Search results for: dft
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The Reactivity of the Imine Bond within Polynuclear Nickel(II) Complexes
PublicationThree novel Ni complexes with the Schiff base ligand 2-methoxy-6-(E-2-pyridyliminomethyl)-phenol (L1) are described. In comparison with the similar 2-(pyridine-2-ylimino-methyl)phenol (pymp), the mode of coordination of L1 is altered due to the presence of methoxy substituent introducing the sterical hindrance. During the synthesis of the complexes, partial hydrolysis of the ligand was observed. Since such immediate hydrolysis...
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Sulfurization of phosphanylphosphinidene ligand: Access to phosphinothioyltrithiophosphonato platinum(II) complexes
PublicationThe reactivity of phosphanylphosphinidene Pt(0) complexes [DppePt(η2-P–PtBu2)] (1) and [(pTol3P)2Pt(η2-P–PtBu2)] (2) toward sulfur was studied. Reactions of 1 and 2 with an excess of sulfur led to the formation of the first transition metal complexes 3 and 4 with phosphinothioyltrithiophosphonato ligands with the formula [tBu2P(=S)–P(=S)S2]2-. In contrast to previous reports on the phosphanylphosphinidene moiety sulfurization,...
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Linear-scaling calculation of Hartree-Fock exchange energy with Non-orthogonal Generalised Wannier Functions
PublicationWe present a method for the calculation of four-centre two-electron repulsion integrals in terms of localised non-orthogonal generalised Wannier functions (NGWFs). Our method has been imple- mented in the ONETEP program and is used to compute the Hartree-Fock exchange energy component of Hartree-Fock and Density Functional Theory (DFT) calculations with hybrid exchange-correlation functionals. As the NGWFs are optimised in situ...
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A comparison of structural and luminescence properties of lead(II) coordination polymers with isomeric thiophenecarboxylate ligands
PublicationTwo new lead(II) coordination polymers with isomeric thiophenecarboxylates, namely [Pb(2tpCOO)2]n (1) and [Pb(3tpCOO)2(H2O)]n (2) (2tpCOO− = thiophene-2-carboxylate, 3tpCOO− = thiophene-3-carboxylate), were synthesized and characterized. Single crystal X-ray crystallography revealed a distorted pentagonal pyramidal geometry {PbO6} around Pb in 1 and a distorted dodecahedral geometry {PbO8} in 2. The distortion derived from the...
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Exploring thiophene-2-acetate and thiophene-3-acetate binding modes towards the molecular and supramolecular structures and photoluminescence properties of Pb(ii) polymers
PublicationTo evaluate the impact of the flexible positional isomeric ligands thiophene-2-acetate (2tpacCOO) andthiophene-3-acetate (3tpacCOO) on the construction and self-assembly process of Pb(II) polymers, twonovel compounds, [Pb(2tpacCOO)2(H2O)]n(1) and [Pb(3tpacCOO)2]n(2), were preparedviaanonhydro-thermal method with respect to green chemistry rules. The obtained polymers were fully characterized byelemental analysis, TG/DTG and PXRD,...
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Emerging oxidized and defective phases in low-dimensional CrCl3
PublicationTwo-dimensional (2D) magnets such as chromium trihalides CrX3 (X ¼ I, Br, Cl) represent a frontier for spintronics applications and, in particular, CrCl3 has attracted research interest due its relative stability under ambient conditions without rapid degradation, as opposed to CrI3. Herein, mechanically exfoliated CrCl3 flakes are characterized at the atomic scale and the electronic structures of pristine, oxidized, and defective...
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Electronic structure calculations in electrolyte solutions: Methods for neutralization of extended charged interfaces
PublicationDensity functional theory (DFT) is often used for simulating extended materials such as infinite crystals or surfaces, under periodic boundary conditions (PBCs). In such calculations, when the simulation cell has non-zero charge, electrical neutrality has to be imposed, and this is often done via a uniform background charge of opposite sign (“jellium”). This artificial neutralization does not occur in reality, where a different...
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In situ transformation boosts the pseudocapacitance of CuNi-MOF via cooperative orientational and electronic governing
PublicationThe disordered arrangement and thereof inferior conductivity of 2D MOF sheets seriously hinder their practical application. Herein, we propose in situ transformation strategy to architect vertically oriented bimetallic CuNi-MOF as a self-supporting electrode, leading to a decuple high specific capacitance of 1262 C g-1 in comparison with the pristine Ni-MOF powder of 114 C g-1 at 2 A g-1. DFT calculations reveal that introduction...
