Sorption-oxidation mechanism for the removal of arsenic (III) using Cu-doped ZnO in an alkaline medium.

1-D oxides Zn1-xCuxO and spherical composites Zn1-xCuxO/CuO were obtained by thermolysis of formate-glycolate complexes Zn1-xCux (HCOO)(OCH2CH2O)1/2 (0 ≤ x ≤ 0.15). The structural and property characteristics showed that Cu was introduced into the Zn site of the ZnO lattice to form the Zn0.95Cu0.05O solid solution. The concentration of copper in the precursors regulates the topological and structural features of the formation of Zn1-xCuxO oxides, which determine their sorption and photocatalytic properties. The materials were tested in As3+ photooxidation reaction under UV and visible radiation. It has been established that Cu+ is an effective dopant in the composition of 1-D oxide Zn1-xCuxO (0 ≤ x < 0.1). The presence of Cu2+ in the shell of Zn1-xCuxO/CuO composite reduces the photoactivity of the material. The maximum efficiency of arsenic extraction (up to 80% for Zn0.95Cu0.05O) was achieved from dilute arsenic-containing solutions (3.8 mg/L As) and an adsorbent concentration of 0.8 g/L for 24 h. In saturated solutions (380 mg/L As) this value is reduced by a factor of 100. According to XPS data, the primary process is As3+ sorption on the catalyst surface followed by its oxidation to As5+. Using the EPR method it was found that singly charged oxygen vacancies V O + $$ {V}_O^{+} $$ associated with Cu in Zn1-xCuxO are directly involved in the photostimulated oxidation of As3+. PRACTITIONER POINTS: Two types of Zn1-x Cux O photocatalysts were obtained by thermolysis of the Zn1-x Сux (HCOO)(OCH2 CH2 O)1/2 complex (0 ≤ x ≤ 0.15) in air. Sorption of arsenic from dilute solutions reaches 80% on 1-D oxide Zn0.95 Cu0.05 O. Sorption of As3+ on the catalyst surface is at primary process followed by its oxidation to As5+ . Removal of As3+ from alkaline solutions occurs due to successful combination of sorption and photocatalytic properties of the 1-D oxides Zn1-x Cux O.

Mosaic of Anodic Alumina Inherited from Anodizing of Polycrystalline Substrate in Oxalic Acid.

The anodizing of aluminium under oscillating conditions is a versatile and reproducible method for the preparation of one-dimensional photonic crystals (PhCs). Many anodizing parameters have been optimised to improve the optical properties of anodic aluminium oxide (AAO) PhCs. However, the influence of the crystallographic orientation of an Al substrate on the characteristics of AAO PhCs has not been considered yet. Here, the effect of Al substrate crystallography on the properties of AAO PhCs is investigated. It is experimentally demonstrated that the cyclic anodizing of coarse-grained aluminium foils produces a mosaic of photonic crystals. The crystallographic orientation of Al grains affects the electrochemical oxidation rate of Al, the growth rate of AAO, and the wavelength position of the photonic band gap.

UV Light Irradiation Effects in P-Doped Diamonds: Total Content Determination of Phosphorus Donors.

Upon the UV light irradiation of single-crystal diamonds doped with phosphorus, several effects have been observed. The integral intensity of phosphorus lines in FTIR absorption spectra under UV radiation was increased. A saturation effect depending on the power of the laser radiation was demonstrated. Narrowing of the phosphorus lines, as well as the redistribution of the intensities in their doublets caused by the Jahn-Teller distortion of the donor ground state, was observed. It was found that these effects are associated with the decompensation of the phosphorus donors. An easy, fast, sensitive, and nondestructive, fully optical method for the determination of the total phosphorus donor's concentration in semiconducting diamonds, as well as its compensation ratio, was proposed.

Privacy Policies of IoT Devices: Collection and Analysis.

