orders of magnitude – and that the selectivity of these sensors can be readily altered by switching the bioreceptor’s binding domain. Our work represents a new paradigm for the design of a family of modular electrochemical biosensors, where access to electrode surfaces can be controlled by protein conformational change.

Complex crystal structures with subtle atomic-scale details are now routinely solved using complementary tools such as X-ray and/or neutron scattering combined with electron diffraction and imaging...

Racemates have recently received attention as nonlinear optical and piezoelectric materials. Here, a machine-learning-assisted composition space approach was applied to synthesize the missing M = Ti, Zr members of the Δ,Λ-[Cu(bpy)2(H2O)]2[MF6]2·3H2O (M = Ti, Zr, Hf; bpy = 2,2'-bipyridine) family (space group: Pna21). In each (CuO, MO2)/bpy/HF(aq) (M = Ti, Zr, Hf) system, the polar noncentrosymmetric racemate (M-NCS) forms in competition with a centrosymmetric one-dimensional chain compound (M-CS) based on alternating Cu(bpy)(H2O)22+ and MF62- basic building units (space groups: Ti-CS (Pnma), Zr-CS (P1), Hf-CS (P2/n)). Machine learning models were trained on reaction parameters to gain unbiased insight into the underlying statistical trends in each composition space. A human-interpretable decision tree shows that phase selection is driven primarily by the bpy:CuO molar ratio for reactions containing Zr or Hf, and predicts that formation of the Ti-NCS compound requires that the amount of HF present be decreased to raise the pH, which we verified experimentally. Predictive leave-one-metal-out (LOO) models further confirm that behavior in the Ti system is distinct from that of the Zr and Hf systems. The chemical origin of this distinction was probed via fluorine K-edge X-ray absorption spectroscopy. Pre-edge features in the F1s X-ray absorption spectra reveal the strong ligand-to-metal π bonding between Ti(3d - t2g) and F(2p) states that distinguishes the TiF62- anion from the ZrF62- and HfF62- anions.

Although compounds of the formula AMoO2F3 (A = K, Rb, Cs, NH4, Tl) have been known for decades, crystal structures have only been reported for CsMoO2F3 and NH4MoO2F3. The three compounds (Rb/NH4/Tl...

In recent years, many nanofabrication methodologies to engineer metal organic frameworks (MOFs) have been investigated. However, there is only a small number of studies that explores scalable and e...

Two experiments were conducted to evaluate the feeding of direct fed microbials (DFMs) on fecal shedding of Escherichia coli O157:H7 in naturally infected cattle (experiment I) and on Salmonella in the feces and peripheral lymph nodes (PLNs) of experimentally infected cattle (experiment II). Thirty cattle, 10 per treatment, were used in each experiment. Treatments in experiment I consisted of a control (lactose carrier only); DFM1, a 1:1 ratio of Enterococcus faecium and Lactobacillus animalis; and DFM2, a 1:1 ratio of Lactobacillus acidophilus and Pediococcus acidilactici. In Experiment II, DFM1 was replaced with DFM3, a 1:2 ratio of Lactobacillus reuteri and other Lactobacillus strains. Additives were mixed in water and applied as a top-dressing to each pen's daily ration for 50 days. Approximately half-way through each experiment, the DFM concentration was doubled for the remainder of the study. Fecal samples were collected throughout experiment I and cultured for E. coli O157:H7. Cattle in experiment II were inoculated intradermally with Salmonella Montevideo on days 32, 37, and 42 and then necropsied on days 49 and 50 (five cattle per treatment on each day). Innate immune function was assessed on days 29, 49, and 50. In experiment I, fecal concentration and prevalence of E. coli O157:H7 were not different (P > 0.10) nor was there an effect (P = 0.95) on the percentage of super shedders (cattle shedding ≥3.0 log CFU/g of feces). In experiment II, no treatment differences (P > 0.05) were observed for Salmonella in the PLNs except for the inguinal nodes, which had a significantly lower Salmonella prevalence in DFM-supplemented cattle than in the controls. Immune function, as measured by monocyte nitric oxide production and neutrophil oxidative burst, was decreased (P < 0.05) in the DFM treatment groups. Although results of this research indicate little to no effect of these DFMs on E. coli O157:H7 or Salmonella in cattle, an increase in the duration of administration to that similar to what is used for commercial cattle might elicit treatment differences.

Artificial Intelligence (AI) has been widely employed in the medical field in recent years in such areas as image segmentation, medical image registration, and computer-aided detection. This study explores one application of using AI in adaptive radiation therapy treatment planning by predicting the tumor volume reduction rate (TVRR). Cone beam computed tomography (CBCT) scans of twenty rectal cancer patients were collected to observe the change in tumor volume over the course of a standard five-week radiotherapy treatment. In addition to treatment volume, patient data including patient age, gender, weight, number of treatment fractions, and dose per fraction were also collected. Application of a stepwise regression model showed that age, dose per fraction and weight were the best predictors for tumor volume reduction rate.