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On thio‐substituted N‐heterocyclic arsines
PublicationMetathesis of N-heterocyclic chloroarsines with sulfur-based nucleophiles furnished thio-substituted 1,3,2-diazarsolidines and 1,3,2-diazarsolenes. Crystallographic and NMR spectroscopic studies revealed that a thiocyanato-diazarsolene exhibits a salt-like structure composed of weakly interacting thiocyanate and arsenium ions, while the remaining products formed neutral molecules. The structural data indicate that the heterocyclic...
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Synthesis and characterization of mononuclear Zn(II), Co(II) and Ni(II) complexes containing a sterically demanding silanethiolate ligand derived from tris(2,6-diisopropylphenoxy)silanethiol
PublicationFour heteroleptic complexes of zinc(II), cobalt(II) and nickel(II) containing a monodentate silanethiolate ligand derived from tris(2,6-diisopropylphenoxy)silanethiol (TDST), were prepared and characterized. The geometries of ligands in the complexes are typical: distorted tetrahedral in zinc and cobalt(II) complexes and square planar in nickel(II) compound. Magnetic studies performed for Ni(II) and Co(II) compounds confirm the...
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Structural properties of hypothetical CeBa2Cu3O7 compound from LSDA+DMFT calculations
PublicationThe hypothetical stoichiometric CeBa2Cu3O7 (Ce123) compound, which has not been synthesized as a single phase yet, was studied by the density functional theory (DFT). We utilized a method which merges the local spin density approximation (LSDA) with the dynamical mean-field theory (DMFT) to account for the electronic correlations. The LSDA+DMFT calculations were performed in the high-temperature range. The particular emphasis was...
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Compressible gas density measurement by means of Fourier analysis of interferograms
PublicationThis paper describes a method for nonintrusive compressible gas density measurement by means of automated analysis of interferograms using FFT (Fast Fourier Transform), and its implementation using DFT (Discrete Fourier Transform), that does make this measurement technique a fairly valuable and accessible experimental method. The presented approach makes it possible to use the finite fringe setting of the interferometer, thus reducing...
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Optimization of Hydrogen - Evolving Photochemical Molecular Devices
PublicationA molecular photocatalyst consisting of a RuII photocenter, a tetrapyridophenazine bridging ligand, and a PtX2 (X=Cl or I) moiety as the catalytic center functions as a stable system for light-driven hydrogen production. The catalytic activity of this photochemical molecular device (PMD) is significantly enhanced by exchanging the terminal chlorides at the Pt center for iodide ligands. Ultrafast transient absorption spectroscopy...
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Stability and phase transition investigation of olanzapine polymorphs
PublicationWe use electrical embedded-fragment QM method with both DFT/ωB97XD/6-31G* and MP2/6-31G* to investigate the phase transformations of olanzapine. Gibbs free energy calculations predict that form I is always the most stable structure and form II is the least stable one, while form IV is more stable than form III below about 200 K but less stable above this temperature, implying a polymorphic phase transformation. This may account...
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Relationship between electronic structure and geometry of silanethiols and their derivatives. Elucidation of copper group silanethiolates
PublicationWyznaczono strukturę elektronową wybranych silanotioli X3SiSH (dla X=H, C2H5, OCH3, F, Cl i Br) oraz powstalych z nich anionów. Geometrię i funkcje falowe wyznaczono przy użyciu teorii funcjonałów gęstości elektronowej DFT. Przeanalizowano wpływ efektów anomerycznych oraz wielkości calki nakładania sigma(Si-S) na obserwowane skrócenie wiązania Si-S przy deprotonowaniu silanotioli. Podano nowe wyjaśnienie wyjątkowo niskiej kwasowości...
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Unassisted formation of hemiaminal ether from 4-aminopyridine and o-vanillin - experimental and theoretical study
PublicationThe reactions between o-vanillin and three isomeric aminopyridines lead to imines of diverse spatial conformation and reactivity. The direct products of these simple reactions carried out in methanol are either imine compounds formed in the reactions of 2- amino- and 3-aminopyridine with o-vanillin or the α-aminoether formed in the reaction of o-vanillin with 4-aminopyridine. The Schiff-type derivative of 4-aminopyridine and o-vanillin,...
