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Search results for: Powder x-ray diffraction
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Spectacular Oxygen Evolution Reaction Enhancement through Laser Processing of the Nickel‐Decorated Titania Nanotubes
PublicationThe selective, laser‐induced modification of the nickel‐decorated titania nanotubes provides remarkable enhancement toward oxygen evolution reaction. Particularly, the irradiation of the laterally spaced crystalline TiO2 nanotubes, results in the formation of the tight closure over irradiated end, preserving their hollow interior. The shape of the absorbance spectra is modulated along with applied energy, and the new absorption...
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Correlation between partial inhibition of hydrogen evolution using thiourea and catalytic activity of AB5-type hydrogen storage alloy towards borohydride electrooxidation
PublicationDirect borohydride fuel cells (DBFCs) are devices which directly convert the chemical energy stored in the borohydride ion and oxidant into electrical energy as a result of redox reactions. Unfortunately, a significant amount of fuel is lost as a result of the undesirable hydrolysis reaction. The selection of an efficient borohydride hydrolysis inhibitor requires detailed knowledge regarding the interaction mechanism between the...
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Effect of Functionalization of Reduced Graphene Oxide Coatings with Nitrogen and Sulfur Groups on Their Anti-Corrosion Properties
PublicationElectrophoretic production of anticorrosion carbonaceous coatings on copper could be successfully performed by anodic oxidation of negatively charged graphene platelets suspended in an aqueous solution. The various platelets were synthesized by Hummer’s method followed by a hydrothermal reduction in the presence of NH4SCN which was expected to substitute some parts of graphene structure with nitrogen and sulfur groups. X-ray photoelectron...
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Spectacular Oxygen Evolution Reaction Enhancement Through Laser Processing of the Nickel-Decorated Titania Nanotubes
PublicationThe selective, laser-induced modification of the nickel-decorated titania nanotubes provides remarkable enhancement toward oxygen evolution reaction. Particularly, the irradiation of the laterally spaced crystalline TiO2 nanotubes, results in the formation of the tight closure over irradiated end, preserving their hollow interior. The shape of the absorbance spectra is modulated along with applied energy, and the new absorption...
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Non-destructive Testing of Wooden Elements
PublicationExamining the condition of wooden elements is crucial from the perspective of proper structure performance. If the deterioration in the internal wood condition, which displays no symptoms visible from the outside, is detected, the further spread of the deterioration can be prevented. Test results often point to the necessity of conducting repairs and, renovations, replacing the structure of wooden beams, or even substituting a...
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In Vitro Biological Characterization of Silver-Doped Anodic Oxide Coating on Titanium
PublicationDespite the high biocompatibility and clinical effectiveness of Ti-based implants, surface functionalization (with complex osteointegrative/antibacterial strategies) is still required. To enhance the dental implant surface and to provide additional osteoinductive and antibacterial properties, plasma electrolytic oxidation of a pure Ti was performed using a nitrilotriacetic acid (NTA)-based Ag nanoparticles (AgNP)-loaded calcium–phosphate...
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Wpływ azotowania jarzeniowego i laserowego nadtapiania na odporność kawitacyjną stali X5CrNi18-10
PublicationNierdzewne stale austenityczne charakteryzują się doskonałą odpornością korozyjną, aczkolwiek niskimi właściwościami mechanicznymi. W wielu przypadkach ogranicza to ich eksploatację w warunkach przemysłowych. Ponadto, nierdzewne stale austenityczne są wrażliwe na korozję lokalną w obecności jonów halogenkowych. Technologie materiałowe, które dają potencjalne możliwości otrzymywania korzystnego wpływu na właściwości mechaniczne...
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Structure and Molecular Dynamics in Renewable Polyamides from Dideoxy-Diamino Isohexide
PublicationThe chemical structure, the conformation, andthe flexibility of the polymer chain fragments present in thepolyamides synthesized from 2,5-diamino-2,5-dideoxy-1,4;3,6-dianhydrosorbitol, 1,4-diaminobutane, and either sebacic orbrassylic acid have been studied by liquid-state 2D NMRspectroscopy viz. correlation spectra (COSY) and heteronuclearmultiple-bond correlation spectra (gHMBC), by 13Ccross-polarization/magic-angle spinning...
