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Preparation and characterisation of solution-cast Nafion membrane
PublicationNafion is a commercial name for a perfluorosulfonic polymer, which has been developed in 1962 by Dupont de Nemours. This polymer consists of a polytetrafluoroethylene backbone and regular spaced long perfluorovinyl ether pendant side chains terminated by a sulfonate ionic group. These sulfonate groups are responsible for cation-exchange properties of Nafion. Thanks to the ion-exchange properties, water permeability, good chemical,...
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Valence and Ionic Lowest-Lying Electronic States of Isobutyl Formate Studied by High-Resolution Vacuum Ultraviolet Photoabsorption, Photoelectron Spectroscopy, and Ab Initio Calculations
PublicationThe highest resolution vacuum ultraviolet photoabsorption spectrum of isobutyl formate, C5H10O2, yet reported is presented over the energy range 4.5−10.7 eV (275.5−118.0 nm) revealing several new spectral features. Valence and Rydberg transitions and their associated vibronic series observed in the photoabsorption spectrum have been assigned in accordance with new ab initio calculations of the vertical excitation energies and oscillator...
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Morphology control through the synthesis of metal-organic frameworks
PublicationDesignable morphology and predictable properties are the most challenging goals in material engineering. Features such as shape, size, porosity, agglomeration ratio significantly affect the final properties of metal- organic frameworks (MOFs) and can be regulated throughout synthesis parameters but require a deep under- standing of the mechanisms of MOFs formation. Herein, we systematically summarize the effects of the indi- vidual...
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Multi-state multi-reference Møller-Plesset second-order perturbation theory for molecular calculations
PublicationThis work presents multi‐state multi‐reference Møller–Plesset second‐order perturbation theory as a variant of multi‐reference perturbation theory to treat electron correlation in molecules. An effective Hamiltonian is constructed from the first‐order wave operator to treat several strongly interacting electronic states simultaneously. The wave operator is obtained by solving the generalized Bloch equation within the first‐order...
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Linear and nonlinear impedance in iron oxide glasses containing alkaline ions and alkali free
PublicationThe linear and nonlinear impedance spectra of oxide glasses were measured in the frequency range of 1 mHz to 1 MHz and in the temperature range of 153K to 483K. Two groups of iron oxide glass samples were prepared, the first one containing alkaline ions and the second one without alkali. In the first group, compositions of glasses were as follows: (in %mol) 50% SiO2 , 25% PbO, 15% Fe2O3 and 15% one of alkaline oxides: Na2O, K2O,...
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Ionic conductivity behavior by activated hopping conductivity (AHC) of barium aluminoborosilicate glass–ceramic system designed for SOFC sealing
PublicationNon-conducting BaO-B2O3-Al2O3-SiO2 parent glasses designed for solid oxide fuel cell (SOFC) sealing applications were prepared using the melt-quenching technique. The glass formation region was determined according to phase equilibrium relations and was found to be in the composition range 70BaO-(x)Al2O3-(10−x)B2O3-20SiO2 where 3.0 < x < 6.0 wt%. The conductivity values obtained conductivity ranged from 10−5 to 10−10 S/cm at temperatures...
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Electrical properties of Na2O-CaO-P2O5 glasses doped with SiO2 and Si3N4
PublicationSodium-calcium-phosphate glasses doped with SiO2 or Si3N4 having similar sodium ion concentrations were prepared by melt quenching. The conductivity was measured by impedance spectroscopy under nitrogen atmosphere in a wide frequency range (10 mHz–1 MHz) and wide temperature range (153–473 K). At 36.6 °C, DC conductivities of all glasses vary between 1.1 ∗ 10−12 and 8.9 ∗ 10−12 S cm−1 and have similar activation energies (between...
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Effect of choline chloride based natural deep eutectic solvents on aqueous solubility and thermodynamic properties of acetaminophen
PublicationIn this work, natural deep eutectic solvents (NADESs) containing choline chloride as hydrogen bond acceptor and 1,2-propanediol, malic acid and tartaric acid as hydrogen bond donors have been synthesized and applied to enhance the aqueous solubility of model sparingly water-soluble drug – acetaminophen. The results indicate that the greatest impact on the solubility of acetaminophen have deep eutectic solvents based on 1,2-propanediol...