During photosynthesis, electrons are transferred between the cytochrome b6f complex and photosystem I. This is carried out by the protein plastocyanin in plant chloroplasts, or by either plastocyanin or cytochrome c6 in many cyanobacteria and eukaryotic algal species. There are three further cytochrome c6 homologs: cytochrome c6A in plants and green algae, and cytochromes c6B and c6C in cyanobacteria. The function of these proteins is unknown. Here, we present a comprehensive analysis of the evolutionary relationship between the members of the cytochrome c6 family in photosynthetic organisms. Our phylogenetic analyses show that cytochromes c6B and c6C are likely to be orthologs that arose from a duplication of cytochrome c6, but that there is no evidence for separate origins for cytochromes c6B and c6C. We therefore propose renaming cytochrome c6C as cytochrome c6B. We show that cytochrome c6A is likely to have arisen from cytochrome c6B rather than by an independent duplication of cytochrome c6, and present evidence for an independent origin of a protein with some of the features of cytochrome c6A in peridinin dinoflagellates. We conclude with a new comprehensive model of the evolution of the cytochrome c6 family which is an integral part of understanding the function of the enigmatic cytochrome c6 homologs.

Simple Summary Pancreatic cancer challenges global health with non-specific symptoms, devastatingly low survival rates, and high treatment resistance profiles. Tissue engineering is advancing to facilitate animal free tissue biomimicry, allowing the replication of tumour tissue specific hallmarks of pancreatic cancer that challenge modern treatments. Here, we report the development and characterisation of a low oxygen (hypoxic) 3D polyurethane scaffold system for long-term analysis of radiation responses. This finely tuned platform more accurately recapitulates bio-physical, bio-chemical, and structural-bio-mechanical in vivo tissue niches as well as tumour hypoxia. The latter is a treatment-limiting feature for radiotherapy, allowing the system to streamline the transition of clinical testing from bench to bedside. Abstract Tissue engineering is evolving to mimic intricate ecosystems of tumour microenvironments (TME) to more readily map realistic in vivo niches of cancerous tissues. Such advanced cancer tissue models enable more accurate preclinical assessment of treatment strategies. Pancreatic cancer is a dangerous disease with high treatment resistance that is directly associated with a highly complex TME. More specifically, the pancreatic cancer TME includes (i) complex structure and complex extracellular matrix (ECM) protein composition; (ii) diverse cell populations (e.g., stellate cells), cancer associated fibroblasts, endothelial cells, which interact with the cancer cells and promote resistance to treatment and metastasis; (iii) accumulation of high amounts of (ECM), which leads to the creation of a fibrotic/desmoplastic reaction around the tumour; and (iv) heterogeneous environmental gradients such as hypoxia, which result from vessel collapse and stiffness increase in the fibrotic/desmoplastic area of the TME. These unique hallmarks are not effectively recapitulated in traditional preclinical research despite radiotherapeutic resistance being largely connected to them. Herein, we investigate, for the first time, the impact of in vitro hypoxia (5% O2) on the radiotherapy treatment response of pancreatic cancer cells (PANC-1) in a novel polymer (polyurethane) based highly macroporous scaffold that was surface modified with proteins (fibronectin) for ECM mimicry. More specifically, PANC-1 cells were seeded in fibronectin coated macroporous scaffolds and were cultured for four weeks in in vitro normoxia (21% O2), followed by a two day exposure to either in vitro hypoxia (5% O2) or maintenance in in vitro normoxia. Thereafter, in situ post-radiation monitoring (one day, three days, seven days post-irradiation) of the 3D cell cultures took place via quantification of (i) live/dead and apoptotic profiles and (ii) ECM (collagen-I) and HIF-1a secretion by the cancer cells. Our results showed increased post-radiation viability, reduced apoptosis, and increased collagen-I and HIF-1a secretion in in vitro hypoxia compared to normoxic cultures, revealing hypoxia-induced radioprotection. Overall, this study employed a low cost, animal free model enabling (i) the possibility of long-term in vitro hypoxic 3D cell culture for pancreatic cancer, and (ii) in vitro hypoxia associated PDAC radio-protection development. Our novel platform for radiation treatment screening can be used for long-term in vitro post-treatment observations as well as for fractionated radiotherapy treatment.

The atmospheric methane burden is increasing rapidly, contrary to pathways compatible with the goals of the 2015 United Nations Framework Convention on Climate Change Paris Agreement. Urgent action is required to bring methane back to a pathway more in line with the Paris goals. Emission reduction from “tractable” (easier to mitigate) anthropogenic sources such as the fossil fuel industries and landfills is being much facilitated by technical advances in the past decade, which have radically improved our ability to locate, identify, quantify, and reduce emissions. Measures to reduce emissions from “intractable” (harder to mitigate) anthropogenic sources such as agriculture and biomass burning have received less attention and are also becoming more feasible, including removal from elevated-methane ambient air near to sources. The wider effort to use microbiological and dietary intervention to reduce emissions from cattle (and humans) is not addressed in detail in this essentially geophysical review. Though they cannot replace the need to reach “net-zero” emissions of CO2, significant reductions in the methane burden will ease the timescales needed to reach required CO2 reduction targets for any particular future temperature limit. There is no single magic bullet, but implementation of a wide array of mitigation and emission reduction strategies could substantially cut the global methane burden, at a cost that is relatively low compared to the parallel and necessary measures to reduce CO2, and thereby reduce the atmospheric methane burden back toward pathways consistent with the goals of the Paris Agreement.