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Nano soil improvement technique using cement
PublicationNano soil-improvement is an innovative idea in geotechnical engineering. Nanomaterials are among the newest additives that improve soil properties. Herein, laboratory tests, such as unconfined compressive strength, direct shear test, and initial tests, were conducted to investigate the geotechnical properties of Kelachay clay with micro- and nanosized cement to evaluate its particles in untreated soil and observe changes in the...
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Non-uniqueness of fracture parameter choice in simulations of concrete cracking at mesoscale level
PublicationIn the paper a non-uniqueness of fracture parameter choice in simulations of cracking process in plain concrete specimens at mesoscale level under monotonic static loading is analysed. The Finite Element Method is used, where cracks are defined in a discrete way using interface cohesive elements with nonlinear material law including softening. The concrete mesostructure (such as: cement matrix, air voids, aggregates, and Interfacial...
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Origin and fate of nanoparticles in marine water – Preliminary results
PublicationThe number, morphology and elemental composition of nanoparticles (<100 nm) in marine water was investigated using Variable Pressure Scanning Electron Microscopy (VP-SEM) and Energy-dispersive X-ray spectroscopy (EDS). Preliminary research conducted in the Baltic Sea showed that the number of nanoparticles in seawater varied from undetectable to 380 (x102) cm-3. Wind mixing and density barriers (thermocline) had a significant impact...
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Tuning of the Electrochemical Properties of Transparent Fluorine-doped Tin Oxide Electrodes by Microwave Pulsed-plasma Polymerized Allylamine
PublicationWe report here the dry, one-step, and low-temperature modification of FTO surfaces using pulsed plasma polymerization of allylamine (PPAAm). PPAAm/FTO surfaces were characterized by X-ray photoelectron spectroscopy, spectroscopic ellipsometry, and contact angles to understand the morphological, structural, and optical properties. FTO were coated with a very thin layer of adherent cross-linked, pinhole-, and additive-free allylamine...
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Lead(II) coordination polymers with imidazole-4- and pyrazole-3-carboxylate isomeric linkers: Structural diversity and luminescence properties
PublicationUsing 1H-imidazole-4-carboxylic acid (4imCOOH) and 1H-pyrazole-3-carboxylic acid (3pyrCOOH) coordination polymers [Pb(4imCOO)2(H2O)]n (1) and [Pb2(3pyrCOO)4]n (2) were constructed. Obtained polymers were characterized via FT-IR, X-ray, PL and TG methods. The coordination polyhedron around Pb(II) in 1 is described as distorted pentagonal pyramid with hemidirected coordination sphere (based on DFT calculations). Compound 2 consists...
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Improved Performance of 1-Ethyl-3-Methylimidazolium Tetrafluoroborate at Steel/HCl Interface by Iodide Ions
PublicationThe corrosion and corrosion inhibition of St37 steel in 0.1 M HCl solution by 1-ethyl-3-methylimidazolium tetrafluoroborate (EMITFB) and the effect of addition of KI on the inhibitive performance of EMITFB have been examined by electrochemical [electrochemical impedance spectroscopy, potentiodynamic polarization, and dynamic electrochemical impedance spectroscopy (DEIS)] and surface examination [scanning electron microscope (SEM)...
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Magnetic semiconductor photocatalysts for the degradation of recalcitrant chemicals from flow back water
PublicationIn the present study treatability of persistent organic compounds from the flow back water after hydrauling fracturing was investigated. The combination of TiO2 photocatalyst and magnetic oxide nanoparticles enhance the separation and recoverable property of nanosized TiO2 photocatalyst. Fe3O4/ TiO2 and Fe3O4@SiO2/TiO2 nanocomposites were prepared by heteroagglomeration. The photocatalysts’ characteristics by X-ray diffractometry...
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Fabrication and Significant Photoelectrochemical Activity of Titania Nanotubes Modified with Thin Indium Tin Oxide Film
PublicationOrdered titanium dioxide nanotubes (TiO2NTs) modified with indium tin oxide (ITO) films were obtained via magnetron sputtering, in which ITO plate was used as a target, onto the as-anodized titania support followed by the calcination process. The morphology of fabricated material with deposited oxide was investigated using scanning electron microscopy. Raman and UV–Vis spectroscopies were utilized to characterize crystalline phase...