Currently, personal data collection and processing are widely used while providing digital services within mobile sensing networks for their operation, personalization, and improvement. Personal data are any data that identifiably describe a person. Legislative and regulatory documents adopted in recent years define the key requirements for the processing of personal data. They are based on the principles of lawfulness, fairness, and transparency of personal data processing. Privacy policies are the only legitimate way to provide information on how the personal data of service and device users is collected, processed, and stored. Therefore, the problem of making privacy policies clear and transparent is extremely important as its solution would allow end users to comprehend the risks associated with personal data processing. Currently, a number of approaches for analyzing privacy policies written in natural language have been proposed. Most of them require a large training dataset of privacy policies. In the paper, we examine the existing corpora of privacy policies available for training, discuss their features and conclude on the need for a new dataset of privacy policies for devices and services of the Internet of Things as a part of mobile sensing networks. The authors develop a new technique for collecting and cleaning such privacy policies. The proposed technique differs from existing ones by the usage of e-commerce platforms as a starting point for document search and enables more targeted collection of the URLs to the IoT device manufacturers' privacy policies. The software tool implementing this technique was used to collect a new corpus of documents in English containing 592 unique privacy policies. The collected corpus contains mainly privacy policies that are developed for the Internet of Things and reflect the latest legislative requirements. The paper also presents the results of the statistical and semantic analysis of the collected privacy policies. These results could be further used by the researchers when elaborating techniques for analysis of the privacy policies written in natural language targeted to enhance their transparency for the end user.

Influence of Laser Beam Wobbling Parameters on Microstructure and Properties of 316L Stainless Steel Multi Passed Repaired Parts.

The results of experimental studies of repair of the supporting structure components made of 316L steel multi-pass laser cladding with filler wire are presented. The influence of the wobbling mode parameters, welding speed, and laser power on the formation of the deposited metal during multi-pass laser cladding with filler wire of 316L steel samples into a narrow slot groove, 6 mm deep and 3 mm wide, are shown. Non-destructive testing, metallographic studies, and mechanical tests of the deposited metal before and after heat treatment (2 h at 450 °C) were carried out. Based on the results of experimental studies, the optimal modes of laser beam wobbling were selected (amplitude-1.3 mm, frequency-100 Hz) at which the formation of a bead of optimal dimensions (height-1672 µm, width-3939 µm, depth of penetration into the substrate-776 µm) was ensured. A laser cladding technology with ESAB OK Autrode 316L filler wire has been developed, which has successfully passed the certification for conformity with the ISO 15614-11 standard. Studies of the chemical elements' distribution before and after heat treatment showed that, after heat treatment along the grain boundaries, particles with a significantly higher Mo content (5.50%) were found in the sample, presumably precipitated phases. Microstructure studies and microhardness measurements showed that the upper part metal of the third pass, which has a lower microhardness (75% of base metal), higher ferrite content, and differently oriented dendritic austenite, significantly differs from the rest of the cladded metal.

Human exome sequence data in support of somatic mosaicism in carotid atherosclerosis.

Understanding the mechanisms underlying the connection between somatic mosaicism and cardiovascular disease is likely essential for the future of personalized medicine. This article is aimed at providing data on somatic mosaicism in human carotid atherosclerosis. An advanced carotid atherosclerotic plaque and white blood cells were collected simultaneously from each patient (eight Slavic males, aged 67 ± 3.8 years [mean ± SD]) to assess the spectrum of germline and somatic genetic variants. Exome sequencing of DNA from the samples was performed with the SureSelect Clinical Research Exome Enrichment Kit (Agilent Technologies) and HiSeq 1500 (Illumina). The dataset contains germline and somatic single-nucleotide variants and small indels identified in the advanced carotid atherosclerotic plaque and white blood cells of each patient. This dataset does not include copy number variants owing to a lack of suitable tools for reliable calculation of copy numbers from exome sequencing data on cancer-unrelated samples. The dataset should help to understand somatic mosaicism in cardiovascular diseases and to identify copy number variants by means of more appropriate newer tools in the future.

Regio- and stereoselective (3 + 2)-cycloaddition reactions of nitrones with cyclic allenes.

An effective approach to access functionalized 2H-cyclonona(deca)[d]isoxazoles and 15-oxo-3,10-methanobenzo[b][1]azacyclododecines has been developed by the reaction of N-aryl-C,C-bis(methoxycarbonyl)nitrones with cyclonona(deca)-1,2-dienes in a one-pot fashion. The reaction of N-aryl-C-(phenylcarbamoyl)nitrones with these allenes proceeds strictly regioselectively giving the mixtures of diastereomeric isoxazolidines containing a double bond at the C4-position of the isoxazolidine ring. The quantum chemical calculations show that the regioselectivity of these reactions is in good agreement with the reactivity indices of the considered compounds.