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SrCe0.9In0.1O3-δ-based reversible symmetrical Protonic Ceramic Cell
PublicationIn-doped SrCe0.9In0.1O3-δ (SCI) perovskite-type oxide is utilized as the solid electrolyte, as well as a component, together with SrFe0.75Mo0.25O3-δ (SFM) compound, in the composite-type electrodes to construct symmetrical Protonic Ceramic Fuel Cells (PCFC). With good mutual stability of SCI and SFM at high temperatures in water vapor-containing reducing and oxidizing conditions, as well as sufficient ionic conductivity with high...
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Study of oxygen electrode reactions on symmetrical porous SrTi0.30Fe0.70O3-δ electrodes on Ce0.8Gd0.2O1.9 electrolyte at 800 °C–500 °C
PublicationIron doped strontium titanates (SrTi1-xFexO3-δ) are an interesting mixed ionic-electronic conductor model used to study basic oxygen reduction/oxidation reactions. In this work, we performed an impedance spectroscopy study on symmetrical porous SrTi0.30Fe0.70O3-δ (STF70) electrodes on a ceriabased electrolyte. The sample was measured in varying oxygen concentration: from 0.3% to 100% in 800 °C - 500 °C temperature range. Low polarisation...
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Influence of rhamnolipids and ionic cross-linking conditions on the mechanical properties of alginate hydrogels as a model bacterial biofilm
PublicationThe literature indicates the existence of a relationship between rhamnolipids and bacterial biofilm, as well as the ability of selected bacteria to produce rhamnolipids and alginate. However, the influence of biosurfactant molecules on the mechanical properties of biofilms are still not fully understood. The aim of this research is to determine the effect of rhamnolipids concentration, CaCl2 concentration, and ionic cross-linking...
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Cytocompatibility of stabilized black phosphorus nanosheets tailored by directly conjugated polymeric micelles for human breast cancer therapy
PublicationThe novel procedure of few-layer black phosphorus (FLBP) stabilization and functionalisation was here proposed. The cationic polymer PLL and non-ionic PEG have been involved into encapsulation of FLBP to allow sufficient time for further nanofabrication process and overcome environmental degradation. Two different spacer chemistry was designed to bind polymers to tumor-homing peptides. The efficiency of functionalisation was examined...
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Enhanced Mechanical and Electromechanical Properties of Compositionally Complex Zirconia Zr1–x(Gd1/5Pr1/5Nd1/5Sm1/5Y1/5)xO2−δ Ceramics
PublicationCompositionally complex oxides (CCOs) or high-entropy oxides (HEOs) are new multi-element oxides with unexplored physical and functional properties. In this work, we report fluorite structure derived compositionally complex zirconia with composition Zr1- x(Gd1/5Pr1/5Nd1/5Sm1/5Y1/5)xO2-δ (x = 0.1 and 0.2) synthesized in solid-state reaction route and sintered via hot pressing at 1350 °C. We explore the evolution of these oxides'...
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O 1s excitation and ionization processes in the CO2 molecule studied via detection of low-energy fluorescence emission
PublicationOxygen 1s excitation and ionization processes in the CO2 molecule have been studied with dispersed and non-dispersed fluorescence spectroscopy as well as with the vacuum ultraviolet (VUV) photon-photoion coincidence technique. The intensity of the neutral O emission line at 845 nm shows particular sensitivity to core-to-Rydberg excitations and core-valence double excitations, while shape resonances are suppressed. In contrast,...
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INNOVATIVE THERMODYNAMICAL CYCLES BASED ON ENHANCEMENT MASS, MOMENTUM, ENTROPY AND ELECTRICITY TRANSPORT DUE TO SLIP, MOBILITY, TRANSPIRATION, ENTROPY AND ELECTRIC JUMPS AS WELL AS OTHER NANO-FLOWS PHENOMENA
PublicationIn our work, a further development of the authors model of thermo-chemical flow of fuel, air, oxygen, steam water, species, ionic and electron currents within nano channels and nano-structures of novel devices is presented. Different transport enhancement models are taken into account -among them the most important are: the velocity slip connected with complex external friction, the Darcy mobility and the Reynolds transpiration....
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Collision Strengths of Astrophysical Interest for Multiply Charged Ions
PublicationThe electron impact excitation and ionization processes are crucial for modeling the spectra of different astrophysical objects, from atmospheres of late-type stars to remnants of supernovae and up to the light emission from neutron star mergers, to name just a few. Despite their signifi- cance, however, little is known quantitatively about these processes for low- and medium-impact energies of, say, Ekin . 5000 eV of the free...
