ZnO Nanoplatelets with Controlled Thickness: Atomic Insight into Facet-Specific Bimodal Ligand Binding Using DNP NMR

Colloidal nanoplatelets (NPLs) and nanosheets with controlled thickness have recently emerged as an exciting new class of quantum-sized nanomaterials with substantially distinct optical properties compared to 0D quantum dots. Zn-based NPLs are an attractive heavy-metal-free alternative to the so far most widespread cadmium chalcogenide colloidal 2D semiconductor nanostructures, but their synthesis remains challenging to achieve. The authors describe herein, to the best of their knowledge, the first synthesis of highly stable ZnO NPLs with the atomically precise thickness, which for the smallest NPLs is 3.2 nm (corresponding to 12 ZnO layers). Furthermore, by means of dynamic nuclear polarization-enhanced solid-state ¹⁵N NMR, the original role of the benzamidine ligands in stabilizing the surface of these nanomaterials is revealed, which can bind to both the polar and non-polar ZnO facets, acting either as X- or L-type ligands, respectively. This bimodal stabilization allows obtaining hexagonal NPLs for which the surface energy of the facets is modulated by the presence of the ligands. Thus, in-depth study of the interactions at the organic–inorganic interfaces provides a deeper understanding of the ligand–surface interface and should facilitate the future chemistry of stable-by-design nano-objects.     

Interactions of Amyloid-β with Membrane Proteins

In developing and developed countries, an increasing elderly population is observed. This affects the growing percentage of people struggling with neurodegenerative diseases, including Alzheimer’s disease. Nevertheless, the pathomechanism of this disease is still unknown. This contributes to problems with early diagnosis of the disease as well as with treatment. One of the most popular hypotheses of Alzheimer’s disease is related to the pathological deposition of amyloid-β (Aβ) in the brain of ill people. In this paper, we discuss issues related to Aβ and its relationship in the development of Alzheimer’s disease. The structure of Aβ and its interaction with the cell membrane are discussed. Not only do the extracellular plaques affect nerve cells, but other forms of this peptide as well.     

Rheological characteristics of oligomeric semiproducts gained via chemical degradation of polyurethane foam using crude glycerin in the presence of different catalysts

Polyurethane (PU) recycling is a topic of growing interest due to the increasing amount of polyurethane waste. The main purpose of polyurethane chemical recycling is to recover the starting polyol. In this study, a method of polyurethane thermochemical recycling, glycerolysis by means of crude glycerin, is proposed. This work presents a comparative study of commercial catalysts used in order to accelerate the decomposition process, namely triethylamine (TEA), potassium acetate (KAc), 1,4‐diazabicyclo[2.2.2]octane (DABCO), sodium hydroxide (NaOH), dibutyltin dilaurate (DbDl), and stannous octoate (StOc).The effect of used catalyst on the chemical structure and rheological properties was studied. The type of catalyst does not have significant influence on the chemical structure, but causes different course of reaction: split‐ and single‐phase in applied conditions. Glycerolysates were measured by Brookfield Rheometer. It was found that repolyols can be described by the Herschel–Bulkely mathematical model in the best accuracy. The investigation showed that the rheological behavior of glycerolysates depended on the catalyst used in glycerolysis process. POLYM. ENG. SCI., 57:891–900, 2017. © 2016 Society of Plastics Engineers     

Synthesis of trimethylene carbonate/ϵ‐caprolactone copolymers initiated with zinc alkoxide: influence of copolymer chain microstructure on thermal and mechanical properties

Ethylzinc(II ) ethoxide is a highly active and efficient initiator for the bulk polymerization of 1,3‐trimethylene carbonate and its copolymerization with ? ‐caprolactone. This initiator allows one to obtain (co)polymers with high molar masses in quite a short time. Significant difference in co‐monomer reactivity and relatively low participation of intermolecular transesterification processes lead to the obtained copolymers being characterized by a gradient chain microstructure. In ¹³C NMR spectra, in all regions, we observed the presence of triads which were distinctly represented by four peaks for the carbonyl signal. Mechanical tests showed that copolymers containing 70% and more of ? ‐caprolactone presented a relatively high Young's modulus and a very high maximum elongation factor; therefore these materials are promising in many biomedical applications. Due to the high reaction rate, we also made an attempt at copolymerization using reactive extrusion which gave promising results. © 2017 Society of Chemical Industry     