Selective and reversible 1,3-dipolar cycloaddition of 6-aryl-1,5-diazabicyclo[3.1.0]hexanes with 1,3-diphenylprop-2-en-1-ones under microwave irradiation.

The first example of the cycloaddition of in situ-generated azomethine imine under microwave conditions is described. The reaction of 6-aryl-1,5-diazabicyclo[3.1.0]hexanes with 1,3-diphenylprop-2-en-1-ones proceeds regio- and stereoselectively giving mostly good yields of the corresponding perhydropyrazolopyrazoles. The products of the reaction undergo cycloreversion under the reaction conditions.

Oxygen surface exchange and diffusion in mayenite single crystal.

Oxygen surface exchange and diffusion in Ca12Al14O33±Î´ single crystal were studied by a unique in situ method based on isotope equilibration in the gas phase. Although the interphase exchange rate and oxygen diffusion coefficient demonstrate good agreement with available data, only the employed method is efficient to isolate the contributions of various types of exchange; thus, for the first time, it is possible to estimate the surface heterogeneity of mayenite. The obtained results disprove conclusions previously developed in the literature; the temperature region of 750 °C to 850 °C is not the intermediate region where two types of oxygen diffusion coexist. Complex discussion of the accumulated information on the temperature-dependent properties of mayenite allowed us to represent a model describing the observed dependencies based on the near-surface layer stability in the studied temperature range.

Distal aortic remodelling after the standard and the elongated frozen elephant trunk procedure.

OBJECTIVES: The aim of this study was to evaluate abdominal aortic remodelling after the standard compared with the elongated frozen elephant trunk (FET) technique in patients with aortic dissection. METHODS: Twenty-six patients underwent surgery and were randomized into 2 groups. Fifteen patients were treated with the standard FET technique. Eleven patients were treated with the advanced FET technique using an additional thoracic stent graft implanted down to the coeliac artery, within 30 days after the first stent graft implantation. Preoperative and postoperative and 5-year follow-up computed tomography aortic scans were obtained along the stent graft (A), between the distal edge of the graft and the coeliac trunk (B) and at the abdominal aorta (C). RESULTS: In the standard FET group, positive and stable aortic remodelling occurred in segments A (100%), B (87%) and C (87%). Negative remodelling was found in 2/15 (13%) patients; 1 patient had an endovascular reintervention. In the elongated FET group, positive and stable remodelling were observed in segments A (100%), B (100%) and C (90.9%). Negative remodelling occurred in 1/11 (9.1%) patients. No reintervention was required. Cumulative survival, freedom from negative remodelling and distal aortic reintervention in the standard FET group and the elongated FET group were 72 vs 100% (P = 0.29); 67.5 vs 80% (P = 0.58) and 75 vs 100% (P = 0.61), respectively. CONCLUSIONS: The standard FET technique is an adequate measure to induce false lumen thrombosis and improve abdominal aortic remodelling. The elongated FET technique seems to be superior to the standard FET procedure in terms of freedom from aortic remodelling and the distal reintervention rate.

Colloidal branched CdSe/CdS 'nanospiders' with 2D/1D heterostructure.

In this paper we report the synthesis of colloidal CdSe/CdS core-shell heteronanoplatelets with epitaxially grown wurtzite (WZ) 1D CdS branches or legs by using cadmium diethyldithiocarbamate as a single-source precursor. The growth of WZ branches was achieved by exploiting zinc blende-wurtzite polytypism of cadmium chalcogenides induced by oleylamine. Synthesized 'nanospiders' exhibit enhanced absorption in the UV-blue region and narrow and relatively intense red photoluminescence depending on the amount of CdS in the heteronanostructure.

Observation of hidden atomic order at the interface between Fe and topological insulator Bi2Te3.

