Synthesis of Novel Phosphonic‐Type Activity‐Based Probes for Neutrophil Serine Proteases and Their Application in Spleen Lysates of Different Organisms

Neutrophils are a type of granulocyte important in the “first line of defense” of the innate immune system. Upon activation, they facilitate the destruction of invading microorganisms by the production of superoxide radicals, as well as the release of the enzymatic contents of their lysozymes. These enzymes include specific serine proteases: cathepsin G, neutrophil elastase, proteinase 3, as well as the recently discovered neutrophil serine protease 4 (NSP4). Under normal conditions, the proteolytic activity of neutrophil proteases is tightly regulated by endogenous serpins; however, this mechanism can be subverted during tissue stress, thereby resulting in the uncontrolled activity of serine proteases, which induce chronic inflammation and subsequent pathology. Herein, we describe the development of low‐molecular‐weight activity‐based probes that specifically target the active sites of neutrophil proteases.     

Photoluminescence and energy transfer in transparent glass-ceramics based on GdF3:RE3+ (RE = Tb,Eu) nanocrystals

In the present work,the transparent oxyfluoride glass-ceramic samples containing GdF_3:RE~(3+)(RE=Tb,Eu) nanocrystals(nGCs) were fabricated via controlled heat-treatment of precursor xerogels prepared using a sol-gel method.The formation of GdF_3 nanocrystalline phase from gadolinium(III) trifluoroacetate was verified based on XRD measurements.The average crystal sizes calculated from Scherrer formula were estimated to～10 nm as well as～6 nm for Tb~(3+)-and Eu~(3+)-doped samples,respectively.The optical behavior of prepared sol-gel samples was evaluated based on photoluminescence excitation(PLE) and emission spectra(PL) as well as luminescence decay analysis.Obtained samples exhibit the ~5D_4→~7F_J(J=6-3,Tb~(3+))and the ~5D_0→~7F_J(J=0-4,Eu~(3+)) emission bands recorded within the visible spectral area under excitation at near-UV(393 nm(Eu~(3+)),351,369,378 nm(Tb~(3+))) as well as middle-UV illumination(273 nm(Gd~(3+))).Additionally,based on recorded decay curves,the luminescence lifetimes(τ_m) for the ~5D_4(Tb3+) and the ~5D_0(Eu~(3+))excited states were also evaluated.In general,recorded luminescence spectra and double-exponential character of decay curves for nGCs indicate a successful migration of Tb~(3+) and Eu~(3+) dopant ions from amorphous silicate framework to lowphonon energy GdF_3 nanocrystal phase.     

Fluorine-Containing Drug Administration in Rats Results in Fluorination of Selected Proteins in Liver and Brain Tissue

In many pharmaceuticals, a hydrogen atom or hydroxyl group is replaced by a fluorine to increase bioavailability and biostability. The fate of fluorine released from fluorine-containing drugs is not well investigated. The aim of this study was to examine possible fluorination of proteins in rat liver and brain after administration of the fluorinated drug cinacalcet. We assigned 18 Wistar rats to a control group (n = 6) and a group treated with cinacalcet (2 mg kg⁻¹/body weight, 5 days/week), divided into 7 day (n = 6) and 21 day (n = 6) treatment subgroups. Fluorinated proteins were identified using a free proteomics approach; chromatographic separation and analysis by high-resolution mass spectrometry; peptide/protein identification using the Mascot search algorithm; manual verification of an experimentally generated MS/MS spectrum with the theoretical MS/MS spectrum of identified fluorinated peptides. Three fluorinated proteins (spectrin beta chain; carbamoyl-phosphate synthase [ammonia], mitochondrial; 6-phosphofructo-2-kinase/fructose-2, 6-bisphosphatase 1) were identified in the liver and four (spectrin beta chain, dihydropyrimidinase-related protein 4, prominin-2, dihydropyrimidinase-related protein 4) in the brain tissue after 21 days of cinacalcet treatment, but not in the control group. Introduction of fluorine into an organism by administration of fluorinated drugs results in tissue-specific fluorination of proteins.     

Structural and electrical properties of Cr-doped SrTiO3 porous materials

Series of single-phase materials with assumed formula SrTi_1?xCr_xO₃ (where x = 0, 1, 4, 6 mol.%) were obtained by sol-gel method. The structure and microstructure of materials were characterised by X-ray diffraction and scanning electron microscopy methods. Moreover, the study of electrical properties and evaluation of chemical stability in CO₂/H₂O atmosphere was performed by electrochemical impedance spectroscopy and thermogravimery methods, respectively. The possibility of participation of Cr-doped strontium titanate in oxidation–reduction processes was analysed by temperature-programed reduction (TPR) and temperature-programed oxidation (TPOx) measurements. The changes of lattice parameters together with XPS analysis, the Seebeck coefficient measurements results and TPR profiles obtained for SrTi_1?xCr_xO₃ materials prove the presence of chromium on +3 and +6 oxidation stages. Thus, chromium can be treated as both acceptor- and donor-type dopant in the SrTiO₃ structure. The Cr³⁺/Cr⁶⁺ ratio strongly affects the electrical properties, as the change of conduction mechanism was observed. The results of performed stability test clearly indicate that incorporation of chromium into SrTiO₃ structure results with decrease of chemical stability in CO₂ atmosphere.     

