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Conducting polymers for biodegradable metallic implants
PublikacjaNowadays permanent metallic cardiovascular stents are long-term implants. The long-time presence of such an implant in human body can cause overgrowth of tissue within the treated portion of the vessel, blockage of the circulatory system and many other clinical complications, such as thrombosis, prolonged physical irritations or chronic inflammation. Therefore, in recent years, there is an interest to create biodegradable metallic...
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Synthesis of compounds with C-P-P and C=P-P bond systems based on the phospha-Wittig reaction
PublikacjaA reactivity study of a β-diketiminate titanium(III) phosphanylphosphido complex [MeNacNacTi(Cl){η2-P(SiMe3)-PtBu2}] (1) towards ketones such as benzophenone, 9-fluorenone, acetophenone, cyclopentanone, cyclohexanone and cycloheptanone is reported. The reactions of 1 with aromatic ketones (without α-protons) directly lead to the Ti(III) complex [MeNacNacTi(μ2-Cl)(OSiMe3)] (5) as well as Ti(IV) complexes with the pinacol condensation...
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Synthesis and characterization of cycloaliphatic hydrophilic polyurethanes, modified with l-ascorbic acid, as materials for soft tissue regeneration
PublikacjaIn this paper we described synthesis and characteristic of obtained hydrophilic polyurethanes (PURs) modified with ascorbic acid (commonly known as vitamin C). Such materials may find an application in the biomedical field, for example in the regenerative medicine of soft tissues, according to ascorbic acid wide influence on tissue regeneration Flora (2009), Szymańska-Pasternak et al. (2011), Taikarimi and Ibrahim (2011), Myrvik...
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Strontium-based nanosized phosphates as anticorrosive fi llers of epoxy and polyurethane coating compositions
PublikacjaAnticorrosive epoxy and polyurethane coatings were compounded using zinc-free nanosized phosphates of strontium (SP) or strontium and aluminum (SAP). For comparison, a nanosized calcium aluminum ammonium phosphate (CAP) and a microsized zinc phosphate (ZP) were tested. Results of salts spray and cyclic corrosion tests revealed better anticorrosive properties of the SAP-based coatings...
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Partial characterization of three Korean white lotus cultivars
PublikacjaThe nutritional and bioactive values of Korean white lotus cultivars (Muan, Chungyang, and Garam)extracted with methanol, water, and acetone solvents were evaluated by the contents of their bioactive compounds and antioxidant activity determined by ABTS, CUPRAC, FRAP, DPPH, and β-carotene-linoleic acid assays. HPLC, fluorometry, and FTIR spectroscopy were employed for evaluation of polyphenols and fatty acids. All lotus cultivar...
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Propensity of salicylamide and ethenzamide cocrystallization with aromatic carboxylic acids
PublikacjaThe cocrystallization of salicylamide (2-hydroxybenzamide, SMD) and ethenzamide (2-ethoxybenzamide, EMD) with aromatic carboxylic acids was examined both experimentally and theoretically. The supramolecular synthesis taking advantage of the droplet evaporative crystallization (DEC) technique was combined with powder diffraction and vibrational spectroscopy as the analytical tools. This led to identification of eleven new cocrystals...
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Optical and chemical characterization of thin TiNx films deposited by DC-magnetron sputtering
PublikacjaThin titanium nitride (tinx) films were deposited on silicon substrates by means of a reactive dc-magnetron plasma. Layers were synthesized under various conditions of discharge power and nitrogen flows in two operation modes of the magnetron (the so-called "balanced" and "unbalanced" modes). The optical constants of the tinx films were investigated by spectroscopic ellipsometry (se). X-ray photoelectron spectroscopy (xps) was...
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Local properties of organic coatings close to glass transition temperature
PublikacjaAcrylic coating applied on copper substrate has been investigated at different temperatures starting from the ambient one up to the level above the glass transition temperature. Its local topographic and electric properties have been examined with the atomic force microscopy (AFM) based approach including dc current mapping and local impedance spectroscopy. The local findings have been compared with the information from global...
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Transparent thin films of Cu-TiO2 with visible light photocatalytic acitivity
PublikacjaThin films of Cu–TiO2 with a high level of transparency were prepared by a dip-coating procedure on the glass surface. CuCl2 was used as a copper precursor added during sol – gel synthesis of TiO2. The extension of optical absorption into the visible region of as-prepared thin films was indicated by UV/Vis spectroscopy. Only the anatase phase was detected by X-ray di ffraction analysis (XRD). The presence of copper in the structure...