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Anion–water interactions of weakly hydrated anions: molecular dynamics simulations of aqueous NaBF4 and NaPF6
PublicationIn aqueous ionic solutions, both the structure and the dynamics of water are altered dramatically with respect to the pure solvent. The emergence of novel experimental techniques makes these changes accessible to detailed investigations. At the same time, computational studies deliver unique possibilities for the interpretation of the experimental data at the molecular level. Here, using molecular dynamics simulations, we demonstrate...
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Toxicity and chemical analyses of airport runoff waters in Poland
PublicationThe aim of this study was to assess the ecotoxicological effects of various compounds in complex airport effluents using a chemical and ecotoxicological integrated strategy. The present work deals with the determination of sum of PCBs, PAHs, pesticides, cations, anions, phenols, anionic, cationic, non-ionic detergents, formaldehyde and metals – as well as TOC and conductivity – in runoff water samples collected from 2009 to 2011...
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A simple route of providing a soft interface for PEDOT: PSS film metallic electrodes without loss of their electrical interface parameters
PublicationThe work presents the development of a soft interface at PEDOT:PSS film without changing its electrical interface parameters. In the first step, PEDOT:PSS is electrodeposited on the commercial platinum electrode under the state-of-the-art conditions desirable for different electrochemical electrodes. Secondly, a pure hydrogel layer is deposited on the top of the electrodeposited PEDOT:PSS film under conditions that provide desirable...
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Surface active fatty acid ILs: Influence of the hydrophobic tail and/or theimidazolium hydroxyl functionalization on aggregates formation
PublicationNine structurally-related fatty acid ionic liquids have been prepared and their thermal behavior as well as their ability to self-assemble in water has been investigated. The thermal properties were studied by thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC), while the aggregation behavior was analyzed by tensiometry, isothermal titration calorimetry (ITC), conductometry, dynamic light scattering (DLS),...
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Tailoring structural properties of lanthanum orthoniobates through an isovalent substitution on the Nb-site
PublicationTetragonal polymorph of lanthanum orthoniobate can be stabilized to room temperature by the substitution of Nb with an isovalent element. LaNb1-xAsxO4 (0 < x ≤ 0.3), where As is an element stabilizing tetragonal structure, were successfully synthesized with combined co-precipitation and solid-state reaction method. The phase transition temperature, above which the material has tetragonal structure, decreases linearly with increasing...
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Betaine and L-carnitine ester bromides: Synthesis and comparative study of their thermal behaviour and surface activity
PublicationSix esters of both betaine and L-carnitine bromides, featuring alkyl groups ranging from C8 to C18 in length, have been synthesized. The thermal behaviour of these twelve bio-based salts has been analyzed and compared by thermal gravimetric analysis and differential scanning calorimetry. The L-carnitine alkyl ester bromides melted below 100 C and can hence be considered ionic liquids (ILs) with full rights. Conversely, the betaine...
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Physical and sealing properties of BaO–Al2O3–SiO2–CaO–V2O5 glasses for solid oxide fuel cell applications
PublicationIn this study, the properties of BaO–Al2O3–SiO2 (SAB) glasses incorporated with CaO and V2O5 as the network modifier and additive, respectively, are evaluated. The electrical resistivities of the glasses decrease upon the addition of CaO but increase upon increasing their V2O5 content because the V5+ species lower the ionic mobility of the glasses. The addition of V2O5 improves the wettability of the glasses on the Crofer 22 APU...
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Synthesis and Characterization of Poly(zwitterionic) Structures for Energy Conversion and Storage
PublicationZwitterions are unique class of molecules that possess two functional groups bearing electric charges, one positive and second negative. This setup results in peculiar properties such as high water retention and anti-fouling capability. Therefore, zwitterionic coatings and gels are commonly applied in e.g. biosensing and bioelectronic devices. Despite those applications, there are other perspectives for zwitterionic materials....
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Albumin–Hyaluronan Interactions: Influence of Ionic Composition Probed by Molecular Dynamics
PublicationThe lubrication mechanism in synovial fluid and joints is not yet fully understood. Nevertheless, intermolecular interactions between various neutral and ionic species including large macromolecular systems and simple inorganic ions are the key to understanding the excellent lubrication performance. An important tool for characterizing the intermolecular forces and their structural consequences is molecular dynamics. Albumin...