Repair of Protein Radicals by Antioxidants

In vivo, proteins are the main targets for radicals and other reactive species. Their reactions result in formation of amino acid radicals on the protein surface that often yield tryptophan and tyrosyl radicals or, in the presence of O₂, protein peroxyl radicals and hydroperoxides. All these species may propagate damage to biomolecules. Low molecular weight antioxidants, such as ascorbate, urate, and glutathione, are part of the defense system and function by repairing damaged proteins. We briefly review the existing knowledge about protein and amino acid radicals and their repair by antioxidants, including results of our investigations. The main question addressed is whether the antioxidants ascorbate, urate, and glutathione are able to repair amino acid radicals in model compounds and in proteins in vitro by pulse radiolysis. We show that ascorbate and urate repair tryptophan and tyrosyl radicals efficiently and inhibit proton-coupled electron transfer from tyrosine residues to tryptophan radicals in a number of proteins. In contrast, repair by glutathione is much slower. Ascorbate also rapidly reduces the peroxyl radicals of the N-acetylamide derivatives of glycine, alanine, and proline, whereas glutathione reduces peroxyl radicals in lysozyme. In vivo urate, ascorbate, and glutathione may prevent biological damage or, at least, reduce its rate, because they: (a) repair tryptophan and tyrosyl radicals in proteins and (b) reduce protein peroxyl radicals to the corresponding protein hydroperoxides. Most likely, in vivo, ascorbate and glutathione do not inhibit the reaction of C-centered amino acid radicals with O₂. Glutathione is less efficient that urate and ascorbate in repairing protein radicals; furthermore, the resulting glutathiyl radical is harmful. Ascorbate may be the more important repair agent in cells and tissues characterized by high ascorbate concentrations, such as the lens and brain; urate may be mainly responsible for repair in tissue compartments with higher urate concentrations, such as in plasma and saliva.     

The impact of a sewage treatment plant's effluent on sediment quality in a small bay in Lake Geneva (Switzerland–France). Part 2: Temporal evolution of heavy metals

The Bay of Vidy is the most contaminated area of Lake Geneva, Switzerland, as a result of the release of treated and untreated waste water from the municipal sewage treatment plant of the city of Lausanne and its surroundings. The reconstruction of the historical deposition of heavy metals in the sediment of the bay has been performed by the analysis of several dated (radiocaesium) sediment cores. The presence of sewage‐derived contaminants in the Bay of Vidy since the beginning of the sewage treatment plant's operations in 1964 is clearly observed, when a sharp increase in heavy metal contents is recorded, with maximum concentrations of cadmium, copper, zinc and lead occurring between the late 1960s and early 1970s. Despite considerable improvement in recent times, the present concentrations of the investigated heavy metals in sediments of the Bay of Vidy are still higher than concentrations measured at the centre of the lake, the latter close to Lake Geneva's natural background values. It is concluded that the quantity of heavy metals deposited in the bay is considerable and, because of sediment instability, will constitute a potential hazard for biota.     