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Classification of submandibular salivary stones based on ultrastructural studies
PublicationIntroduction: Sialolithiasis remains a clinical problem with unclear etiopathogenesis, lack of prevention methods, and only surgical treatment. Materials and methods: An ultrastructure examination of submandibular sialoliths obtained from patients with chronic sialolithiasis was conducted using a scanning electron microscope and X‐ray photoelectron spectroscopy. Results: Based on the results, we divided sialoliths into three types:...
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Electrochemical, theoretical and surface physicochemical studies of the alkaline copper corrosion inhibition by newly synthesized molecular complexes of benzenediamine and tetraamine with π acceptor
PublicationTwo charge transfer complexes, namely [(BDAH)+(PA−)] CT1 [(BTAH)2+(PA−)2] and CT2 (BDAH = 1,2-benzenediamine, BTAH = 1,2,4,5-benzenetetramine, and PA− = 2,4,6-trinitrophenolate), were synthesized and fully characterized using various spectroscopic techniques. CT1 and CT2 were tested as inhibitors to effectively control the uniform and anodic corrosion processes of copper in an alkaline electrolyte (1.0 M KOH) using various electrochemical...
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Evolution of Ag nanostructures created from thin films: UV–vis absorption and its theoretical predictions
PublicationAg-based plasmonic nanostructures were manufactured by thermal annealing of thin metallic films. Structure and morphology were studied using scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HR-TEM) and X-ray photoelectron spectroscopy (XPS). SEM images show that the formation of nanostructures is influenced by the initial layer thickness as well as the...
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Partial inhibition of borohydride hydrolysis using porous activated carbon as an effective method to improve the electrocatalytic activity of the DBFC anode
PublicationCarbon materials are commonly used catalyst supports in various types of fuel cells. Due to the possibility of designing their properties, they seem to be attractive and functional additives. In Direct Borohydride Fuel Cells (DBFCs), the electrooxidation reaction of borohydride competes with the undesirable hydrolysis reaction, therefore our work aimed to modify anodes based on a multi-component hydrogen storage alloy with a small...
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Ordered TiO2 nanotubes with improved photoactivity through self-organizing anodization with the addition of an ionic liquid: effects of the preparation conditions
PublicationModifying the geometric and surface parameters of oriented TiO2 nanotubes (NTs) is beneficial to the utilization of solar energy for chemical reactions, and this performance may be further improved. Thus, the effects of adding an ionic liquid (IL), 1-butylpiridinium chloride [BPy][Cl], and the effects of the water content and preparation conditions on the surface morphological, physicochemical, photocatalytic and photoelectrochemical...
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The Influence of Gas Mixture in the Glow-Discharge Nitriding Process of Austenitic Stainless Steel on Characteristic of Nitrided Cases
PublicationAustenitic stainless steels characterize with excellent corrosion resistance, although low mechanical properties. In many cases that limits their exploitation in industrial applications. Moreover, austenitic stainless steel is susceptible to local corrosion in the presence of halide ions. In present works, it was emphasized that the nitriding of austenitic stainless steels gives some potential abilities to obtain beneficial effect...
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Correlations of structural, thermal and electrical properties of sodium doped complex borophosphosilicate glass
PublicationBorophosphosilicate glasses with varying sodium ion concentrations were investigated for their, structural, thermal, and electrical properties. All the obtained glasses were transparent except the glass with the highest sodium content, which exhibited translucency due to inhomogeneities. Increasing sodium content led to reduced boron and silicon content while maintaining a constant B/Si ratio, indicating progressive depolymerization...
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Explainable machine learning for diffraction patterns
PublicationSerial crystallography experiments at X-ray free-electron laser facilities produce massive amounts of data but only a fraction of these data are useful for downstream analysis. Thus, it is essential to differentiate between acceptable and unacceptable data, generally known as ‘hit’ and ‘miss’, respectively. Image classification methods from artificial intelligence, or more specifically convolutional neural networks (CNNs), classify...
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Thin layer of ordered boron-doped TiO2 nanotubes fabricated in a novel type of electrolyte and characterized by remarkably improved photoactivity
PublicationThis paper reports a novel method of boron doped titania nanotube arrays preparation by electrochemical anodization in electrolyte containing boron precursor – boron trifluoride diethyl etherate (BF3 C4H10O), simultaneously acting as an anodizing agent. A pure, ordered TiO2 nanotubes array, as a reference sample, was also prepared in solution containing a standard etching compound: ammonium fluoride. The doped and pure titania...