Radiotherapy dose calculation requires accurate Computed Tomography (CT) imaging while tissue delineation may necessitate the use of contrast agents (CA). Acquiring these two sets is a common practice in radiotherapy. This study aims to evaluate the effect of CA on the dose calculations. Two hundred and twenty-six volumetric modulated arc therapy (VMAT) patients that had planning CT with contrast (CCT) and non-contrast CT (NCCT) of different cancer sites (e.g., brain, head, and neck (H&amp, N), chest, abdomen, and pelvis) were evaluated. Treatment plans were recalculated using CCT, then compared to NCCT. The variation in Hounsfield units (HU) and dose distributions for critical structures and target volumes were analyzed using mean HU, mean and maximum relative dose values, D2%, D98%, and 3D gamma analysis. HU variations were statistically significant for most structures. However, this was not clinically significant as the difference in mean HU values was within 30 HU for soft tissue and 50 HU for lungs. Variation in target volumes’ D2% and D98% were insignificant for all sites except brain and nasopharynx. Dose maximum differences were within 2% for the majority of critical structures and target volumes. 3D gamma analysis results revealed that majority of plans satisfied the 2% and 2 mm criteria. CCT may be acquired for VMAT radiotherapy planning purposes instead of NCCT, since there is no clinically significant difference in dose calculations based on either image set.

The methane emissions from the Hungarian Pannonian Basin are not well qualified, due to a lack of measurements of CH4 mole fraction and δ13CCH4 in the air. This study reports methane measurements in air samples from Hungary, placing them in the context of regional and global background data, to investigate the inputs to the methane burden in Central Europe. CH4 mole fraction and δ13CCH4 from the Hungarian tall tower station, Hegyhátsál, and additional data from Mace Head (Ireland) and Zeppelin (Svalbard) are used with back-trajectory modeling to identify central European source areas and their seasonal variation between the summer vegetation and winter heating periods. Methane measurements in air masses sampled in the European interior, have significantly higher maxima and seasonal amplitudes than at the Mace Head and Zeppelin European background sites. The mean CH4 mole fraction value is about 80 ppb higher than the comparable marine background, and values above 2000 ppb were frequently observed between February 2013 and December 2015. The mean δ13CCH4 value -47.5±0.3 ‰ (2σ) was comparable to values at all three monitoring sites, but specific pollution events were detected at Hegyhátsál. Concentration weighted trajectory modeling, meteorological parameters, stable carbon isotopic composition (δ13CCH4), and Miller-Tans analysis show that the main factors influencing CH4 at the Hegyhátsál, apart from diurnal and seasonal changes in the Planetary Boundary Layer, are emissions from residential heating and industrial CH4 emissions during the winter.

Made available in DSpace on 2022-04-28T19:44:08Z (GMT). No. of bitstreams: 0 Previous issue date: 2021-09-02 The amount of carbon stored in deadwood is equivalent to about 8 per cent of the global forest carbon stocks1. The decomposition of deadwood is largely governed by climate2–5 with decomposer groups—such as microorganisms and insects—contributing to variations in the decomposition rates2,6,7. At the global scale, the contribution of insects to the decomposition of deadwood and carbon release remains poorly understood7. Here we present a field experiment of wood decomposition across 55 forest sites and 6 continents. We find that the deadwood decomposition rates increase with temperature, and the strongest temperature effect is found at high precipitation levels. Precipitation affects the decomposition rates negatively at low temperatures and positively at high temperatures. As a net effect—including the direct consumption by insects and indirect effects through interactions with microorganisms—insects accelerate the decomposition in tropical forests (3.9% median mass loss per year). In temperate and boreal forests, we find weak positive and negative effects with a median mass loss of 0.9 per cent and −0.1 per cent per year, respectively. Furthermore, we apply the experimentally derived decomposition function to a global map of deadwood carbon synthesized from empirical and remote-sensing data, obtaining an estimate of 10.9 ± 3.2 petagram of carbon per year released from deadwood globally, with 93 per cent originating from tropical forests. Globally, the net effect of insects may account for 29 per cent of the carbon flux from deadwood, which suggests a functional importance of insects in the decomposition of deadwood and the carbon cycle. Ecosystem Dynamics and Forest Management Group School of Life Sciences Technical University of Munich Berchtesgaden National Park Epidemiology Biostatistics and Prevention Institute University of Zurich Southern Research Station USDA Forest Service Field Station Fabrikschleichach University of Würzburg Biological Sciences University of Toronto Scarborough Fenner School of Environment and Society The Australian National University Department of Biogeography University of Bayreuth Department of Disturbance Ecology University of Bayreuth Instituto de Ecología Regional CONICET-Universidad Nacional de Tucumán Department of Animal Ecology and Tropical Biology University of Würzburg Laboratory of Environmental Microbiology Institute of Microbiology The Czech Academy of Sciences Agricultural and Natural Resources Research Centre of Mazandaran Lancaster Environment Centre Lancaster University Universidade Federal de Lavras Department of Biodiversity Conservation Goethe-University Frankfurt Bavarian Forest National Park CIRAD UMR Ecologie des Forêts de Guyane (EcoFoG) AgroParisTech CNRS INRA Universite des Antilles Universite de Guyane Environmental Change Institute University of Oxford Grassland Vegetation Lab Federal University of Rio Grande do Sul Faculty of Environmental Sciences and Natural Resource Management Norwegian University of Life Sciences Institute of Ecology and Botany Centre for Ecological Research Institute for Wildlife Management and Nature Conservation Hungarian University of Agriculture and Life Sciences Animal Ecology University of Marburg École d’Ingénieurs de Purpan Université de Toulouse UMR 1201 Dynafor Ecosystem Science and Management Program University of Northern British Columbia Laboratory of Applied Ecology University of Abomey-Calavi Department of Ecology University of Granada Réserves Naturelles de France Royal Alberta Museum Conservation Ecology University of Marburg Science and Engineering Faculty Queensland University of Technology Centre for the Environment Institute for Future Environments Forest Research Institute Malaysia International Institute of Tropical Forestry USDA Forest Service Forest Entomology Swiss Federal Research Institute WSL Evolutionary Zoology University of Salzburg Natural Resources Canada Canadian Forest Service Eurofins Ahma Oy Department of Plant Systematics University of Bayreuth Department of Wildlife Fish and Environmental Studies Swedish University of Agricultural Sciences Applied Landscape Ecology Chuo University School of Forest Sciences University of Eastern Finland School of Agricultural Forest and Food Sciences Bern University of Applied Sciences CAS Key Laboratory for Plant Diversity and Biogeography of East Asia Kunming Institute of Botany Chinese Academy of Sciences ECNU-Alberta Joint Lab for Biodiversity Study Tiantong National Station for Forest Ecosystem Research East China Normal University Institute of Biological Sciences University of the Philippines Los Banos Department of Thermodynamics Universidad Nacional del Nordeste Tropical Forests and People Research Centre University of the Sunshine Coast Forest Ecosystem Monitoring Laboratory National University of Mongolia School of Environment and Science Griffith University School of Biological Earth and Environmental Sciences University College Cork Edge Hill University Institute of Forestry Tribhuvan University Institute of Evolution University of Haifa Scion (New Zealand Forest Research Institute) School of Forestry University of Canterbury Institute of Zoology University of Hamburg Faculté des Sciences Université d’Antananarivo Tropical Biodiversity and Social Enterprise Departamento de Ecologia Universidade Estadual Paulista Ecology Group University Erlangen-Nuremberg H. J. Andrews Experimental Forest Environmental and Conservation Sciences Murdoch University Environmental Futures Research Institute Griffith University Ashoka Trust for Research in Ecology and the Environment ARC Centre for Forest Value University of Tasmania Terrestrial Ecology Research Group School of Life Sciences Technical University of Munich EcoBank Team National Institute of Ecology College of Forestry Beijing Forestry University Departamento de Ecologia Universidade Estadual Paulista