Direct determination of benzodiazepines in biological fluids by restricted-access solid-phase microextraction

A biocompatible solid-phase microextraction (SPME) fiber was prepared using an alkyl-diol-silica (ADS) restricted-access material as the SPME coating. The ADS-SPME fiber was able to simultaneously fractionate the protein component from a biological sample, while directly extracting several benzodiazepines, overcoming the present disadvantages of direct sampling in biological matrixes by SPME. The fiber was interfaced with an HPLC-UV system, and an isocratic mobile phase was used to desorb, separate, and quantify the extracted compounds. The calculated clonazepam, oxazepam, temazepam, nordazepam, and diazepam detection limits were 600, 750, 333, 100, and 46 ng/mL in urine, respectively. The method was confirmed to be linear over the range of 500-50000 ng/mL with an average linear coefficient (R2) value of 0.9918. The injection repeatability and intraassay precision of the method were evaluated over 10 injections, resulting in a RSD of approximately 6%. The ADS-SPME fiber was robust and simple to use, providing many direct extractions and subsequent determination of benzodiazepines in biological fluids.     

Lecane tenuiseta rotifers improves activated sludge settleability in laboratory scale SBR system at 13°C and 20°C

Two experiments at different temperatures were conducted in five laboratory‐scale bioreactors with enhanced nutrient removal simulating the work of sequencing batch reactors (SBRs). The process was operated in three 8‐hour cycles. The oxygen concentration, pH and temperature were controlled and maintained at 1 mg of O₂/L, 7 and 13°C, respectively, throughout the first two weeks and at 20°C for the next 10 days. The introduction of Lecane tenuiseta improved the settling properties of the activated sludge dominated by Microthrix parvicella at both temperatures tested. L. tenuiseta rotifers led to a reduction in filamentous bacteria abundance and did not negatively affect the chemical parameters of the effluent. For each temperature, there were no differences in COD, N_tot, N‐NH₄ or P‐PO₄ values between the treatment and control bioreactors. The results have shown that the application of L. tenuiseta is a promising biological tool for bulking prevention especially in a cold season.     

Selected elements of rock burst state assessment in case studies from the Silesian hard coal mines

Exploitation of coal seams in the Upper Silesian Coal Basin is conducted in complex and difficult conditions. These difficulties are connected with the occurrence of many natural mining hazards and limitations resulting from the existing in this area surface infrastructure. One of the most important problems of Polish mining is the rock burst hazard and reliable evaluation of its condition. During long-years' mining practice in Poland a comprehensive system of evaluation and control of this hazard was de-veloped. In the paper the main aspects of rock burst hazard state evaluation will be presented, comprising: 1) rock mass inclination for rock bursts, I.e., rock strength properties investigation, comprehensive parametric evaluation of rock mass inclination for rock bursts, prognosis of seismic events induced by mining operations, methods of computer-aided modelling of stress and rock mass deformation parameters distribution, strategic rock mass classification under rock burst degrees; 2) immediate seismic and rock burst hazard state evaluation, I.e., low diameter test drilling method, seismologic and seismoacoustic method, comprehensive method of rock burst hazard state evaluation, non-standard methods of evaluation; 3) legal aspects of rock burst hazard state evaluation. Selected elements of the hazard state evaluation system are illustrated with specific practical examples of their applica-tion.     

Surface morphology of steel and titanium induced by ion beam bombardment – Comprehensive analysis

It is well known that ion bombardment of solid surface modifies its physical and chemical properties, among others, surface morphology. In this paper we try to concentrate on four aspects of ion beam induced surface morphology, i.e.: (a) surface topography, (b) surface roughness, (c) rate of profile shape variability, and (d) surface morphology arrangement. Surface topographies (in micro- and nanometre range) were observed by means of scanning electron and near-field microscopes. High quality profilograph and atomic force microscope were utilised to measure surface roughness parameters. To do that, surface profiles must be well known. To detect any profile shape alteration during ion beam bombardment we used fractal analysis, and especially fractal dimension D that can give information about rate of profile shape variability. Surface morphology arrangement, i.e. a question whether it is random or determined, was studied with the use of frequency plots resulting from harmonic analysis of profiles.We studied surface topographies, selected roughness parameters, fractal dimensions and frequency plots relating to stainless steel and polycrystalline 99.5% titanium bombarded with perpendicular low energy (800 eV) broad argon ion beam as well as neutralized narrow argon or krypton ion beam (up to 6 keV).