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Enhanced Electrochemical Performance of MnCo1.5Fe0.5O4Spinel for Oxygen Evolution Reaction through Heat Treatment
PublikacjaMnCo1.5Fe0.5O4 spinel oxide was synthesized using the sol−gel technique, followed by heat treatment at various temperatures (400, 600, 800, and 1000 °C). The prepared materials were examined as anode electrocatalysts for watersplitting systems in alkaline environments. Solid-state characterization methods, such as powder X-ray diffraction and X-ray absorption spectroscopy (XAS), were used to analyze the materials’ crystallographic...
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Effects of V2O5 Additive on Structure and Dielectric Properties of BiNbO4 Ceramics
PublikacjaGoal of the present research was to investigate the influence of V2O5 additive on the structure and dielectric properties of BiNbO4 ceramics. To fabricate BiNbO4 ceramics with V2O5 added the solid state reaction route and pressureless sintering was utilized. Thus obtained ceramics was characterized in terms of its microstructure (SEM), chemical composition (EDS), phase composition and crystalline structure (X-ray phase and structural...
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Novel cast polyetherurethanes based on dispersed polymeric polyols
PublikacjaOur study was focused on obtaining polyetherurethanes synthesized with using polymeric polyether based polyols differing in dispersed copolymer content (10, 20 and 40 wt%). The polyetherurethane materials were synthesized via two step method. The influence of different polymeric polyether based polyols on the chemical structure, morphology, mechanical and thermal properties of the obtained polyetherurethanes was investigated. The...
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Advances in mass spectrometry for iron speciation in plants
PublikacjaIron is an important nutrient essential for plants and critical for human health. The state-of-the art of methods for iron speciation in cereal grains and plant fluids is critically reviewed. Particular attention is given to the latest developments in the coupling of HPLC with the parallel ICP MS and electrospray ionization (ESI) MS/MS detection, usually QTOF MS or Q-Orbitrap MS, for the identification and quantification of iron...
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Reduced Graphene Oxide Joins Graphene Oxide To Teach Undergraduate Students Core Chemistry and Nanotechnology Concepts
PublikacjaNovel carbon nanomaterials such as reduced graphene oxide (rGO) and graphene oxide (GO) can be easily incorporated into the undergraduate curriculum to discuss basic chemistry and nanotechnology concepts. This paper describes a laboratory experiment designed to study the differences between GO and rGO regarding their physico-chemical properties (e.g. color, hydrophobicity, type of functional groups, electrical conductivity etc.)....
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Wykorzystanie fourierowskiej spektroskopii w podczerwieni do badania stężenia gazów wylotowych z tlenkowego ogniwa paliwowego zasilanego biogazem
PublikacjaW dzisiejszych czasach bardzo ważne jest pozyskiwanie energii ze źródeł odnawialnych i bezpiecznych dla środowiska. Jedną z obiecujących technologii są tlenkowe ogniwa paliwowe (ang. Solid Oxide Fuel Cell, SOFC). Stanowią one bezpieczną i ekologiczną alternatywę dla energii uzyskanej z paliw kopalnych. SOFC charakteryzuje się sprawnością energetyczną na poziomie 45-60 %, podczas gdy sprawność klasycznych elektrowni cieplnych nie...
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Influence of chemical structure on physicochemical properties and thermal decomposition of the fully bio-based poly(propylene succinate-co-butylene succinate)s
PublikacjaIn this work, two polyesters and four copolyesters were studied. All materials were synthesized to obtain the monomers dedicated for thermoplastic polyurethane elastomers. For this type of PUR, the monomers should characterize by appropriate selected physicochemical properties and macromolecular structure distribution, which depends on synthesis conditions. The study of chemical structure with extensive and knowledgeable analysis...
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Time evolution of Electrochemical Impedance spectra of cathodically protected steel in artificial seawater
PublikacjaUsability of Electrochemical Impedance Spectroscopy data for better cathodic protection control was investigated. Carbon steel – S235JR2 grade specimen were exposed in artificial seawater environment. Samples were polarized and their potentials corresponded to four different cathodic protection degrees. Time evolution of Electrochemical Impedance spectra was investigated. Goodness of fit function (X2) was analysed in terms of proper...