Strategies are sought to reduce the carriage and dissemination of zoonotic pathogens and antimicrobial-resistant microbes within food-producing animals and their production environment. Thymol (an essential oil) is a potent bactericide in vitro but in vivo efficacy has been inconsistent, largely due to its lipophilicity and absorption, which limits its passage and subsequent availability in the distal gastrointestinal tract. Conjugation of thymol to glucose to form thymol-β-d-glucopyranoside can decrease its absorption, but in vivo passage of effective concentrations to the lower gut remains suboptimal. Considering that contemporary swine diets often contain 5% or more added fat (to increase caloric density and reduce dustiness), we hypothesized that there may be sufficient residual fat in the distal intestinal tract to sequester free or conjugated thymol, thereby limiting the availability and subsequent effectiveness of this biocide. In support of this hypothesis, the anti-Salmonella Typhimurium effects of 6 mM free or conjugated thymol, expressed as log10-fold reductions of colony-forming units (CFU) ml−1, were diminished 90 and 58%, respectively, following 24-h in vitro anaerobic fecal incubation (at 39°C) with 3% added vegetable oil compared to reductions achieved during culture without added oil (6.1 log10 CFU ml−1). The antagonistic effect of vegetable oil and the bactericidal effect of free and conjugated thymol against Escherichia coli K88 tested similarly were diminished 86 and 84%, respectively, compared to reductions achieved in cultures incubated without added vegetable oil (5.7 log10 CFU ml−1). Inclusion of taurine (8 mg/ml), bile acids (0.6 mg/ml), or emulsifiers such as polyoxyethylene-40 stearate (0.2%), Tween 20, or Tween 80 (each at 1%) in the in vitro incubations had little effect on vegetable oil-caused inhibition of free or conjugated thymol. Based on these results, it seems reasonable to suspect that undigested lipid in the distal gut may limit the effectiveness of free or conjugated thymol. Accordingly, additional research is warranted to learn how to overcome obstacles diminishing bactericidal activity of free and conjugated thymol in the lower gastrointestinal tract of food-producing animals.

Background: This study aims to investigate whether or not uric acid and bilirubin have a role in the development of type 2 diabetes mellitus (T2DM) in prediabetic patients. Methods: 93 patients were included in the study. These patients were diagnosed as being prediabetic using the oral glucose tolerance test, and they also had their serum uric acid and total bilirubin measured during the follow-up application (1 - 5 years). Results: 17 out of the 93 patients developed T2DM during the study period. The only significant difference between the T2DM group and the non-T2DM group was OGTT 0.min and 120.min (p=0.001 and p=0.007, respectively). Analysis of the relationship between age, sex, HbA1c, uric acid, total bilirubin, direct bilirubin levels and T2DM development showed that none of the aforementioned risk factors were related with diabetes development. In the non-T2DM group, the median total bilirubin level was only found to be higher in the baseline assessment (p=0.042). Conclusion: It was found that uric acid and bilirubin had no effect on the development of diabetes in the 1-5-year follow-up of prediabetic patients. Randomized-controlled studies of a larger number of patients and sufficient follow-up time are required to provide clearer data on this topic.