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Protein thermal stabilization in aqueous solutions of osmolytes
PublicationProteins’ thermal stabilization is a significant problem in various biomedical, biotechnological, and technological applications. We investigated thermal stability of hen egg white lysozyme in aqueous solutions of the following stabilizing osmolytes: Glycine (GLY), N-methylglycine (NMG), N,N-dimethylglycine (DMG), N,N,N-trimethylglycine (TMG), and trimethyl-N-oxide (TMAO). Results of CD-UV spectroscopic investigation were compared...
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Do positrons measure atomic and molecular diameters?
PublicationWe report on density functional calculations (DFT) of elastic integral scattering cross-sections for positron collisions with argon, krypton, nitrogen and methane. The long-range asymptotic polarization potential is described using higher-order terms going much beyond an induced dipole potential (−α / r 4) while the short-range interaction is modeled by two different forms of electron – positron correlation potential (Boroński-Nieminen...
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Prediction of Overall In Vitro Microsomal Stability of Drug Candidates Based on Molecular Modeling and Support Vector Machines. Case Study of Novel Arylpiperazines Derivatives
PublicationOther than efficacy of interaction with the molecular target, metabolic stability is the primary factor responsible for the failure or success of a compound in the drug development pipeline. The ideal drug candidate should be stable enough to reach its therapeutic site of action. Despite many recent excellent achievements in the field of computational methods supporting drug metabolism studies, a well-recognized procedure to model...
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Li nucleation on the graphite anode under potential control in Li-ion batteries
PublicationApplication of Li-ion batteries in electric vehicles requires improved safety, increased lifetime and high charging rates. One of the most commonly used intercalation anode material for Li-ion batteries, graphite, is vulnerable to Li nucleation, a side reaction which competes with the intercalation process and leads to loss of reversible capacity of the battery, ageing and short-circuits. In this study, we deploy a combined grand...
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Mixed-ligand complexes of zinc(II), cobalt(II) and cadmium(II) with sulfur, nitrogen and oxygen ligands. Analysis of the solid state structure and solution behavior. Implications for metal ion substitution in alcohol dehydrogenase
PublicationScharakteryzowano strukturę heteroleptycznych kompleksów cynku(II), kobaltu(II) i kadmu(II) z 2-(2'-hydroksyetylopirydyną), tri-tert-butoksysilanotiolem i metanolem. Przy pomocy widm UV-Vis i NMR stwierdzono szybką wymianę N-liganda w roztworach tych kompleksów. Wyznaczono przesunięcia 15N NMR 2-(2'-hydroksyetylopirydyny) w kompleksach cynku(II) i kadmu(II). Na podstawie widm w podczerwieni i obliczeń DFT oszacowano względną moc...
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Crystal structure and electronic structure of CePt2In7
PublicationWe report a corrected crystal structure for the CePt2In7 superconductor, refined from single crystal x-ray diffraction data. The corrected crystal structure shows a different Pt–In stacking along the c-direction in this layered material than was previously reported. In addition, all of the atomic sites are fully occupied with no evidence of atom site mixing, resolving a discrepancy between the observed high resistivity ratio of...
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Theoretical study of the structure, energetics and vibrational frequencies of water-acetone and water-2-butanone complexes
PublicationKompleksy acetonu i 2-butanonu z 0-2 cząsteczkami wody połączonymi wiązaniem wodorowym z tlenem karbonylowym zbadano z wykorzystaniem teorii funkcjonału gęstości (DFT) na poziomie B3LYP/6-311++G(d,p). Obliczenia w fazie gazowej uzupełniono o optymalizacje w otoczeniu rozpuszczalnika, symulowanego za pomocą modelu polaryzowalnego kontinuum (PCM). Częstości drgań oscylacyjnych otrzymane na podstawie zależności empirycznej sa zgodne...
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Carboxylation Enhances Fragmentation of Furan upon Resonant Electron Attachment
PublicationWe report a dissociative electron attachment study to 2-furoic acid (C5H4O3) isolated in a gas phase, which is a model molecule consisting of a carboxylic group and a furan ring. Dissociation of furan by low energy electrons is accessible only via electronic excited Feshbach resonances at energies of incident electrons above 5 eV. On the other hand, carboxylic acids are well- known to dissociate via attachment of electrons at subexcitation energies....