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Arbutin: Isolation, X-ray structure and computional studies
PublikacjaArbutin, an active component originated from Serratula quinquefolia for skin-whitening use and treating skin related allergic inflammation, was characterized by microanalysis, FTIR, UV-Vis, multinuclear NMR spectroscopy, and single crystal X-ray diffraction method. The geometries of the studied compound were optimized in singlet states using the density functional theory (DFT) method with B3LYP functional. Electronic spectra were...
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Thickness and structure change of titanium (IV) oxide thin films synthesized by the sol–gel spin coating method
PublikacjaTitanium dioxide is a well-known material in nanotechnology, while it provides new opportunities due to its interesting properties, for example, as a semiconductor with a quite significant forbidden band gap energy of 3.2 eV. In this study, thin films of titanium dioxide (TiO2) were synthesized in amorphous and crystallographic systems using the sol–gel process. Atomic Force Microscopy (AFM), Raman spectroscopy and X-ray diffraction...
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Electrochemical and photoelectrochemical characterization of photoanodes based on titania nanotubes modified by a BiVO4 thin film and gold nanoparticles
PublikacjaTitania nanotubes (TNT) modified with thin films of bismuth vanadate (BiVO4) and gold nanoparticles (GNP) were photoelectrochemically characterized as photoanodes for water photooxidation. Presence of bismuth vanadate enhanced efficiency of photocurrent generation in comparison with pristine TNTs under visible light illumination. Besides an extended range of absorbed light, the presence of both BiVO4 and GNP reduced the charge...
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Portable Raman spectrometer - design rules and applications
PublikacjaRaman spectroscopy has become more popular due to its new prospective field applications in forensic sciences, war against terrorism, environment protection and other field chemical analysis. Raman spectrometers can be miniaturised to portable devices and their price is decreasing due to development of optoelectronics components. Unfortunately, this technology has still numerous limitations that influence their design and limit...
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Superexcited states in the vacuum-ultraviolet photofragmentation of isoxazole molecules
PublikacjaThe photofragmentation of isoxazole molecules producing excited atomic and molecular fragments has been investigated over the energy range 16-50 eV, using photon-induced fluorescence spectroscopy. The following fragments have been identified by their fluorescence: the excited hydrogen atoms H(n), n = 3-7 and the diatomic CH(A2Δ, B2Σ−), CN(B2Σ+) and C2(d3Πg) fragments. The diatomic fragments are vibrationally and highly rotationally...
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Chromogenic amides of pyridine-2,6-dicarboxylic acid as anion receptors
PublikacjaThe synthesis of simple, chromogenic pyridine-2,6-dicarboxylic acid amides, derivates of isomeric nitroanilines and aminonitrophenols, and their ion binding properties are described. The ligands' response to ionic species was examined by naked eye and was studied with the use of UV-Vis spectroscopy in DMSO and its mixture with water. The effect of the localisation and the type of the substituents in aromatic rings were discussed....
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Selective detection of F- by chromogenic tetrazole receptor
PublikacjaA chromogenic anion host 4, containing two amide functionalities linked to azo dye and tetrazole rings was synthesized and its complexes with various anions were investigated. The results show that receptor 4 can recognize selectively biologically important F- ion. The binding affinity for F- was investigated by naked-eye colour change, UV-Vis and 1H NMR spectroscopy. Addition F- ion in CH3CN and DMSO to receptor 4 cause a colour...
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Comparison of the coordination geometries of Zn(II) and Cd(II) ions in complexes with water, methanol and bulky aryloxysilanethiolate ligands
PublikacjaZinc and cadmium complexes containing silanethiolate anions and methanol or water were synthesized and characterized by X-ray diffraction, FT-IR and NMR spectroscopy, and DFT calculations. Contrary to zinc, the cadmium ion utilizes very weak donors to complete its coordination sphere; it forms contacts to phenyl rings of the silanethiolate ligand. Two zinc analogs of the general formula [Zn{SSi(OAr)3}2(L)2] where L = CH3OH (2)...