A noncentrosymmetric mixed alkali metal borate–bicarbonate, NaRb3B6O9(OH)3(HCO3), was synthesized and characterized. The compound crystallizes in the monoclinic space group P21 (No. 4) with a = 8.9...

Objective To demonstrate the in vitro activities of panthenol, palmitoylethanolamide (PEA), and niacinamide (NAM) and determine the biophysical properties, clinical safety, tolerability together with efficacy of two developmental anti‐redness (AR) formulations containing these ingredients, in alleviating facial redness associated with winter xerosis in healthy volunteers with sensitive skin. Methods The anti‐inflammatory and skin protective properties of panthenol, PEA and NAM were evaluated in vitro. The physical properties of the AR formulations were analysed using measurement of water vapour transport rate (WVTR) and infrared spectroscopy. Clinical studies were performed between the months of December and April (2014–2015) with efficacy assessed during the winter. Facial redness, irritation, sensitization potential, photo‐irritation, and photo‐sensitization were evaluated. Self‐assessed adverse reactions were reported in diaries of use. Results Panthenol and PEA reduced prostaglandin E2, interleukin‐6, and thymic stromal lymphopoietin levels in vitro, while NAM induced nicotinamide adenine dinucleotide (NAD) levels and the keratinocyte differentiation markers: filaggrin (2‐fold increase, P, This article demonstrates the in vitro activities of panthenol, palmitoylethanolamide (PEA), and niacinamide (NAM) and determines the biophysical properties, clinical safety, tolerability together with efficacy of two developmental anti‐redness formulations containing these ingredients, in alleviating facial redness associated with winter xerosis in healthy volunteers with sensitive skin.

We present the results of a comprehensive study on the concentrations of first-row transition elements (FRTE: Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn), as well as Ga and Ge, in liquidus olivine from 2.7–3.5 Ga old Al-undepleted and Al-depleted komatiites from the Kaapvaal and Zimbabwe Cratons in southern Africa, the Yilgarn Craton in Australia, and the Superior Craton in Canada. The sample set includes komatiites that remained sulfur-undersaturated upon emplacement, as well as komatiites that reached sulfide saturation owing to assimilation of crustal sulfur.All olivine grains display concentrations of Mn, Zn, Ge, Co, Fe, Mg, and Ni similar to the Bulk Silicate Earth (BSE) values, with significant negative anomalies in Sc, Ti, V, Cr, Ga, and Cu. Olivine from the studied Al-depleted komatiites displays on average higher 100×Ga/Sc ratios (>5) than olivine from Al-undepleted komatiites (≤5). Because garnet preferentially incorporates Sc over Ga, the data suggest that elevated Ga/Sc ratios in komatiitic olivine are indicative of garnet retention in the source region of komatiites, highlighting the potential of olivine trace element chemistry as a proxy for the depth of komatiite melting and separation of the magma from the melting residue. Copper concentrations in the studied olivine grains are controlled by sulfur saturation of the host komatiite during olivine crystallization. Olivine from sulfur-undersaturated komatiite systems displays Cu concentrations mostly between 1 and 10 ppm, whereas olivine from sulfide-bearing komatiites has Cu contents of Olivine from the Paleo-Archean (3.5–3.3 Ga) komatiites displays overall higher V/Sc ratios (V/Sc = 2.1 ± 0.96; 2 S.D.) than olivine from their Neo-Archean (2.7 Ga) counterparts (V/Sc = 1.0 ± 0.81, 2 S.D.). Vanadium and Sc behave similarly during partial melting of the mantle and are similarly compatible in majorite garnet. However, V is redox-sensitive and its compatibility in olivine increases as the system becomes less oxidized, whereas Sc is redox-insensitive. We argue that olivine from the studied Paleo-Archean komatiites crystallized from more reduced magmas than their Neo-Archean counterparts. Elevated Fe/Mn ratios in olivine from Paleo-Archean komatiites mimic the V/Sc signatures and are interpreted to reflect that Fe2+ is more compatible in olivine than Fe3+. These results imply that V/Sc and Fe/Mn in komatiitic olivine may potentially provide insight into the evolution of the oxidation state of the Archean mantle. Additional studies that integrate the chemistry of komatiitic olivine with those of relict interstitial glass and melt/fluid inclusions are encouraged to fully understand and quantify the potential of FRTE in olivine as a proxy for the oxidation state of the mantle sources of komatiite magmas.

The effects of the charged ion species 4He, 12C and 20Ne on glioblastoma multiforme (GBM) T98G, U87 and LN18 cell lines were compared with the effects of 200 kVp X-rays (1.7 keV/μm). These cell lines have different genetic profiles. Individual GBM relative biological effectiveness (RBE) was estimated in two ways: the RBE10 at 10% survival fraction and the RBE2Gy after 2 Gy doses. The linear quadratic model radiosensitivity parameters α and β and the α/β ratio of each ion type were determined as a function of LET. Mono-energetic 4He, 12C and 20Ne ions were generated by the Heavy Ion Medical Accelerator at the National Institute of Radiological Sciences in Chiba, Japan. Colony-formation assays were used to evaluate the survival fractions. The LET of the various ions used ranged from 2.3 to 100 keV/μm (covering the depth–dose plateau region to clinically relevant LET at the Bragg peak). For U87 and LN18, the RBE10 increased with LET and peaked at 85 keV/μm, whereas T98G peaked at 100 keV/μm. All three GBM α parameters peaked at 100 keV/μm. There is a statistically significant difference between the three GBM RBE10 values, except at 100 keV/μm (P < 0.01), and a statistically significant difference between the α values of the GBM cell lines, except at 85 and 100 keV/μm. The biological response varied depending on the GBM cell lines and on the ions used.