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Manifestation of Intermolecular Interactions in the IR Spectra of 2- and 4-Methylmethcathinones Hydrochlorides: DFT Study and Hirshfeld Surfaces Analysis
PublicationThis paper reports a Hirshfeld surfaces analysis of crystalline 2- and 4-methylmethcathinone (2-MMC and 4-MMC) hydrochlorides to analyze NH∙Cl and CH∙∙∙Cl intermolecular interactions and approve the formation of the NН2+–Cl– salt fragment in both 2-MMC∙HCl and 4-MMC∙HCl crystals. Two isomeric dimers were separated from the corresponding crystal packing to model IR spectra of the crystalline 2-MMC∙HCl...
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Effect of alkyl sulfate on the phase behavior of microemulsions stabilized with monoacylglycerols
PublicationIn this study the effect of an anionic surfactant (sodium dodecyl sulfate SDS) and oils (hydrocarbons: C12-C16) on the formation and phase behavior of the systems of oil/monoacylglycerols (MAG):SDS/propylene glycol/water has been investigated. The effects of the surfactant mixture on the phase behavior and the concentrationof water or oil in the systems were studied at three temperatures (50, 55, 60 C). Electrical conductivity...
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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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Effects of thermal history on the performance of low-temperature solid oxide fuel cells with Sm0.2Ce0.8O2-δ electrolyte and LiNi0.81Co0.15Al0.04O2 electrodes
PublicationIn this study, low-temperature solid oxide fuel cells with an ∼560 μm thick Sm0.2Ce0.8O2−δ (SDC) electrolyte and ∼890 μm thick LiNi0.81Co0.15Al0.04O2−δ (NCAL) electrodes are constructed and characterized under three experimental conditions. The cell with an NCAL cathode pre-reduced under an H2 atmosphere at 550 °C presents the best electrochemical performance. This is ascribed to facts that the reduction reaction generating Ni–Co...
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Direct solid phase microextraction combined with gas chromatography – Mass spectrometry for the determination of biogenic amines in wine
PublicationA direct method based on immersion solid phase microextraction (DI-SPME) gas chromatography mass-spectrometry (GC-MS) was optimized and validated for the determination of 16 biogenic amines in Polish wines. In the analysis two internal standards were used: 1,7-diaminoheptane and bis-3-aminopropylamine. The method allows for simultaneous extraction and derivatization, providing a simple and fast mode of extraction and enrichment....
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Fabrication of Durable Ordered Ta2O5 Nanotube Arrays Decorated with Bi2S3 Quantum Dots
PublicationOne of the most important challenges in the fabrication of ordered tantalum pentaoxide (Ta2O5) nanotube arrays (NTs) via the electrochemical method is the formation of nanotubes that adhere well to the Ta substrate. In this paper, we propose a new protocol that allows tight-fitting Ta2O5 nanotubes to be obtained through the anodic oxidation of tantalum foil. Moreover, to enhance their activity in the photocatalytic reaction, in...
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Improvement of Oxygen Electrode Performance of Intermediate Temperature Solid Oxide Cells by Spray Pyrolysis Deposited Active Layers
PublicationIntermediate temperature solid oxide fuel cells oxygen electrodes are modified by active interfacial layers. Spray pyrolysis is used to produce thin (≈500 nm) layers of mixed ionic and electronic conductors: Sm0.5Sr0.5CoO3−δ (SSC), La0.6Sr0.4CoO3−δ (LSC), La0.6Sr0.4Co0.2Fe0.8O3−δ (LSCF), and Pr6O11 (PrOx) on the electrode–electrolyte interface. The influence of the annealing temperature on the electrode polarization (area specific...
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Why do G-quadruplexes dimerize through the 5’-ends? Driving forces for G4 DNA dimerization examined in atomic detail
PublicationG-quadruplexes (G4) are secondary structures formed by guanine-rich nucleic acid sequences and shown to exist in living cells where they participate in regulation of gene expression and chromosome maintenance. G-quadruplexes with solvent-exposed guanine tetrads show the tendency to associate together through cofacial stacking, which may be important for packaging of G4-forming sequences and allows for the design of higher-order...