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Site-selective magnetic order of neptunium inNp2Ni17
PublikacjaWe present the results obtained by superconducting quantum interference device (SQUID) magnetometry, specific heat, and Mossbauer spectroscopy measurements carried out on Np2Ni17 polycrystalline samples. We show that long-range magnetic order, with a moment mu((2b)) similar to 2.25 mu(B), occurs below T-N = 17.5 K on the Np (2b) sites. A nontrivial situation is observed in that the other Np sites (2d) do not take part to the order...
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Spray deposited carbon nanotubes counter electrodes for dye-sensitized solar cells
PublikacjaCarbon nanotubes due to their catalytic properties are a promising alternative to platinum counter electrodes (CE) for dye-sensitized solar cells (DSSC). In this study, counter electrodes were made from double-walled carbon nanotube (DWCNT) ink using the spray printing technique and afterwards thermally treated at temperatures ranging from 120 to 300 °C. Morphology and structure was studied using scanning electron microscopy and...
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Spray-deposited carbon-nanotube counter-electrodes for dye-sensitized solar cells
PublikacjaCarbon nanotubes due to their catalytic properties are a promising alternative to platinum counter electrodes (CE) for dye-sensitized solar cells (DSSC). In this study, counter electrodes were made from double-walled carbon nanotube (DWCNT) ink using the spray printing technique and afterwards they were thermally treated at temperatures ranging from 120 to 300 °C. Morphology and structure was studied using scanning electron microscopy...
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Few-Layer Black Phosphorus/Chitosan Nanocomposite Electrodes via Controlled Electrodeposition for Enhanced Electrochemical Kinetic Performance
PublikacjaThis study presents the preparation and characterization of few-layer black phosphorus (FLBP) chitosan electrodes by controlled electrochemical deposition of chitosan nanoparticles on FLBP-modified glassy carbon electrodes. FLBP was prepared by solvent-assisted exfoliation of bulk BP and was further modified with chitosan forming together a nanocomposite, including easy cross-linking with nanomaterials and film-forming properties....
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Reactivity of bulky aminophosphanes towards small molecules: Activation of dihydrogen and carbon dioxide by aminophosphane/borane frustrated Lewis pairs
PublikacjaA series of mono- and bisaminophosphanes with formulas R2NPR’R’’ and (R2N)2PR’ (R = iPr, Cy; R’ = Ph, Cy; R’’ = iPr) were characterized by X-ray analysis, NMR spectroscopy and computational methods. The common structural futures of these species are short and polarized PAN bonds, a pyramidal geometry at the P atom and an almost planar geometry at the N atoms. According to DFT calculations, these...
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Polynomial analysis as a new way of describing dynamic impedance spectra – Differential and relative impedance spectra
PublikacjaModel measurements of an equivalent electrical system were carried out using the technique of Dynamic Electrochemical Impedance Spectroscopy. The measurement took the form of potentiodynamic changes imposed on the tested system. Using the possibility of continuous impedance measurements, an attempt was made to develop an original and innovative method of analyzing impedance spectrograms, which is termed polynomial analysis. As...
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Synthesis of Phosphonated Carbon Nanotubes: New Insight into Carbon Nanotubes Functionalization
PublikacjaCarbon nanotubes were successfully functionalized for the first time in a free radical phosphonylation reaction. Three synthetic protocols were proposed. Carbon nanotubes and diethylphosphite reacted in the presence of known radical initiator, such as azobisisobutyronitrile, single electron oxidant—Mn(OAc)3, or under UV radiation. The functionalized material was fully characterized by means of spectroscopic methods, together with...
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Polynomial description of dynamic impedance spectrogram—introduction to a new impedance analysis method
PublikacjaThis paper presents a polynomial description of spectrograms obtained using Dynamic Electrochemical Impedance Spectroscopy. A method to fit the polynomial degree correctly is discussed. A simple electrical system of a diode connected in parallel with a capacitor was used for testing. Dynamic impedance measurements during potentiodynamic polarization were conducted. This paper presents an alternative analysis method that allows...
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The Influence of Thin Gold Electrodes on the High-Temperature Impedance of Oxide Glasses
PublikacjaThe influence of thin gold electrodes on the electrical measurements of glasses at high temperatures was studied using impedance spectroscopy. The impedance was measured several times over a wide frequency range from 10 mHz to 1 MHz and the temperature ranged from 213 to 673 K under air and nitrogen atmospheres. The results showed a drop in the conductivity of more than an order of magnitude at a temperature around 603 K during...