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Reactivity of bulky aminophosphanes towards small molecules: Activation of dihydrogen and carbon dioxide by aminophosphane/borane frustrated Lewis pairs
PublicationA 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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Comparison of the coordination geometries of Zn(II) and Cd(II) ions in complexes with water, methanol and bulky aryloxysilanethiolate ligands
PublicationZinc 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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Analizator do spektroskopii wysokoimpedancyjnej obiektów technicznych modelowanych obwodami elektrycznymi.
PublicationW pracy przedstawiono prototyp analizatora do spektroskopii wysokoimpedancyjnej przeznaczonego do diagnostyki powłok antykorozyjnych w warunkach laboratoryjnych oraz terenowych. Obiekt mierzony o module impedancji do 100Gohm jest dołączany do analizatora za pomocą sondy pomiarowej dwuzaciskowej dla obiektów uziemionych lub trzyzaciskowej w przypadku obiektów nieuziemionych. W sondzie są wydzielane dwa sygnały proporcjonalne do...
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Current harmonic controller in multiple reference frames for series active power filter integrated with 18-pulse diode rectifier
PublicationThe paper presents the control system and selected results of experimental tests of the AC/DC power converter consisting of an 18-pulse diode rectifier based on coupled reactors and a serial active power filter. Proportional integral controllers with decoupling components are implemented in multiple reference frames for selective line current harmonic suppression. The regulator is provided with a backtracking anti-windup mechanism...
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Local Conformation and Cocrystallization Phenomena in Renewable Diaminoisoidide-Based Polyamides Studied by FT-IR, Solid State NMR, and WAXD
PublicationBiobased polyamides synthesized from diaminoisoidide (DAII), 1,4-diaminobutane, and sebacic acid are investigated by FT-IR, 13C{1H} magic-angle spinning/cross-polarization (CP/MAS) NMR spectroscopy, and WAXD. Their molecular conformation and mobility undergo distinct changes as a function of temperature and diaminoisoidide content in the compositions. The presence of randomly distributed diaminoisoidide (DAII) in the polyamides...
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Hydration of Simple Carboxylic Acids from Infrared Spectra of HDOand Theoretical Calculations
PublicationBadanie hydratacji kwasów karboksylowych w rozcieńczonych roztworach wodnych ma duże znaczenie dla zrozumienia ich funkcji biologicznych. Metodą stosowaną w badaniach była spektroskopia oscylacyjna FTIR z zastosowaniem techniki rozcieńczenia izotopowego wody półciężkiej HDO w roztworze wody zwykłej. Do analizy danych widmowych wykorzystano ''metodę widm różnicowych''. Widma HDO zaburzonej przez kwasy: mrówkowy, octowy i propionowy...
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Experimental and theoretical studies on the photodegradation of 2-ethylhexyl 4-methoxycinnamate in the presence of reactive oxygen and chlorine species
Publication2-Ethylhexyl 4-methoxycinnamate (EHMC) is one of the most commonly used sunscreen ingredient. In this study we investigated photodegradation of EHMC in the presence of such common oxidizing and chlorinating systems as H2O2, H2O2/HCl, H2O2/UV, and H2O2/HCl/UV. Reaction products were detected by gas chromatography with a mass spectrometric detector (GC-MS). As a result of experimental studies chloro-substituted 4-methoxycinnamic...
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Theoretical pKa prediction of O-phosphoserine in aqueous solution
PublicationSprawdzono zdolność modelu polaryzowalnego kontinuum (PCM) do przewidywania wartości pKa w roztworze wodnym dla O-fosfoseryny (P-Ser). Obliczenia przeprowadzono w ramach teorii funkcjonału gęstości (DFT) przy użyciu funkcjonałów B3LYP i M06-2X oraz baz 6-31+G(d) and 6-31+G(d,p). Obliczenia na poziomie B3LYP/6-31+G(d,p) przy użyciu modelu solwatacji SMD zapewniają doskonałą zgodność z doświadczeniem, pod warunkiem uwzględnienia...
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Method using square-pulse excitation for high-impedance spectroscopy of anticorrosion coatings
PublicationArtykuł prezentuje metodę spektroskopii impedancyjnej przeznaczonej do diagnostyki powłok antykorozyjnych na obiektach bezpośrednio w terenie. Aby skrócić czas uzyskania widma impedancji (w zakresie od 1 mHz do 1 MHz) do kilku minut, wykorzystano sygnały harmoniczne do pomiaru widma powyżej 10 Hz a impuls prostokątny w dolnym zakresie częstotliwości. Do wyznaczania widma użyto algorytmów DSP odpowiednich do sygnału pobudzenia....