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Towards azeotropic MeOH-MTBE separation using pervaporation chitosan-based deep eutectic solvent membranes
PublicationDeep eutectic solvents (DESs) are a new class of solvents that can offset some of the major drawbacks of common solvents and ionic liquids. When dealing with the preparation of dense membranes, the use of DESs is still challenging due to their low compatibility with the polymer phase. In this research, a novel L-proline:sulfolane (molar ratio 1:2) DES was synthesized and used for the preparation of more sustainable bio-based membranes...
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Application of Aqueous Biphasic Systems Extraction in Various Biomolecules Separation and Purification: Advancements Brought by Quaternary Systems
PublicationAqueous biphasic systems (ABS) extraction is a simple, selective, efficient and easy to scale-up technology that, over the years, has attracted a considerable attention from the researcher community as an alternative methodology in downstream processing of a wide variety of biomolecules. This review summarizes and discusses the fundamental features of ABS, as well as its advantages and disadvantages, as a separation and purification...
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Recent developments and future trends in solid phase microextraction techniques towards green analytical chemistry
PublicationSolid phase microextraction find increasing applications in the sample preparation step before chromatographic determination of analytes in samples with a complex composition. These techniques allow for integrating several operations, such as sample collection, extraction, analyte enrichment above the detection limit of a given measuring instrument and the isolation of analytes from sample matrix. In this work the information about...
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Transparent TiO2 nanotubes supporting silver sulfide for photoelectrochemical water splitting
PublicationDifferences between photoelectrochemical and electrochemical activity were thoroughly investigated for the oxygen evolution reaction mediated by Ag2S deposited on two types of ordered titania substrates. Titanium dioxide nanotubes were fabricated by anodization of magnetron sputtered Ti films on ITO-coated glass substrates or directly from Ti foil. Further, Ag2S deposition on the nanotubes was carried out using successive ionic...
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Development of novel optoelectronic sensory structures utilising colour centres in nanodiamonds and their interactions with analytes
PublicationThe goal of this dissertation was to develop and assess surface modifications of fluorescent nanodiamonds (NDs) for optical sensing. Three modification routes were tested, each aimed at a different application. Modification with poly-L-lysine (pLys) was verified for optical sensing of pH via an interrelationship between electrically negative (NV¯) and neutral (NV0) nitrogen-vacancy centres. Immobilisation of Ochratoxin A (OTA),...
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Fabrication of the cross-linked PVA/TiO2/C nanocomposite membrane for alkaline direct methanol fuel cells
PublicationA crosslinked Poly(vinyl alcohol) based composite membrane was developed through a phase inversion process for use in alkaline direct methanol fuel cells (ADMFCs). The titanium dioxide (TiO2) and carbon nanoparticles (NPs) have been incorporated into the PVA polymer matrix to improve the mechanical and thermal properties. The membrane samples were further modified with maleic acid, a carboxylic acid acting as the cross-linker,...
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A method to monitor urinary carbon dioxide in patients with septic shock
PublicationSevere sepsis and septic shock are life-threatening conditions with mortality rates exceeding 31% (Levy et al., 2012) [1]. Septicemia was the most expensive US hospital condition in 2011 (Torio and Andrews, 2006)[2]. Urinary carbon dioxide may provide rapid, clinically useful information about a patient’s status, empowering physicians to intervene earlier and improve septic shock mortality. The objective of this paper is to validate...
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Progressing Pollutant Elution from Snowpack and Evolution of its Physicochemical Properties During Melting Period— a Case Study From the Sudetes, Poland
PublicationMain aim of the work assumed recognition of physicochemical changes in snowpack occurring during the melting period. Properties of snow cover had been identified at two sites in Western Sudetes mountains (860 and 1228 m asl) in SW Poland since the end of January, and monitored until the disappearance of snow in late Spring. Snow pit measurements and sample collection at both sites were made followed by chemical analyses with the...
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Solubility of Carbon Dioxide in Deep Eutectic Solvents Based on 3-Amino-1-Propanol and Tetraalkylammonium Salts at Low Pressure
PublicationDeep eutectic solvents (DESs) became an object of a great interest as an alternative to ionic liquids (ILs) and commonly used in CO2 capture amine solutions. In the present study, five different DESs based on 3-amino-1-propanol as physical-chemical CO2 absorbents were used. The composition was chosen in order to estimate the effects of hydrogen bond acceptor:hydrogen bond donor (HBA:HBD) molar ratio, anion type and length of alkyl...