Rapid loss of ash (Fraxinus spp.) trees in riparian forests from an invasive insect, the emerald ash borer (EAB; Agrilus planipennis Fairmaire, 1888), could pose risk of altering organic matter inputs to water bodies that underpin many aquatic ecosystem processes. We measured the composition of riparian forests and their leaf-litter contributions to headwater streams and determined the relative palatability of ash leaves and leaves of three other common riparian trees to aquatic invertebrate leaf-litter consumers (the stonefly (Pteronarcys sp.) and the cranefly (Tipula sp.)) in laboratory microcosms and whole invertebrate communities in forest streams. Ash trees contributed, on average, 24% to riparian tree density and 20% to total litterfall. Among the four common streamside trees accounting for 65% of total litterfall, ash was the first or second most preferred food source for consumers. Leaf packs without ash decomposed at slower rates than packs containing 25%–100% ash leaves. Preferential feeding on ash leaves infers a high-quality food source selected by consumers, and this concurred with comparatively high N content and low C–N ratio of ash leaves. Aquatic invertebrate communities on leaf packs in streams differed among leaf mixtures with or without ash, although community dissimilarity was low. The loss of ash in riparian forests represents an EAB-induced reduction in a high-quality resource subsidy to organic matter consumers in streams. We discuss how this has implications for risk predictions and management response strategies.

This contribution presents a thermodynamic model revealing the mechanisms responsible for separation of Heavy and Light Rare Earth (HREE and LREE) phosphates in natural hydrothermal systems at temperatures of 250–350 °C. Our calculations were performed for an isothermal column of rock containing 0.5 wt% of apatite (Ca phosphate), which served as an immobilizing agent for REE dissolved in the solution. REE were transported by 10 wt% NaCl acidic solution. The model accounted for formation of REE phosphate solid solutions through a regular mixing model. It demonstrates that hydrothermal flushing can efficiently separate REE forming xenotime (HREE phosphate solid solutions) at the beginning of the column, and re-transportation of monazite (LREE rich) to the end of the column. This separation is primarily due to the fact that at elevated temperatures stability LREE chloride complexes is significantly higher than that for HREE. The model also evaluates behavior of U and Th, which accompany REE in vast majority of natural locations. It was found that U strongly fractionates to xenotime, whereas Th fractionates to monazite. This phenomenon can be explained by the differences in crystal-chemical characteristics between monazite and xenotime, and the mobility of Th in aqueous solutions at elevated temperatures.

Following the Fukushima Daiichi accident, significant efforts from industry and the scientific community have been directed towards the development of alternative nuclear reactor fuels with enhanced accident tolerance. Among the proposed materials for such fuels is a uranium silicide compound (U3Si2), which has been selected for its enhanced thermal conductivity and high density of uranium compared to the reference commercial light water reactor (LWR) nuclear fuel, uranium oxide (UO2). To be a viable candidate LWR fuel, however, U3Si2 must also demonstrate that, in the event of this fuel coming in contact with aqueous media, it will not degrade rapidly. In this contribution, we report the results of experiments investigating the stability of U3Si2 in pressurized water at elevated temperatures and identify the mechanisms that control the interaction of U3Si2 under these conditions. Our data indicate that the stability of this material is primarily controlled by the formation of a layer of USiO4 (the mineral, coffinite) at the surface of U3Si2. The results also show that these layers are destabilized at T > 300 °C, leading to the complete decomposition of U3Si2 and its pulverization due to its full oxidation to UO2.

High atomic number nanoparticles are of increasing interest in radiotherapy due to their significant positive impact on the local dose applied to the treatment site. In this work, three types of metal nanoparticles were utilized to investigate their dose enhancement based on the GATE Monte Carlo simulation tool. Gold, gadolinium, and silver were implanted at three different concentrations to a 1 cm radius sphere to mimic a cancerous tumor inside a 10 × 10 × 30 cm3 water phantom. The innermost layer of the tumor represents a necrotic region, where the metal nanoparticles uptake is assumed to be zero, arising from hypoxic conditions. The nanoparticles were defined using the mixture technique, where nanoparticles are added to the chemical composition of the tumor. A directional 2 × 2 cm2 monoenergetic photon beam was used with several energies ranging from 50 keV to 4000 keV. The dose enhancement factor (DEF) was measured for all three metal nanoparticles under all beam energies. The maximum DEF was ~7 for silver nanoparticles with the 50 keV beam energy at the highest nanoparticle concentration of 30 mg/g of water. Gold followed the same trend as it registered the highest DEF at the 50 keV beam energy with the highest concentration of nanoparticles at 30 mg/g, while gadolinium registered the highest at 100 keV.