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A facile method for Tauc exponent and corresponding electronic transitions determination in semiconductors directly from UV–Vis spectroscopy data
PublicationIn this work, a facile method allowing for estimation of the exponent in the Tauc equation directly from the UV–vis spectra is presented. It is based on the Taylor expansion of the logarithmic version of the Tauc equation. The Tauc exponent is calculated from the tangent slope of the absorption data. Knowledge of this coefficient provides information about the optical transition types and is used as an input for the calculations...
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Proton transfer and hydrogen bonds in supramolecular, self-assembled structures of imidazolium silanethiolates. X-ray, spectroscopic and theoretical studies
PublicationThe reaction of 1-methylimidazole, 2-ethyl-4-methylimidazole and 2-ethylimidazole with tris(2,6- diisopropylphenoxy)silanethiol (TDST) leads to the formation of three new salts, which have been characterized by elemental analyses, thermogravimetric analyses, FTIR spectroscopy, and their structures were determined by single-crystal X-ray diffraction. Structural analyses indicate that in all three compounds a proton transfer has...
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Absorptive Desulfurization of Model Biogas Stream Using Choline Chloride-Based Deep Eutectic Solvents
PublicationThe paper presents a synthesis of deep eutectic solvents (DESs) based on choline chloride (ChCl) as hydrogen bond acceptor and phenol (Ph), glycol ethylene (EG), and levulinic acid (Lev) as hydrogen bond donors in 1:2 molar ratio. DESs were successfully used as absorption solvents for removal of dimethyl disulfide (DMDS) from model biogas steam. Several parameters affecting the absorption capacity and absorption rate have been...
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Comparison of effectiveness of musical sound separation algorithms employing neural networks.
PublicationNiniejszy referat przedstawia kilka algorytmów służących do separacji dźwięków instrumentów muzycznych. Zaproponowane podejście do dekompozycji miksów dźwiękowych opiera się na założeniu, że wysokość dźwięków w miksie jest znana, tzn. wejściem dla algorytmów jest przebieg zmian wysokości dźwięków składowych miksu. Proces estymacji fazy i amplitudy składowych harmonicznych wykorzystuje dopasowywanie zespolonych przebiegów harmonicznych...
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Photoinduced electron transfer in 5-bromouracil labeled DNA. A contrathermodynamic mechanism revisited by electron transfer theories
PublicationThe understanding of the 5-bromouracil (BrU) based photosensitization mechanism of DNA damage is of large interest due to the potential applications in photodynamic therapy. Photoinduced electron transfer (ET) in BrU labeled duplexes comprising the 50 -GBrU or 50 -ABrU sequence showed that a much lower reactivity was found for the 50 -GBrU pattern. Since the ionization potential of G is lower than that of A, this sequence selectivity...
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Electronic structure of TbBa2Cu3O7
PublicationW pracy wykonano obliczenia kwantowomechaniczne struktury elektronowej hipotetycznego materiału TbBa2Cu3O7 (Dy123) metodą FP-LAPW (full potential - linearized augmented plane wave) w ramach formalizmu DFT (density functional theory) stosując przybliżenie GGA (generalized gradient approximation). Ze względu na silne oddziaływania korelacyjne elektronów 4f w atomie Tb zastosowano dodatkowo poprawkę kulombowską U w ramach modelu...
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Hydration of simple amides. FTIR spectra of HDO and theoretical studies
PublicationZastosowano metodę ważonych widm różnicowych do opisu hydratacji amidów w roztworach wodnych: formamidu, N-metyloformamidu, N,N-dimetyloformaidu, acetamidu, N-metyloacetamidu, N,N-dimetyloacetamidu. Narzędziem wspomagającym interpretację wyników eksperymentalnych są struktury agregatów solwatacyjnych wokół cząsteczki substancji rozpuszczonej uzyskane na podstawie obliczeń teoretycznych metodą ab initio z korelacją elektronową...
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Symmetrical and unsymmetrical diphosphanes with diversified alkyl, aryl and amino substituents
PublicationWe present the comprehensive study of diphosphanes with diversified substituents regarding their syntheses, structures, and properties. To this end, we have synthesized a series of novel unsymmetrical alkyl, aryl and amino-substituted diphosphanes of the general formula R1R2P-PR3R4 (where R1, R2, R3, R4 = tBu, Ph, Et2N or iPr2N) via salt metathesis reactionof halophosphanes with metal phosphides in high yield. We vastly expanded...