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Hybrid cross-linked chitosan/protonated-proline:glucose DES membranes with superior pervaporation performance for ethanol dehydration
PublikacjaThis work explores a protonated L-proline:glucose (molar ratio 5:1) deep eutectic solvent (DES) in fabricating biopolymer membranes utilizing chitosan (CS). Initially, the miscibility of CS and DES to prepare homogeneous dense blend membranes has been investigated. Different techniques, such as scanning electron microscopy, contact angle (CA), atomic force microscopy (AFM), Fourier transformed infrared spectroscopy (FTIR) and swelling...
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Hydrogen Production Mechanism in Low-Temperature Methanol Decomposition Catalyzed by Ni3Sn4 Intermetallic Compound: A Combined Operando and Density Functional Theory Investigation
PublikacjaHydrogen production from methanol decomposition to syngas (H2 + CO) is a promising alternative route for clean energy transition. One major challenge is related to the quest for stable, cost-effective, and selective catalysts operating below 400 °C. We illustrate an investigation of the surface reactivity of a Ni3Sn4 catalyst working at 250 °C, by combining density functional theory, operando X-ray absorption spectroscopy, and high-resolution...
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Influence of controlled crystallization and SrF2 content on the structure and properties of Eu3+ doped phosphate glasses
PublikacjaNew phosphate glasses and glass-ceramics P2O5–Bi2O3–K2O–Nb2O5-SrF2 doped with Eu were synthesized and studied in this work. The influence of the SrF2 content (0–15 mol%) and the parameters of the heat treatment on their structural and optical properties were investigated. For the above purpose, the structural characterization by FTIR spectroscopy and XRD measurements was carried out, which showed a significant effect of SrF2 on...
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Classification and fingerprinting of kiwi and pomelo fruits by multivariate analysis of chromatographic and spectroscopic data
PublikacjaThe fingerprinting capacity of two analytical techniques, HPLC and UV-Vis spectroscopy in the case of fruits samples (kiwi and pomelo) has been investigated. The multivariate exploratory techniques were used for sample discrimination according to the fruit species and subspecies. The combination of principal component analysis with linear discriminant analysis is opening new directions in the fingerprinting analysis. The classifications...
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Development of Microstructured Carbon Coatings by Substrate-Catalytic CVD
PublikacjaCarbon nanostructured films were synthesized by chemical vapor deposition (CVD) on H18 stainless steel (AISI 440C) sheets with an H2/CH4/N2 gas mixture at various substrate temperatures. During the synthesis, the iron and chromium oxide layer was formed between the steel and carbonaceous layer. The carbon films exhibited wall-like and spherical morphologies and structures, as characterized by scanning electron microscopy and Raman...
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Structural and catalytic properties of ceria layers doped with transition metals for SOFCs fueled by biogas
PublikacjaThe aim of this paper was to investigate an influence of the nanocrystalline Ce0.8A0.2O2-δ (A = Mn, Fe, Co, Ni, Cu) materials on the direct internal reforming of biogas in SOFC. Structural analysis of fabricated compounds has been done. An in-situ analysis of a composition of outlet gases from operating SOFC was performed using FTIR spectroscopy with simultaneous electrical tests. It was found out, that type of dopant strongly...
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The effect of morphology and crystalline structure of Mo/MoO3 layers on photocatalytic degradation of water organic pollutants
PublikacjaMolybdenum oxide layers were formed by anodization of the Mo metallic foil in a water/ethylene glycol-based electrolyte containing fluoride ions. The as-prepared, amorphous samples were annealed in air at different temperatures in a range from 100 �C to 700 �C. The crystal phase and morphology of anodized and annealed MoO3 layers were investigated using X-ray diffraction, Raman spectroscopy, and scanning electron microscopy. The...
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Highly Oriented Zirconium Nitride and Oxynitride Coatings Deposited via High‐Power Impulse Magnetron Sputtering: Crystal‐Facet‐Driven Corrosion Behavior in Domestic Wastewater
PublikacjaHerein, highly crystalline ZrxNy and ZrxNyOz coatings are achieved by the deposition via high‐power impulse magnetron sputtering. Various N2 and N2/O2 gas mixtures with argon are investigated. The chemical composition and, as a result, mechanical properties of the deposited layer can be tailored along with morphological and crystallographic structural changes. The corrosion resistance behavior is studied by potentiodynamic measurements...