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Direct amination of boron-doped diamond by plasma polymerized allylamine film
PublicationA novel microwave pulsed-plasma based method for the modification of the hydrogen-terminated polycrystalline boron-doped diamond (BDD) with a thin film of polymerized allylamine (PPAAm) is reported. A modified BDD surface is resistant to hydrolysis and delamination and is characterized by a high density of positively charged amino groups. Pulsed microwave plasma was applied to improve the degree of cross-linking and bonding of...
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Silica-Based Ionogels: Nanoconfined Ionic Liquid-Rich Fibers for Headspace Solid-Phase Microextraction Coupled with Gas Chromatography–Barrier Discharge Ionization Detection
PublicationIn this work, hybrid silica-based materials with immobilized ionic liquids (ILs) were prepared by sol–gel technology and evaluated as solid-phase microextraction (SPME) fiber coatings. High loadings of the IL 1-methyl-3-butylimidazolium bis(trifluoromethylsulfonyl)imide ([C4MIM][TFSI]) were confined within the hybrid network. Coatings composition and morphology were evaluated using scanning electron microscopy and energy dispersive...
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On the Structure and Volumetric Properties of Solvated Lanthanoid(III) Ions in Amide Solutions
PublicationThe coordination chemistry and the volumetric properties of three representative lanthanoid(III) ions lanthanum-(III), gadolinium(III), and lutetium(III) have been studied in three amide solvents with gradually increasing spatial demand upon coordination: N,N-dimethylformamide (dmf)
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Physical properties of homogeneous TiO2 films prepared by high power impulse magnetron sputtering as a function of crystallographic phase and nanostructure
PublicationOptical, photo-electrochemical, crystallographic and morphological properties of TiO2 thin films prepared by high power impulse magnetron sputtering at low substrate temperatures (<65 ◦C) without post-deposition thermal annealing are studied. The film composition-anatase, rutile or amorphous TiO2-is adjusted by the pressure (p ∼ 0.75-15 Pa) in the deposition chamber. The different crystallographic phases were determined with grazing...
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Preparation of platinum modified titanium dioxide nanoparticles with the use of laser ablation in water
PublicationWe report on the preparation method of nanocrystalline titanium dioxide modified with platinum by using nanosecond laser ablation in liquid (LAL). Titania in the form of anatase crystals has been prepared in a two-stage process. Initially, irradiation by laser beam of a titanium metal plate fixed in a glass container filled with deionized water was conducted. After that, the ablation process was continued, with the use of a platinum...
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Optimization of electrochemical doping approach resulting in highly photoactive iodine-doped titania nanotubes
PublicationThe paper focuses on the optimization procedure concerning the synthesis method resulting in highly ordered titania nanotubes doped with iodine atoms. The doping process was based on the electrochemical treatment of a titania nanotube layer immersed in a potassium iodide (KI) solution acting as an iodine precursor. A number of endeavors were undertaken in order to optimize the doping conditions. Electrolyte concentration, reaction...
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Structural analysis and physico-chemical characterization of mononuclear manganese(II) and polynuclear copper(II) complexes with pyridine-based alcohol
PublicationTwo novel manganese(II) and copper(II) complexes, mononuclear [Mn(H2O)2(2-(CH2)2OHpy)2](NO3)2 (1) and polynuclear [Cu(SO4)(2-(CH2)2OHpy)2]n (2), based on 2-(hydroxyethyl)pyridine (2-(CH2)2OHpy) were synthesised and fully characterised using X-ray structure analysis as well as spectroscopic, magnetic and thermal methods. Both central metal ions Mn(1) and Cu(1) are coordinated by two N,O-donor 2-(CH2)2OHpy ligands and possess an...
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Raman investigation of the patina layers on Hungarian copper ingots from a fifteenth century shipwreck
PublicationWe report results of the patina study of underwater archeological finding ofmedieval copper objects performed by means of the Raman and complementary spectroscopic techniques. The objects were found submerged in the sea as cargo part of the ship which sunk in the Gulf of Gdańsk in 1408. The excavated collection consists of 230 oval ingots of the size and mass up to about 60 cm and 18 kg (total of 2 tons), respectively. In the Raman...