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Theoretical and Experimental Studies on the Visible Light Activity of TiO2 Modified with Halide-Based Ionic Liquids
PublicationFormation of a surface complex between organic molecules and TiO2 is one of the possible strategies for the development of visible light-induced TiO2 photoactivity. Herein, three ionic liquids (ILs) with the same cation and dierent anions (1-butylpirydynium chloride/bromide/iodide) have been applied for the surface modification of TiO2 and to understand the role of anions in visible light-induced activity of ILs-TiO2 systems. Photocatalytic...
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Theoretical studies of fragmentation processes of neutral and ionized furan molecule
PublicationThis PhD thesis focuses on the fragmentation mechanism of the furan molecule in the gas phase. The approach taken in this work comprised of three theoretical methodologies considering the dynamical, energetical and entropic aspects of the studied process. First, molecular dynamics simulations were performed. Next, the potential energy surfaces were explored at the DFT/B3LYP level of theory. Finally, a new statistical Microcanonical...
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Density functional LCAO calculations of vibrational modes and phonon density of states in the strained single-layer phosphorene
PublicationThe paper presents an investigation of phosphorene under axial strain on the phonon density of states and vibrational modes. The studies were performed by means of density functional theory (DFT) within the linear combination of atomic orbitals (LCAO). The strained models were constructed using optimised supercell techniques. The vibrational mode spectra were estimated for strains applied for both the zigzag and armchair directions...
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Mechanism of Li nucleation at graphite anodes and mitigation strategies
PublicationLithium metal plating is a critical safety issue in Li-ion cells with graphite anodes, and contributes significantly to ageing, drastically limiting the lifetime and inducing capacity loss. Nonetheless, the nucleation mechanism of metallic Li on graphite anodes is still poorly understood. But in-depth understanding is needed to rationally design mitigation measures. In this work, we conducted FirstPrinciples studies to elucidate...
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Mechanochemically synthesized Mn3O4@β-cyclodextrin mediates efficient electron transfer process for peroxymonosulfate activation
PublicationThe rational surface engineering of heterogeneous catalysts is of great significance in advanced oxidation processes (AOPs) for eliminating refractory contaminants but remains challenging. In this study, β-cyclodextrin modified Mn3O4 (Mn3O4@β-CD) was prepared through a mechanochemical approach for peroxymonosulfate (PMS) activation, which achieved efficient bisphenol A (BPA) removal via electron transfer process (ETP). The reactive...
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Synthetic, Structural, and Spectroscopic Characterization of a Novel Family of High-Spin Iron(II) [(β-Diketiminate)(phosphanylphosphido)] Complexes
PublicationThis work describes a series of iron(II) phosphanylphosphido complexes. These compounds were obtained by reacting lithiated diphosphanes R2PP(SiMe3)Li (R = t-Bu, i-Pr) with an iron(II) β-diketiminate complex, [LFe(μ2-Cl)2Li(DME)2] (1), where DME = 1,2-dimethoxyethane and L = Dippnacnac (β-diketiminate). While the reaction of 1 with t-Bu2PP(SiMe3)Li yields [LFe(η1-Me3SiPPt- Bu2)] (2), that of 1 with equimolar amounts of i-Pr2PP(SiMe3)Li,...
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The electronic structure of p-xylylene and its reactivity with vinyl molecules
PublicationThe electronic states of p-xylylene molecule were described at the multi-configurational CASSCF/MRMP2 level of theory. The closed-shell singlet state representing the quinoidal p-xylylene molecule was pre-dicted to be the ground electronic state whereas the triplet (benzoidal) and the singlet open-shell states were found to be much higher in energy (by 159 and 423 kJ/mol, respectively, as found at the CASSCF(8,8)/6-31+G(d) level)....
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Towards sugar-derived polyamides as environmentally friendly materials
PublicationAs part of our ongoing study investigating isohexide-based polyamides, we have synthesized isosorbide(bis(propan-1-amine)) (DAPIS) and studied its reactivity in the polymerization towards fully biobased polyamides. Polycondensation of nylon salts with various contributions of DAPIS afforded a family of homo- and copolyamides, which were characterized using complementary spectroscopic techniques. The chemical structure of the materials...
