Potential influence of birds on soil testate amoebae in the Arctic

Birds can be an important agent of environmental change in High Arctic ecosystems, particularly due to the role of seabirds as a vector transferring nutrients from the marine to terrestrial realms. The soils of bird nesting sites are known to host distinct plant communities but the consequences of bird modification for microorganisms are much less clear. Our focus here is testate amoebae: a widely-distributed group of protists with significant roles in many aspects of ecosystem functioning. We compared the testate amoeba assemblages of a site on Spitsbergen (Svalbard archipelago) affected by nesting birds, with nearby control sites. We found differences in assemblage between sites, typified by reduced relative abundance of Phryganella acropodia and Centropyxis aerophila in bird-modified soils. These changes may reflect a reduced availability of fungal food sources. We found no evidence for differences in assemblage diversity or test concentration between bird-modified and control soils. Our dataset is small but results provide the first evidence for the potential effect of bird modification of soils on testate amoebae in the Arctic. Results show only limited similarity to experimental studies of nutrient addition, implying that response mechanisms may be more complicated than simply additional nutrient supply

A past capture event at Sagittarius A* inferred from the fluorescent X-ray emission of Sagittarius B clouds

The fluorescent X-ray emission from neutral iron in the molecular clouds (Sgr B) indicates that the clouds are being irradiated by an external X-ray source. The source is probably associated with the Galactic central black hole (Sgr A*), which triggered a bright outburst one hundred years ago. We suggest that such an outburst could be due to a partial capture of a star by Sgr A*, during which a jet was generated. By constraining the observed flux and the time variability ($\sim$ 10 years) of the Sgr B's fluorescent emission, we find that the shock produced by the interaction of the jet with the dense interstellar medium represents a plausible candidate for the X-ray source emission.Comment: 7 pages, 1 figure, accepted for publication in MNRA

The Role of 5-ALA in Low-Grade Gliomas and the Influence of Antiepileptic Drugs on Intraoperative Fluorescence

Objectives: Intraoperative tumor visualization with 5-aminolevulinic acid (5-ALA) induced protoporphyrin IX (PpIX) fluorescence is widely applied for improved resection of high-grade gliomas. However, visible fluorescence is present only in a minority of low-grade gliomas (LGGs) according to current literature. Nowadays, antiepileptic drugs (AEDs) are frequently administered to LGG patients prior to surgery. A recent in-vitro study demonstrated that AEDs result in significant reduction of PpIX synthesis in glioma cells. The aim of this study was thus to investigate the role of 5-ALA fluorescence in LGG surgery and the influence of AEDs on visible fluorescence.Patients and Methods: Patients with resection of a newly diagnosed suspected LGG after 5-ALA (25 mg/kg) administration were initially included. During surgery, the presence of visible fluorescence (none, mild, moderate, or bright) within the tumor and intratumoral fluorescence homogeneity (diffuse or focal) were analyzed. Tissue samples from fluorescing and/or non-fluorescing areas within the tumor and/or the assumed tumor border were collected for histopathological analysis (WHO tumor diagnosis, cell density, and proliferation rate). Only patients with diagnosis of LGG after surgery remained in the final study cohort. In each patient, the potential preoperative intake of AEDs was investigated.Results: Altogether, 27 patients with a histopathologically confirmed LGG (14 diffuse astrocytomas, 6 oligodendrogliomas, 4 pilocytic astrocytomas, 2 gemistocytic astrocytomas, and one desmoplastic infantile ganglioglioma) were finally included. Visible fluorescence was detected in 14 (52%) of 27. In terms of fluorescence homogeneity (n = 14), 7 tumors showed diffuse fluorescence, while in 7 gliomas focal fluorescence was noted. Cell density (p = 0.03) and proliferation rate (p = 0.04) was significantly higher in fluorescence-positive than in fluorescence-negative samples. Furthermore, 15 (56%) of 27 patients were taking AEDs before surgery. Of these, 11 patients (73%) showed no visible fluorescence. In contrast, 10 (83%) of 12 patients without prior AEDs intake showed visible fluorescence. Thus, visible fluorescence was significantly more common in patients without AEDs compared to patients with preoperative AED intake (OR = 0,15 (CI 95% 0.012–1.07), p = 0.046).Conclusions: Our study shows a markedly higher rate of visible fluorescence in a series of LGGs compared to current literature. According to our preliminary data, preoperative intake of AEDs seems to reduce the presence of visible fluorescence in such tumors and should thus be taken into account in the clinical setting