The rising number of operational biogas plants in the UK brings a new emissions category to consider for methane monitoring, quantification and reduction. Minimising methane losses from biogas plants to the atmosphere is critical not only because of their contribution of methane to global warming but also with respect to the sustainability of renewable energy production. Mobile greenhouse gas surveys were conducted to detect plumes of methane emissions from the biogas plants in southern England that varied in their size, waste feed input materials and biogas utilization. Gaussian plume modelling was used to estimate total emissions of methane from ten biogas plants based on repeat passes through the plumes. Methane emission rates ranged from 0.1 to 58.7 kg CH4 hr-1, and the percentage of losses relative to the calculated production rate varied between 0.02 and 8.1%. The average emission rate was 15.9 kg CH4 hr-1, and the average loss was 3.7%. In general, methane emission rates from smaller farm biogas plants were higher than from larger food waste biogas plants. We also suggest that biogas methane emissions may account for between 0.4 and 3.8%, with an average being 1.9% of the total methane emissions in the UK excluding the sewage sludge biogas plants.

One of the main pathological hallmarks of Alzheimer’s disease (AD) is the intraneuronal accumulation of hyperphosphorylated tau. Passive immunotherapy is a promising strategy for the treatment of AD and there are currently a number of tau-specific monoclonal antibodies in clinical trials. A proposed mechanism of action is to engage and clear extracellular, pathogenic forms of tau. This process has been shown in vitro to be facilitated by microglial phagocytosis through interactions between the antibody-tau complex and microglial Fc-receptors. As this interaction is mediated by the conformation of the antibody's Fc domain, this suggests that the antibody isotype may affect the microglial phagocytosis and clearance of tau, and hence, the overall efficacy of tau antibodies. We therefore aimed to directly compare the efficacy of the tau-specific antibody, RN2N, cloned into a murine IgG1/κ framework, which has low affinity Fc-receptor binding, to that cloned into a murine IgG2a/κ framework, which has high affinity Fc-receptor binding. Our results demonstrate, for RN2N, that although enhanced microglial activation via the IgG2a/κ isotype increased extracellular tau phagocytosis in vitro, the IgG1/κ isoform demonstrated enhanced ability to reduce tau pathology and microgliosis following passive immunisation of the P301L tau transgenic pR5 mouse model.

Airborne measurements of methane (CH4) were recorded over three major wetland areas in Zambia in February 2019 during the MOYA (Methane Observations and Yearly Assessments) ZWAMPS field campaign. Enhancements of up to 600 ppb CH4 were measured over the Bangweulu (11°36’ S, 30°05’ E), Kafue (15°43’ S, 27°17’ E), and Lukanga (14°29’ S, 27°47’ E) wetlands. Three independent methods were used to quantify methane emission fluxes; aircraft mass balance, aircraft eddy covariance, and atmospheric inversion modelling. Results yielded methane emission fluxes of 10-20 mg CH4 m-2 hr-1, which were up to an order of magnitude greater than the emission fluxes simulated by various wetland process models (WetCHARTs ensemble and LPX-Bern). Independent column CH4 observations from the TROPOMI instrument were used to verify these fluxes, and investigate their applicability for timescales longer than the duration of the MOYA flight campaign.

Biological methane oxidation in landfill cover material can be characterised using stable isotopes. Methane oxidation fraction is calculated from the carbon isotopic signature of emitted CH4, with enhanced microbial consumption of methane in the aerobic portion of the landfill cover indicated by a shift to less depleted isotopic values in the residual methane emitted to air. This study was performed at four southwest England landfill sites. Mobile mole fraction measurement at the four sites was coupled with Flexfoil bag sampling of air for high-precision isotope analysis. Gas well samples collected from the pipeline systems and downwind plume air samples were utilized to estimate methane oxidation rate for whole sites. This work was designed to assess the impact on carbon isotopic signature and oxidation rate as UK landfill practice and waste streams have changed in recent years.The landfill status such as closed and active, seasonal variation, cap stripping and site closure impact on landfill isotopic signature and oxidation rate were evaluated. The isotopic signature of 13C-CH4 values of emissions varied between -60 and -54‰, with an averaged value of -57 +- 2‰ for methane from closed and active landfill sites. Methane emissions from older, closed landfill sites were typically more enriched in 13C than emissions from active sites. This study found that the isotopic signature of 13C-CH4 of fugitive methane did not show a seasonal trend, and there was no plume observed from a partial cap stripping process to assess changes in 13C-CH4 isotopic signatures of emitted methane. Also, the closure of an active landfill cell caused a significant decrease in mole fraction of measured CH4, which was less depleted 13C in the emitted plume due to a higher oxidation rate. Methane oxidation, estimated from the isotope fractionation, ranged from 3 to 27%, with mean values of 7% and 15% for active and closed landfills, respectively. These results indicate that the oxidation rate is highly site specific.

During photosynthesis, electrons are transferred between the cytochrome b6f complex and photosystem I. This is carried out by the protein plastocyanin in plant chloroplasts. In contrast, electron transfer can be carried out by either plastocyanin or cytochrome c6 in many cyanobacteria and eukaryotic algal species. There are three further cytochrome c6 homologues: cytochrome c6A in plants and green algae, and cytochromes c6B and c6C in cyanobacteria. The function of these proteins is unknown. Here, we present a comprehensive analysis of the evolutionary relationship between the members of the cytochrome c6 family in photosynthetic organisms. Our phylogenetic analyses show that cytochrome c6B and cytochrome c6C are likely to be orthologues that arose from a duplication of cytochrome c6, but that there is no evidence for separate origins for cytochrome c6B and c6C. We therefore propose re-naming cytochrome c6C as cytochrome c6B. We show that cytochrome c6A is likely to have arisen from cytochrome c6B rather than by an independent duplication of cytochrome c6, and present evidence for an independent origin of a protein with some of the features of cytochrome c6A in peridinin dinoflagellates. We conclude with a new comprehensive model of the evolution of the cytochrome c6 family which is an integral part of understanding the function of the enigmatic cytochrome c6 homologues.