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The potential of imogolite nanotubes as (co-)photocatalysts: a linear-scaling density functional theory study
PublicationWe report a linear-scaling density functional theory (DFT) study of the structure, wall-polarization absolute band-alignment and optical absorption of several, recently synthesized, open-ended imogolite (Imo) nanotubes (NTs), namely single-walled (SW) aluminosilicate (AlSi), SW aluminogermanate (AlGe), SW methylated aluminosilicate (AlSi-Me), and double-walled (DW) AlGe NTs. Simulations with three different semi-local and dispersion-corrected...
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Enhanced photocatalytic properties of lanthanide-TiO2 nanotubes: An experimental and theoretical study
PublicationA series of Er-, Yb-, Ho-, Tb-, Gd-, Pr-TiO2 nanotubes (RE-NTs) was prepared via an electrochemical method. The as-prepared photocatalysts were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), UV–vis absorption, scanning electron microscopy (SEM) and luminescent spectroscopy. The experiments demonstrated that toluene in the gas phase was successfully degraded under visible light (LEDs λmax = 465...
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Polymerization of chloro-p-xylylenes, quantum-chemical study
PublicationThe p-xylylene monomers of parylene N, C and D have similar high polymerization reactivity. For effective copolymerization processes this fact is basically a draw- back and for instance the copolymerization with styrene doesn't go at all (Corley et al. J Pol Sc 13(68):137156, 1954). Substitution of terminal hydrogen atoms by chlorine atoms reduces reactivity dramatically. 7,7,8,8-tetrachloro-p- xylylene and 2,5,7,7,8,8-hexachloro-p-xylylene...
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Extractive detoxification of feedstocks for the production of biofuels using new hydrophobic deep eutectic solvents – Experimental and theoretical studies
PublicationThe paper presents a synthesis of novel hydrophobic deep eutectic solvents (DESs) composed of natural components, which were used for removal of furfural (FF) and 5-hydroxymethylfurfural (HMF) from lignocellulosic hydrolysates. The main physicochemical properties of DESs were determined, followed by explanation of the DES formation mechanism, using 1H NMR, 13C NMR and FT-IR analysis and density functional theory (DFT). The most...
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Deep eutectic solvents based highly efficient extractive desulfurization of fuels – Eco-friendly approach
PublicationThe developed process is based on alternative, green and cheap solvents for efficient desulfurization of fuels. Several deep eutectic solvents (DESs) were successfully synthesized and studied as extraction solvents for desulfurization of model fuel containing thiophene (T), benzothiophene (BT) and dibenzothiophene (DBT). The most important extraction parameters (i.e. kind of DES, DES: fuel volume ratio, hydrogen bond acceptor:...
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Effect of urea and glycine betaine on the hydration sphere of model molecules for the surface features of proteins
PublicationWater properties may significantly affect protein stability. Osmolytes are compounds that intrinsically affect water in many different ways and thus can influence proteins with this type of indirect mechanism. In this study, we characterize water properties in ternary solutions: model–water–osmolyte, with two model molecules: N-methylacetamide (NMA) and dimethyl sulfoxide (DMSO) and two osmolytes: glycine betaine (TMG)and urea....
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Unexpected Z/E isomerism of N-methyl-O-phosphothioyl benzohydroxamic acids, their oxyphilic reactivity and inertness to amines
PublicationThiophosphinoylation of N-methyl p-substituted benzohydroxamic acids using disulfanes (method A) or diphenylphosphinothioyl chloride (method B) provides only one conformer of the respective O-phosphothioyl derivative (Xray and NMR analysis). Undergoing the P-transamidoxylation reaction is an evidence of the reversibility of thiophosphinoylation. Only those products containing strong EWG substituents in the aroyl residue or bulky...
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Effects of Urea and Trimethylamine-N-oxide on the Properties of Water and the Secondary Structure of Hen Egg White Lysozyme
PublicationW celu określenia sposobu hydratacji mocznika i N-tlenku trimetyloaminy, wykorzystano spektroskopię oscylacyjną FTIR. Dane eksperymentalne, otrzymane z pomiarów widm oscylacyjnych wody półciężkiej (HDO) rozcieńczonej izotopowo w wodnych roztworach badanych związków, analizowane były za pomocą "metody widm różnicowych". Strukturalno-energetyczna charakterystyka wody zaburzonej przez cząsteczki osmolitów wskazuje, że woda zaburzona...