Nuclear Interaction Gamma-Ray Lines from the Galactic Center Region

Aims. The accretion of stars onto the central supermassive black hole at the center of the Milky Way is predicted to generate large fluxes of subrelativistic ions in the Galactic center region. We analyze the intensity, shape and spatial distribution of de-excitation gamma-ray lines produced by nuclear interactions of these energetic particles with the ambient medium. Methods. We first estimate the amount and mean kinetic energy of particles released from the central black hole during star disruption. We then calculate from a kinetic equation the energy and spatial distributions of these particles in the Galactic center region. These particle distributions are then used to derive the characteristics of the main nuclear interaction gamma-ray lines. Results. Because the time period of star capture by the supermassive black hole is expected to be shorter than the lifetime of the ejected fast particles against Coulomb losses, the gamma-ray emission is predicted to be stationary. We find that the nuclear de-excitation lines should be emitted from a region of maximum 5$^\circ$ angular radius. The total gamma-ray line flux below 8 MeV is calculated to be $\approx10^{-4}$ photons cm$^{-2}$ s$^{-1}$. The most promising lines for detection are those at 4.44 and $\sim$6.2 MeV, with a predicted flux in each line of $\approx$$10^{-5}$ photons cm$^{-2}$ s$^{-1}$. Unfortunately, it is unlikely that this emission can be detected with the INTEGRAL observatory. But the predicted line intensities appear to be within reach of future gamma-ray space instruments. A future detection of de-excitation gamma-ray lines from the Galactic center region would provide unique information on the high-energy processes induced by the central supermassive black hole and the physical conditions of the emitting region.Comment: 7 pages, 5 figures, accepted for publication in A&

Relationship between TEC jumps and auroral substorm in the high-latitude ionosphere

The influence of an auroral substorm on the total electron content (TEC) jumps and cycle slips on Global Positioning System (GPS) at high-latitudes is studied. For the first time, optical data from the all-sky imager, as well as interplanetary magnetic field and magnetometer data are used to complete the analysis of the slips occurrence and to monitor the substorm evolution. Two types of slips are considered: (i) instrumental slips including losses in the measured phase of the GPS signal and (ii) sharp TEC variations (TEC jumps) It is demonstrated that the jumps in TEC determined from the GPS signals are mainly related to the auroral particle precipitation that normally occurs during geomagnetic substorms in the polar ionosphere. The GPS frequency L2 is consistently subject to more slips than frequency L1 both for quiet and disturbed conditions. The probability of TEC jumps is higher than for cycle slips in phase at frequencies L1 and L2. The maximum of TEC jumps is observed during the recovery phase of the auroral substorm. Our findings are based on a data set obtained for a particular event. A generalization of the obtained numerical estimates to other events requires additional research and further analysis

Property-activity relations of multifunctional reactive ensembles in cation-exchanged zeolites: a case study of methane activation on Zn²⁺-modified zeolite BEA