To realize spintronic devices based on topological insulators (TIs), well-defined interfaces between magnetic metals and TIs are required. Here, we characterize atomically precisely the interface between the 3d transition metal Fe and the TI Bi2Te3 at different stages of its formation. Using photoelectron diffraction and holography, we show that after deposition of up to 3 monolayers Fe on Bi2Te3 at room temperature, the Fe atoms are ordered at the interface despite the surface disorder revealed by our scanning-tunneling microscopy images. We find that Fe occupies two different sites: a hollow adatom deeply relaxed into the Bi2Te3 quintuple layers and an interstitial atom between the third (Te) and fourth (Bi) atomic layers. For both sites, our core-level photoemission spectra and density-functional theory calculations demonstrate simultaneous chemical bonding of Fe to both Te and Bi atoms. We further show that upon deposition of Fe up to a thickness of 20 nm, the Fe atoms penetrate deeper into the bulk forming a 2-5 nm interface layer containing FeTe. In addition, excessive Bi is pushed down into the bulk of Bi2Te3 leading to the formation of septuple layers of Bi3Te4 within a distance of ∼25 nm from the interface. Controlling the magnetic properties of the complex interface structures revealed by our work will be of critical importance when optimizing the efficiency of spin injection in TI-based devices.

Regioselective Synthesis of 7-(Trimethylsilylethynyl)pyrazolo[1,5-a]pyrimidines via Reaction of Pyrazolamines with Enynones.

Condensation of enynones readily available from cheap starting material with pyrazolamines provides easy access to fluorescent 7-(trimethylsilylethynyl)pyrazolo[1,5-a]pyrimidines. The reaction is straightforward, does not require the use of any additional reagents or catalysts, and can be performed without inert atmosphere. Various substituents and functional groups in both enynone and pyrazolamine are tolerated. The presented method features full regioselectivity, high isolated yields, and simplicity of both setup and product purification. Fluorescent properties of the obtained pyrazolopyrimidines were studied.

Large-Scale Sublattice Asymmetry in Pure and Boron-Doped Graphene.

The implementation of future graphene-based electronics is essentially restricted by the absence of a band gap in the electronic structure of graphene. Options of how to create a band gap in a reproducible and processing compatible manner are very limited at the moment. A promising approach for the graphene band gap engineering is to introduce a large-scale sublattice asymmetry. Using photoelectron diffraction and spectroscopy we have demonstrated a selective incorporation of boron impurities into only one of the two graphene sublattices. We have shown that in the well-oriented graphene on the Co(0001) surface the carbon atoms occupy two nonequivalent positions with respect to the Co lattice, namely top and hollow sites. Boron impurities embedded into the graphene lattice preferably occupy the hollow sites due to a site-specific interaction with the Co pattern. Our theoretical calculations predict that such boron-doped graphene possesses a band gap that can be precisely controlled by the dopant concentration. B-graphene with doping asymmetry is, thus, a novel material, which is worth considering as a good candidate for electronic applications.

Synthesis of di-, tri- and tetracyclopropylhydrazines.

Previously unknown 1,1-dicyclopropylhydrazine was obtained in two steps starting from dicyclopropylamine. It serves as a convenient starting material to tri- and tetracyclopropylhydrazines, which have not been described in the literature either. Tricyclopropylhydrazine was prepared in an overall four-step sequence featuring the de Meijere-Chaplinski modification of the Kulinkovich reaction as a key step. Tetracyclopropylhydrazine was obtained by the reductive amination of the cyclopropanone ethyl trimethylsilyl acetal with 1,1-dicyclopropylhydrazine or with the parent hydrazine. Synthetic utility of these cyclopropylhydrazine building blocks is presented as well.

Thiazol-4-one derivatives from the reaction of monosubstituted thioureas with maleimides: structures and factors determining the selectivity and tautomeric equilibrium in solution.

2-(Alkyl(aryl)amino)thiazol-4(5H)-ones can regioselectively be prepared from monoalkyl(aryl)thioureas and maleimides. In solution, the former heterocycles exist in a tautomeric equilibrium with 2-(alkyl(aryl)imino)thiazolidin-4-ones and the substituent on the exocyclic nitrogen atom governs the ratio of these tautomers. Isomers with the alkyl group in the endocyclic position can be obtained from N-methyl(ethyl)thioureas. 2D NMR spectroscopy and DFT calculations rationalize experimental results.