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Phosphanylphosphido and phosphanylphosphinidene complexes of zirconium(IV) supported by bidentate N,N ligands
PublicationPhosphanylphosphido complexes of zirconium, [NacNacZrCl2(η2-R2P–PSiMe3)] (R = t-Bu, i-Pr), were synthesized in the reaction of R2P–P(SiMe3)Li·nTHF (R = t-Bu, i-Pr) with a β-diketiminate complex, [NacNacZrCl3], in toluene. Elimination of Me3SiCl from [NacNacZrCl2(η2-R2P–PSiMe3)] provided the phosphanylphosphinidene complexes [NacNacZrCl(η2-R2P–P)] (R = t-Bu, i-Pr). Moreover, the reaction of [NacNacZrCl2(η2-R2P–PSiMe3)] with R2P–P(SiMe3)Li·nTHF...
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Polyurethane Composite Scaffolds Modified with the Mixture of Gelatin and Hydroxyapatite Characterized by Improved Calcium Deposition
PublicationThe skeleton is a crucial element of the motion system in the human body, whose main function is to support and protect the soft tissues. Furthermore, the elements of the skeleton act as a storage place for minerals and participate in the production of red blood cells. The bone tissue includes the craniomaxillofacial bones, ribs, and spine. There are abundant reports in the literature indicating that the amount of treatments related...
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Core–shell excitation of isoxazole at the C, N, and O K-edges – an experimental NEXAFS and theoretical TD-DFT study
PublicationThe near-edge X-ray absorption fine structure (NEXAFS) spectra of the gas-phase isoxazole molecule have been measured by collecting total ion yields at the C, N, and O K-edges. The spectral structures have been interpreted using time-dependent density functional theory (TD-DFT) with the short-range corrected SRC2-BLYP exchange–correlation functional. Experimental and calculated energies of core excitations are generally in good...
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Exploring multi-step glucose oxidation kinetics at GOx-functionalized nanotextured gold surfaces with differential impedimetric technique
PublicationFor a few past years, we can observe the enormous growth of investigations related to ultrasensitive electrochemical sensors capable of reliable determination of important body parameters and analytes. Utilized procedures rely on standard electrochemical methods, demanding electrode polarization, and information about the initial characteristics of the working electrode. More and more complex electrode materials are characterized...
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POM/EVA Blends with Future Utility in Fused Deposition Modeling
PublicationPolyoxymethylene (POM) is one of the most popular thermoplastic polymers used in the industry. Therefore, the interest in its potential applications in rapid prototyping is understandable. Nevertheless, its low dimensional stability causes the warping of 3D prints, limiting its applications. This research aimed to evaluate the effects of POM modification with ethylene-vinyl acetate (EVA) (2.5, 5.0, and 7.5 wt.%) on its processing...
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Classification of submandibular salivary stones based on ultrastructural studies
PublicationIntroduction: Sialolithiasis remains a clinical problem with unclear etiopathogenesis, lack of prevention methods, and only surgical treatment. Materials and methods: An ultrastructure examination of submandibular sialoliths obtained from patients with chronic sialolithiasis was conducted using a scanning electron microscope and X-ray photoelectron...
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Electrochemical cobalt oxidation in chloride media
PublicationThe green transition, despite recent advances in cobalt-free battery technologies, is still highly dependent on the availability of critical cobalt-based materials. Consequently, there has been increasing interest towards the development of new methods that maximize critical metals recovery from industrial hydrometallurgical solutions. In the current study, direct anodic oxidation of cobalt species from cobalt chloride solutions...
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Mechanical Properties of Additively Manufactured Polymeric Materials—PLA and PETG—For Biomechanical Applications
PublicationThe study presented herein concerns the mechanical properties of two common polymers for potential biomedical applications, PLA and PETG, processed through fused filament fabrication (FFF)—Material Extrusion (ME). For the uniaxial tension tests carried out, two printing orientations—XY (Horizontal, H) and YZ (Vertical, V)—were considered according to the general principles for part positioning, coordinates, and orientation typically...
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Enhancing colloidal stability of nanodiamond via surface modification with dendritic molecules for optical sensing in physiological environments
PublicationPre-treatment of diamond surface in low-temperature plasma for oxygenation and in acids for carboxylation was hypothesized to promote the branching density of the hyperbranched glycidol polymer. This was expected to increase the homogeneity of the branching level and suppress interactions with proteins. As a result, composite nanodiamonds with reduced hydrodynamic diameters that are maintained in physiological environments were...