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Silicon Oxycarbide-Graphite Electrodes for High-Power Energy Storage Devices
PublikacjaHerein we present a study on polymer-derived silicon oxycarbide (SiOC)/graphite composites for a potential application as an electrode in high power energy storage devices, such as Lithium-Ion Capacitor (LIC). The composites were processed using high power ultrasound-assisted sol-gel synthesis followed by pyrolysis. The intensive sonication enhances gelation and drying process, improving the homogenous distribution of the graphitic...
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High-Temperature Structural and Electrical Properties of BaLnCo2O6 Positrodes
PublikacjaThe application of double perovskite cobaltites BaLnCo2O6−δ (Ln = lanthanide element) in electrochemical devices for energy conversion requires control of their properties at operating conditions. This work presents a study of a series of BaLnCo2O6−δ (Ln = La, Pr, Nd) with a focus on the evolution of structural and electrical properties with temperature. Symmetry, oxygen non-stoichiometry, and cobalt valence state have been examined...
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Copper-based 2D-coordination polymer as catalyst for allylation of aldehydes
PublikacjaA copper-tartrate, [Cu2(Tart)2(H2O)2]·4H2O, was synthesized at room temperature in aqueous media using copper chloride and D-tartaric acid. The compound crystallizes in the monoclinic system P21 space group and was characterized by infrared spectroscopy, thermogravimetry, X-ray powder diffraction and the results are in good agreement with the single crystal...
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Synthesis, structural and spectroscopic properties of asymmetric schiff bases derived from 2,3-diaminopyridine
PublikacjaTwo Schiff base derivatives, 4-(2-amino-3-pyridyliminomethyl)phenol (I) and 3-(2-amino-3- pyridyliminomethyl)nitrobenzene (II ), were synthesised and characterised by spectroscopy. The structure of I was determined by single crystal X-ray diffraction studies. The asymmetric Schiff base derived from 2,3-diaminopyridine selectively recognise transition and heavy metal cations, and some anion. Ligands I and II form stable complexes...
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Phase separation in poly(butylene terephthalate)-based materials prepared by solid-state modification
PublikacjaThe morphology of a series of poly(butylene terephthalate) (PBT)/fatty acid dimer diol (FADD)-based copolyesters prepared by solid-state modi fi cation (SSM) was studied. It was shown that in copolyesters containing less than 10 wt% FADD two different phases, i.e. a PBT crystalline phase and a PBT-rich amorphous phase, are present. The FADD residues were more or less homogeneously distributed throughout the interlamellar regions....
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Ultrafast Intramolecular Relaxation and Wave-Packet Motion in a Ruthenium-Based Supramolecular Photocatalyst
PublikacjaThe hydrogen-evolving photocatalyst [(tbbpy)2 Ru(tpphz)Pd(Cl)2 ](2+) (tbbpy=4,4'-di-tert-butyl-2,2'-bipyridine, tpphz=tetrapyrido[3,2-a:2',3'-c:3'',2''-h:2''',3'''-j]phenazine) shows excitation-wavelength-dependent catalytic activity, which has been correlated to the localization of the initial excitation within the coordination sphere. In this contribution the excitation-wavelength dependence of the early excited-state relaxation...
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Photophysics of Ru(II) Dyads Derived from Pyrenyl-Substitued Imidazo[4,5-f][1,10]phenanthroline Ligands.
PublikacjaThe photophysics of a series of Ru(II) dyads based on the 2-(1-pyrenyl)-1H-imidazo[4,5-f][1,10]-phenanthroline ligand was investigated. The ability of these metal complexes to intercalate DNA and induce cell death upon photoactivation makes them attractive photosensitizers for a range of photobiological applications, including photodynamic therapy. In the present study, time-resolved transient absorption and emission spectroscopy...
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Influence of reactive oxygen species during deposition of iron oxide films by high power impulse magnetron sputtering.
PublikacjaIron oxide films were deposited using high power impulse magnetron sputtering (HiPIMS) of an iron cathode in an argon/oxygen gas mixture at different gas pressures (0.5~Pa, 1.5~Pa, and 5.0~Pa). The HiPIMS system was operated at a repetition frequency $f = 100$~Hz with a duty cycle of 1~\%. A main goal is a comparison of film growth during conventional and electron cyclotron wave resonance-assisted HiPIMS. The deposition plasma...