Regioselective Transition-Metal-Free Synthesis of 2-(Trimethylsilylmethylene)pyrrol-3-ones by Thermal Cyclization of Acetylenic Enamines.

Acetylenic enamines generated in situ from readily available enynones and primary amines undergo thermal cyclization in diphenyl ether providing easy access to 4-aryl-2-(trimethylsilylmethylene)-1,2-dihydro-3H-pyrrol-3-ones. This reaction is inherently versatile, allowing for variations of substituents in both enynone and amine. Full regioselectivity along with short reaction time (1-2 h) and simple workup afford single products in good to excellent isolated yields. Fluorescent properties of the obtained compounds were studied.

Synthesis of 2-(hetero)aryl-5-(trimethylsilylethynyl)oxazoles from (hetero)arylacrylic acids.

A three-step method for the synthesis of 2-(hetero)aryl-5-(trimethylsilylethynyl)oxazoles is described. Easily accessible bis(trimethylsilyl)acetylene and acrylic acid derivatives are used as starting materials for the preparation of mono- and disubstituted 5-(trimethylsilyl)pent-1-en-4-yn-3-ones. Oxidative phthalimidoaziridination of these enynones provides the key 2-acyl-1-phthalimidoaziridines that are further utilized in the thermal expansion of the three-membered ring to furnish the target functionalizable oxazoles.

Inter-electrode spacing of surface EMG sensors: reduction of crosstalk contamination during voluntary contractions.

We investigated the influence of inter-electrode spacing on the degree of crosstalk contamination in surface electromyographic (sEMG) signals in the tibialis anterior (target muscle), generated by the triceps surae (crosstalk muscle), using bar and disk electrode arrays. The degree of crosstalk contamination was assessed for voluntary constant-force isometric contractions and for dynamic contractions during walking. Single-differential signals were acquired with inter-electrode spacing ranging from 5 mm to 40 mm. Additionally, double differential signals were acquired at 10 mm spacing using the bar electrode array. Crosstalk contamination at the target muscle was expressed as the ratio of the detected crosstalk signal to that of the target muscle signal. The crosstalk contamination ratio approached a mean of 50% for the 40 mm spacing for triceps surae muscle contractions at 80% MVC and tibialis anterior muscle contractions at 10% MVC. For single differential recordings, the minimum crosstalk contamination was obtained from the 10 mm spacing. The results showed no significant differences between the bar and disk electrode arrays. During walking, the crosstalk contamination on the tibialis anterior muscle reached levels of 23% for a commonly used 22 mm spacing single-differential disk sensor, 17% for a 10 mm spacing single-differential bar sensor, and 8% for a 10 mm double-differential bar sensor. For both studies the effect of electrode spacing on crosstalk contamination was statistically significant. Crosstalk contamination and inter-electrode spacing should therefore be a serious concern in gait studies when the sEMG signal is collected with single differential sensors. The contamination can distort the target muscle signal and mislead the interpretation of its activation timing and force magnitude.

Filtering the surface EMG signal: Movement artifact and baseline noise contamination.

The surface electromyographic (sEMG) signal that originates in the muscle is inevitably contaminated by various noise signals or artifacts that originate at the skin-electrode interface, in the electronics that amplifies the signals, and in external sources. Modern technology is substantially immune to some of these noises, but not to the baseline noise and the movement artifact noise. These noise sources have frequency spectra that contaminate the low-frequency part of the sEMG frequency spectrum. There are many factors which must be taken into consideration when determining the appropriate filter specifications to remove these artifacts; they include the muscle tested and type of contraction, the sensor configuration, and specific noise source. The band-pass determination is always a compromise between (a) reducing noise and artifact contamination, and (b) preserving the desired information from the sEMG signal. This study was designed to investigate the effects of mechanical perturbations and noise that are typically encountered during sEMG recordings in clinical and related applications. The analysis established the relationship between the attenuation rates of the movement artifact and the sEMG signal as a function of the filter band pass. When this relationship is combined with other considerations related to the informational content of the signal, the signal distortion of filters, and the kinds of artifacts evaluated in this study, a Butterworth filter with a corner frequency of 20 Hz and a slope of 12 dB/oct is recommended for general use. The results of this study are relevant to biomechanical and clinical applications where the measurements of body dynamics and kinematics may include artifact sources.