Influence of addition of green tea and green coffee extracts on the properties of fine yeast pastry fried products

This study investigated the influence of antioxidants of green tea aqueous extract (GTE) and green coffee aqueous extract (GCE) in concentrations of 0.25, 0.5 and 1 g·100 g^? 1 on the nutritional properties of fine yeast pastry fried products such as donuts. Yeast donuts were made according to the traditional processing technology. In fried donuts physical properties (water activity, pH, hardness and color with the use of instrumental methods) as well as sensory properties were established. Moreover, quality of fat extracted from donuts (composition of fatty acids and peroxide value), content of acrylamide, composition of polyphenols and antioxidant activity were analyzed. Obtained extracts of GTE and GCE contained 26 and 41% of polyphenols, respectively, and the degree of polyphenol degradation during production of donuts was less when the dilution in dough was greater. Both tests indicated that the highest antioxidant activity had donuts with the highest analyzed addition of extract, however depending on the applied test or GTE or GCE had better antioxidant properties. Fatty acid composition was the most beneficial when the addition of GTE and GCE was on a level of 0.25 and 0.5 g·100 g^? 1, respectively. In fried donuts relatively low amounts of acrylamide were obtained, amounting to 18–46 μg·kg^? 1. Only the lowest addition of GTE and the highest addition of GCE caused an increase of acrylamide content in donuts, while all other levels of added extracts caused a decrease in the content of formed acrylamide.     

Selectivity enhancement in the catalytic heterogeneous hydrogenation of limonene in supercritical carbon dioxide by an ionic liquid

Ionic liquids as coated catalysts or additives tremendously alter the selectivity pattern of the heterogeneous solid catalyst in the selective hydrogenation of limonene. The conventional monometallic ruthenium over alumina catalyst combined with an ionic liquid enables the one-pot synthesis of the intermediate p-menthene through limonene hydrogenation in supercritical carbon dioxide. Among eight screened imidazolium ILs, [C₁₀mim]NTf₂ was employed as additive, or as the coating agent of ruthenium catalyst in the reaction under supercritical conditions.The coating of the heterogeneous catalyst allows the selective production of p-menthene and increases the conversion level of limonene (>99%) compared to the conversion of limonene in the reaction carried out in the presence of an ionic liquid as an additive. Results of the catalyst recycling indicate that there is no depletion of catalyst reactivity even after four successive cycles of operation under the studied reaction conditions. Further hydrogenation of p-menthene is strongly inhibited by employing an ionic liquid. The solubility of limonene or p-menthene in an ionic liquid governs the selective hydrogenation of limonene towards p-menthene.     

Optimizing Grid-Based Workflow Execution

Large-scale applications can be expressed as a set of tasks with data dependencies between them, also known as application workflows. Due to the scale and data processing requirements of these applications, they require Grid computing and storage resources. So far, the focus has been on developing easy to use interfaces for composing these workflows and finding an optimal mapping of tasks in the workflow to the Grid resources in order to minimize the completion time of the application. After this mapping is done, a workflow execution engine is required to run the workflow over the mapped resources. In this paper, we show that the performance of the workflow execution engine in executing the workflow can also be a critical factor in determining the workflow completion time. Using Condor as the workflow execution engine, we examine the various factors that affect the completion time of a fine granularity astronomy workflow. We show that changing the system parameters that influence these factors and restructuring the workflow can drastically reduce the completion time of this class of workflows. We also examine the effect on the optimizations developed for the astronomy application on a coarser granularity biology application. We were able to reduce the completion time of the Montage and the Tomography application workflows by 90% and 50%, respectively.     

Defect depth profiling after sphere indentation and blasting in aluminum and aluminum alloy detected by positron annihilation

The paper presents the experimental results of positron annihilation measurements of the subsurface zones in aluminum and aluminum alloy exposed to the indentation of the small steel ball or blasting by the silicon carbide particles. The measurements of the Doppler broadening of the annihilation line and positron lifetime (PL) enabled the depth profile of open volume defects induced by indentation and blasting processes to be obtained. The coincidence of the von Mises criterion for yield with the onset of the increase of the defect concentration at certain depth was detected. It was established that the defects created in the pure aluminum and the aluminum alloy detected by positrons are different. However, the kinds of induced defects do not change with depth. The PL measurements indicate the presence of vacancy clusters in samples exposed to blasting. The vacancy clusters created in the aluminum alloy are larger than in the pure aluminum.     

Quantification of Protein‐Induced Membrane Remodeling Kinetics In Vitro with Lipid Multilayer Gratings

The dynamic self‐organization of lipids in biological systems is a highly regulated process that enables the compartmentalization of living systems at micro‐ and nanoscopic scales. Consequently, quantitative methods for assaying the kinetics of supramolecular remodeling such as vesicle formation from planar lipid bilayers or multilayers are needed to understand cellular self‐organization. Here, a new nanotechnology‐based method for quantitative measurements of lipid–protein interactions is presented and its suitability for quantifying the membrane binding, inflation, and budding activity of the membrane‐remodeling protein Sar1 is demonstrated. Lipid multilayer gratings are printed onto surfaces using nanointaglio and exposed to Sar1, resulting in the inflation of lipid multilayers into unilamellar structures, which can be observed in a label‐free manner by monitoring the diffracted light. Local variations in lipid multilayer volume on the surface is used to vary substrate availability in a microarray format. A quantitative model is developed that allows quantification of binding affinity (K _D) and kinetics (k_on and k_off). Importantly, this assay is uniquely capable of quantifying membrane remodeling. Upon Sar1‐induced inflation of single bilayers from surface supported multilayers, the semicylindrical grating lines are observed to remodel into semispherical buds when a critical radius of curvature is reached.