The reactivity theories and characterization studies for metal-containing zeolites are often focused on probing the metal sites. We present a detailed computational study of the reactivity of Zn-modified BEA zeolite towards C-H bond activation of the methane molecule as a model system that highlights the importance of representing the active site as the whole reactive ensemble integrating the extra-framework ZnEF2+ cations, framework oxygens (OF2−), and the confined space of the zeolite pores. We demonstrate that for our model system the relationship between the Lewis acidity, defined by the probe molecule adsorption energy, and the activation energy for methane C-H bond cleavage performs with a determination coefficient R2 = 0.55. This suggests that the acid properties of the localized extra-framework cations can be used only for a rough assessment of the reactivity of the cations in the metal-containing zeolites. In turn, studying the relationship between the activation energy and pyrrole adsorption energy revealed a correlation, with R2 = 0.80. This observation was accounted for by the similarity between the local geometries of the pyrrole adsorption complexes and the transition states for methane C-H bond cleavage. The inclusion of a simple descriptor for zeolite local confinement allows transferability of the obtained property-activity relations to other zeolite topologies. Our results demonstrate that the representation of the metal cationic species as a synergistically cooperating active site ensembles allows reliable detection of the relationship between the acid properties and reactivity of the metal cation in zeolite materials.ChemE/Inorganic Systems Engineerin

The accuracy challenge of the DFT-based molecular assignment of ¹³C MAS NMR characterization of surface intermediates in zeolite catalysis

The influence of the model and method choice on the DFT predicted 13C NMR chemical shifts of zeolite surface methoxide species has been systematically analyzed. Twelve 13C NMR chemical shift calculation protocols on full periodic and hybrid periodic-cluster DFT calculations with varied structural relaxation procedures are examined. The primary assessment of the accuracy of the computational protocols has been carried out for the Si-O(CH3)-Al surface methoxide species in ZSM-5 zeolite with well-defined experimental NMR parameters (chemical shift, δ(13C) value) as a reference. Different configurations of these surface intermediates and their location inside the ZSM-5 pores are considered explicitly. The predicted δ value deviates by up to ±0.8 ppm from the experimental value of 59 ppm due to the varied confinement of the methoxide species at different zeolite sites (model accuracy). The choice of the exchange-correlation functional (method accuracy) introduces ±1.5 ppm uncertainty in the computed chemical shifts. The accuracy of the predicted 13C NMR chemical shifts for the computational assignment of spectral characteristics of zeolite intermediates has been further analyzed by considering the potential intermediate species formed upon methane activation by Cu/ZSM-5 zeolite. The presence of Cu species in the vicinity of surface methoxide increases the prediction uncertainty to ±2.5 ppm. The full geometry relaxation of the local environment of an active site at an appropriate level of theory is critical to ensure a good agreement between the experimental and computed NMR data. Chemical shifts (δ) calculated via full geometry relaxation of a cluster model of a relevant portion of the zeolite lattice site are in the best agreement with the experimental values. Our analysis indicates that the full geometry optimization of a cluster model at the PBE0-D3/6-311G(d,p) level of theory followed by GIAO/PBE0-D3/aug-cc-pVDZ calculations is the most suitable approach for the calculation of 13C chemical shifts of zeolite surface intermediates.ChemE/AlgemeenChemE/Inorganic Systems Engineerin

Effect of C-terminal His-tag and Purification Routine on the Activity and Structure of the Metalloenzyme, L-alanyl-d-glutamate Peptidase of the Bacteriophage T5

In this work, we studied the effect of the C-terminally attached poly-histidine tag (His-tag), as well as the peculiarities of the protein purification procedure by the immobilized metal affinity chromatography (IMAC) on the activity and structure of the metalloenzyme, l-alanyl-d-glutamate peptidase of bacteriophage T5 (EndoT5), whose zinc binding site and catalytic aspartate are located near the C-terminus. By itself, His-tag did not have a significant effect on either activity or folding of the polypeptide chain, nor on the binding of zinc and calcium ions to the protein. However, the His-tagged EndoT5 samples had low shelf-life, with storage of these samples resulting in an increased propensity for protein self-association and decreased enzymatic activity of EndoT5. Furthermore, disastrous effects on the activity of the enzyme were exerted by the presence of imidazole and nickel ions accompanying metal chelate chromatography. The activity of the protein can be restored by thorough washing off of these low molecular impurities via the prolonged dialysis of the His-tagged EndoT5 samples at the specifically elaborated conditions