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Multi-Technique Investigation of Grave Robes from 17th and 18th Century Crypts Using Combined Spectroscopic, Spectrometric Techniques, and New-Generation Sequencing
PublicationThe textile fragments of the funeral clothes found in the 17th and 18th century crypts were subjected to spectroscopic, spectrometric, and microbial investigation. The next-generation sequencing enabled DNA identification of microorganisms at the genus and in five cases to the species level. The soft hydrofluoric acid extraction method was optimized to isolate different classes of dyes from samples that had direct contact with...
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The role of electrolysis and enzymatic hydrolysis treatment in the enhancement of the electrochemical properties of 3D-printed carbon black/poly(lactic acid) structures
PublicationAdditive manufacturing, also known as 3D printing, is beginning to play an unprecedented role in developing many applications for industrial or personalized products. The conductive composite structures require additional treatment to achieve an electroactive surface useful for electrochemical devices. In this paper, the surfaces of carbon black/poly(lactic acid) CB-PLA printouts were activated by electrolysis or enzymatic digestion...
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Modeling and optimization of chemical-treated torrefaction of wheat straw to improve energy density by response surface methodology
PublicationToday, torrefaction is important technique for extending the potential of biomass for improvement of energy density. The independent variables investigated for torrefaction study were temperature, retention time, acid concentration, and particle size. The experiment was designed by central composite design (CCD) method using design expert (version 11). The three dependent variables were higher heating value (HHV), energy enhancement...
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Polaronic and Mott insulating phase of layered magnetic vanadium trihalide VCl3
PublicationTwo-dimensional (2D) van der Waals (vdW) magnetic 3d-transition metal trihalides are a new class of functional materials showing exotic physical properties useful for spintronic and memory storage applications. In this article, we report the synthesis and electromagnetic characterization of single-crystalline vanadium trichloride, VCl 3 , a novel 2D layered vdW Mott insulator, which has a rhombohedral structure (R3, No. 148) at...
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BODIPY‐Perylene Charge Transfer Compounds; Sensitizers for Triplet‐Triplet Annihilation Up‐conversion
PublicationBODIPY heterochromophores, asymmetrically substituted with perylene and/or iodine at the 2 and 6 positions were prepared and investigated as sensitizers for triplet-triplet annihilation up conversion (TTA-UC). Single-crystal X-ray crystallographic analyses show that the torsion angle between BODIPY and perylene units lie between 73.54 and 74.51, though they are not orthogonal. Both compounds show intense, charge transfer absorption...
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Fabrication and characterization of composite TiO2 nanotubes/ boron-doped diamond electrodes towards enhanced supercapacitors
PublicationThe composite TiO2 nanotubes / boron-doped diamond electrodes were deposited using Microwave Plasma Enhanced Chemical Vapor Deposition resulting in the improved electrochemical performance. This composite electrode can deliver high specific capacitance of 7.46 mF cm‐− 2 comparing to boron-doped diamond (BDD) deposited onto flat Ti plate (0.11 mF cm‐− 2).The morphology and composition of composite electrode were characterized...
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Cadmium complex possessing simultaneously silanethiolato- and dithiocarbamato-ligands. A novel single-source precursor of cadmium sulfide
PublicationThermal decomposition of suitable coordination compounds may be used as efficient route for fabrication of semiconducting layers. A new potential CdS precursor—a cadmium complex with all-sulfur Cd-coordination sphere [Cd{l-SSi(OBut)3}(S2CNC4H8)]2 (1) —has been prepared and its properties are investigated. The complex was obtained in the reaction between dimeric bis(tri-tert-butoxysilanethiolato) cadmium(II) [Cd{SSi(OBut)3}2]2 and...
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Study of the formation of calcareous deposits on cathodically protected steel in Baltic sea water
PublicationPurpose – The purpose of this paper is to investigate whether the sedimentation of calcareous deposits occurs on cathodically protected steel in Baltic sea water. Design/methodology/approach – Steel electrodes were cathodically polarized in natural Baltic sea water at potential þ0.150 V vs Zn electrode in potentiostatic mode. During exposure chronoamperometric measurements were carried out. After the exposure, the electrode’s surface...