Nutritional and contaminant stressors influence organismal physiology, trophic interactions, community structure, and ecosystem-level processes; however, the interactions between toxicity and elemental imbalance in food resources have been examined in only a few ecotoxicity studies. Integrating well-developed ecological theories that cross all levels of biological organization can enhance our understanding of ecotoxicology. In the present article, we underline the opportunity to couple concepts and approaches used in the theory of ecological stoichiometry (ES) to ask ecotoxicological questions and introduce stoichiometric ecotoxicology, a subfield in ecology that examines how contaminant stress, nutrient supply, and elemental constraints interact throughout all levels of biological organization. This conceptual framework unifying ecotoxicology with ES offers potential for both empirical and theoretical studies to deepen our mechanistic understanding of the adverse outcomes of chemicals across ecological scales and improve the predictive powers of ecotoxicology.

In regions where there are multiple sources of methane (CH4) in close proximity, it can be difficult to apportion the CH4 measured in the atmosphere to the appropriate sources. In the Surat Basin, Queensland, Australia, coal seam gas (CSG) developments are surrounded by cattle feedlots, grazing cattle, piggeries, coal mines, urban centres and natural sources of CH4. The characterization of carbon (δ13C) and hydrogen (δD) stable isotopic composition of CH4 can help distinguish between specific emitters of CH4. However, in Australia there is a paucity of data on the various isotopic signatures of the different source types. This research examines whether dual isotopic signatures of CH4 can be used to distinguish between sources of CH4 in the Surat Basin. We also highlight the benefits of sampling at nighttime. During two campaigns in 2018 and 2019, a mobile CH4 monitoring system was used to detect CH4 plumes. Sixteen plumes immediately downwind from known CH4 sources (or individual facilities) were sampled and analysed for their CH4 mole fraction and δ13CCH4 and δDCH4 signatures. The isotopic signatures of the CH4 sources were determined using the Keeling plot method. These new source signatures were then compared to values documented in reports and peer-reviewed journal articles. In the Surat Basin, CSG sources have δ13CCH4 signatures between −55.6 ‰ and −50.9 ‰ and δDCH4 signatures between −207.1 ‰ and −193.8 ‰. Emissions from an open-cut coal mine have δ13CCH4 and δDCH4 signatures of -60.0±0.6 ‰ and -209.7±1.8 ‰ respectively. Emissions from two ground seeps (abandoned coal exploration wells) have δ13CCH4 signatures of -59.9±0.3 ‰ and -60.5±0.2 ‰ and δDCH4 signatures of -185.0±3.1 ‰ and -190.2±1.4 ‰. A river seep had a δ13CCH4 signature of -61.2±1.4 ‰ and a δDCH4 signature of -225.1±2.9 ‰. Three dominant agricultural sources were analysed. The δ13CCH4 and δDCH4 signatures of a cattle feedlot are -62.9±1.3 ‰ and -310.5±4.6 ‰ respectively, grazing (pasture) cattle have δ13CCH4 and δDCH4 signatures of -59.7±1.0 ‰ and -290.5±3.1 ‰ respectively, and a piggery sampled had δ13CCH4 and δDCH4 signatures of -47.6±0.2 ‰ and -300.1±2.6 ‰ respectively, which reflects emissions from animal waste. An export abattoir (meat works and processing) had δ13CCH4 and δDCH4 signatures of -44.5±0.2 ‰ and -314.6±1.8 ‰ respectively. A plume from a wastewater treatment plant had δ13CCH4 and δDCH4 signatures of -47.6±0.2 ‰ and -177.3±2.3 ‰ respectively. In the Surat Basin, source attribution is possible when both δ13CCH4 and δDCH4 are measured for the key categories of CSG, cattle, waste from feedlots and piggeries, and water treatment plants. Under most field situations using δ13CCH4 alone will not enable clear source attribution. It is common in the Surat Basin for CSG and feedlot facilities to be co-located. Measurement of both δ13CCH4 and δDCH4 will assist in source apportionment where the plumes from two such sources are mixed.

Hemorrhage remains a significant cause of morbidity and mortality following trauma and during complex surgeries. A variety of nanomaterials, including oxidized cellulose nanofibers (OCNFs), have been studied to overcome the disadvantages of current commercial topical hemostats. However, the relationship between nano-structural characteristics and hemostatic efficacy of non-oxidized cellulose nanofibers (CNFs) has not been elucidated. Herein, we present the first report of the correlation between structure and hemostatic performance of CNFs. In vitro thromboelastometry studies on CNFs, synthesized by ball-milling, showed that there is an optimum balance point between the aspect ratio (AR) and specific surface area (SSA) of nanofibers in terms of their maximum contribution to platelet function and plasma coagulation. The optimized CNFs with high SSA (17 m2/g) and a high AR (166) shortened normal whole blood clotting time by 68 %, outperforming cellulose-based hemostats. Additionally, CNFs reduced clotting time in platelet-deficient blood (by 80 %) and heparinized blood (by 54 %).