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Effect of synthesis method parameters on properties and photoelectrocatalytic activity under solar irradiation of TiO2 nanotubes decorated with CdS quantum dots
PublicationThe growing research interest on photoelectrocatalysis has encouraged the search for new materials with high activity and the development of methods for their synthesis. The successive ionic layer adsorption and reaction (SILAR) method is an effective way to synthesize materials with photoelectrocatalytic (PEC) properties that are active under visible radiation. Therefore, studies on the impact of the parameters of the SILAR method...
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Deep eutectic solvents – A new platform in membrane fabrication and membrane-assisted technologies
PublicationDeep eutectic solvents (DESs) are a new class of solvents that can offset some of the primary drawbacks of typical solvents and ionic liquids (ILs). Since DESs fall into the guidelines of “Twelve Principles of Green Chemistry”, their implementation in several types of applications has exponentially increased over the last years. The usage of DESs has been directed to the designing, manufacture and purification of new materials...
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First evaluation of wastewater discharge influence on marine water contamination in the vicinity of Arctowski Station (Maritime Antarctica)
PublicationIn Antarctica,waste is generatedmainly during scientific research programmes and related logistics. In this study, the impact ofwastewater on the western shore of Admiralty Baywas investigated during austral summer in 2017 and 2019. A range of physicochemical parameters and the presence of selected trace metals, formaldehyde and different groups of surfactants were determined in wastewater coming from Arctowski Station and in nearby coastal...
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Deep eutectic solvents microbial toxicity: Current state of art and critical evaluation of testing methods
PublicationDeep eutectic solvents (DESs) were described at the beginning of 21st century and they consist of a mixture of two or more solid components, which gives rise to a lower melting point compared to the starting materials. Over the years, DESs have proved to be a promising alternative to traditional organic solvents and ionic liquids (ILs) due to their low volatility, low inflammability, easy preparation, and usually low cost of compounds...
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Influence of iron content on water uptake and charge transport in BaCe0.6Zr0.2Y0.2−xFexO3−δ triple-conducting oxides
PublicationIn this work, we studied the BaCe0.6Zr0.2Y0.2−xFexO3−δ system which belongs to the triple-conducting oxides (TCOs) group. The electrochemical properties of BaCe0.6Zr0.2Y0.2−xFexO3−δ were investigated using electrochemical impedance spectroscopy (EIS) and the water uptake was analyzed using thermogravimetry (TG). All investigated materials exhibited water uptake, with proton concentration increasing with decreasing iron content....
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Reactions of cobalt(ii) chloride and cobalt(ii) acetate with hemisalen-type ligands: ligand transformation, oxidation of cobalt and complex formation. Preliminary study on the cytotoxicity of Co(ii) and Co(iii) hemisalen complexes
PublicationSeveral molecular cobalt(II) complexes, one Co(II) coordination polymer, and one ionic cobalt(III) complex with imine hemisalen ligands were synthesized. The hemisalen ligands were synthesized from o-vanillin (oVP) and diverse aminopyridines (compounds HL1–HL4) or aminophenol (compound HL5). It was observed that cobalt(II) chloride in dry acetonitrile catalyzes a transformation of HL1 and HL3 instead of complex formation. The conversion...
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DL_MG: A Parallel Multigrid Poisson and Poisson–Boltzmann Solver for Electronic Structure Calculations in Vacuum and Solution
PublicationThe solution of the Poisson equation is a crucial step in electronic structure calculations, yielding the electrostatic potential -- a key component of the quantum mechanical Hamiltonian. In recent decades, theoretical advances and increases in computer performance have made it possible to simulate the electronic structure of extended systems in complex environments. This requires the solution of more complicated variants of the...
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Solvent Impact on the Diversity of Products in the Reaction of Lithium Diphenylphosphide and a Ti(III) Complex Supported by a tBu2P–P(SiMe3) Ligand
PublicationWe present two important trends in the reactivity ofthe titanium complex [MeNacNacTi(Cl){η2-P(SiMe3)-PtBu2}](MeNacNac− = [Ar]NC(Me)CHC(Me)N[Ar]; Ar = 2,6-iPr2Ph)with nucleophilic reagents RLi (R = Ph2P,tBuO, (Me3Si)2N, andtBu2N) depending on the reaction medium. Reaction in nonpolarsolvent (toluene) leads to three main products: via an autoredoxprocess and nucleophilic substitution at the Ti-atom to afford theTi(IV) complex [MeNacNacTi(R){η2-P-PtBu2}]...