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Electronic structure and charge distribution in DyBa2Cu3O7: The ab initio approach
PublicationW pracy wykonano obliczenia kwantowomechaniczne struktury elektronowej nadprzewodzącego materiału DyBa2Cu3O7 (Dy123) metodą FP-LAPW (full potential - linearized augmented plane wave) w ramach formalizmu DFT (density functional theory) stosując przybliżenie GGA (generalized gradient approximation). Ze względu na silne oddziaływania korelacyjne elektronów 4f w atomie Dy zastosowano dodatkowo poprawkę kulombowską U w ramach modelu...
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Conformation Properties, Chiroptical Spectra, and Molecular Self-Assembly of 2,3-Piperazinodiones and Their Dithiono Analogues
PublicationRodzina chiralnych cyklicznych oksamidów została otrzymana przez kondensację optycznie czynnych 1,2-diamin ze szczawianem dietylu. Tionowanie produktów odczynnikiem Lawessona doprowadziło do chiralnych 2,3-dipiperazynodionów. Geometrie cząsteczkowe badano z użyciem obliczeń kwantowo-mechanicznych DFT i porównano z wynikami analizy krystalograficznej. Sześcioczłonowy pierścień heterocykliczny przyjmuje konformację półkrzesłową,...
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Theoretical Assessment of Excited State Gradients and Resonance Raman Intensities for the Azobenzene Molecule
PublicationThe ground state geometries and vibrational frequencies as well as the excitation energies and excited state gradients of the S 1(nπ*) and S 2(ππ * ) states of trans - and cis -azobenzene are investigated by several DFT methods, namely B3LYP, PBE, M06-2X, CAM-B3LYP, and ω B97X. Excited state properties and in particular gradients are also assessed using the wave function based methods EOM-CCSD and RASPT2/RASSCF. Comparison with...
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Anticancer and antimicrobial properties of novel η6-p-cymene ruthenium(ii) complexes containing a N,S-type ligand, their structural and theoretical characterization
PublicationRuthenium(II) complexes are lately of great scientific interest due to their chemotherapeutic potential asanticancer and antimicrobial agents. Here we present the synthesis of new pyrazole carbothioamidederivatives and their four arene–ruthenium complexes. The title compounds were characterized with theapplication of IR, NMR, mass spectrometry, elemental analysis and X-ray diffraction. Additionally, for newcomplexes DFT calculations...
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A novel (Ti/Ce)UiO-X MOFs@TiO2 heterojunction for enhanced photocatalytic performance: Boosting via Ce4+/Ce3+ and Ti4+/Ti3+ redox mediators
PublicationTitanium-substituted cerium-oxo-based UiO MOFs with terephthalate linkers modified by various groups (–Br, –NH2, –NO2) or their derivatives (N-heterocyclic or biphenyl groups) were combined with titanium dioxide in a multistep route to obtain a core-shell-like architecture. DFT simulations showed that Ce- and bimetallic Ti/Ce- MOFs exhibited different charge compensation. Extended characterization revealed the formation of heterojunctions between...
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Structural Insights into New Bi(III) Coordination Polymers with Pyridine-2,3-Dicarboxylic Acid: Photoluminescence Properties and Anti-Helicobacter pylori Activity
PublicationTwo novel coordination polymers, [Bi2(2,3pydc)2(2,3pydcH)2(H2O)]n(1) and {(Et3NH)2[Bi(2,3pydc)(2,3pydcH)Cl2]}n(2) were prepared using as a prolinker pyridine-2,3-dicarboxylic acid(2,3pydcH2). The obtained complexes were fully characterized by elemental analysis, TG/DTG, FT-IR,solid-state photoluminescence, DFT calculations and single-crystal X-ray diffraction. The obtainedcomplexes crystallized in the triclinicP-1 space group (1)...
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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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Reactive imines: Addition of 2-aminopyrimidine to the imine bond and isolation of the aminal from the equilibrium mixture aminal/imine
PublicationThe reaction between o-vanillin and 2-aminopyrimidine leads to the formation of a single crystalline product: aminal, 1, which results from the reaction of the initially formed imine with 2-aminopyrimidine. The reaction was followed by the NMR spectroscopy. VT NMR studies prove that in solution two major species are observed: aminal and imine and their ratio depends on the time or/and temperature with the imine content increasing...
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Superconductivity in a breathing kagome metals ROs2 (R = Sc, Y, Lu)
PublicationWe have successfully synthesized three osmium-based hexagonal Laves compounds ROs2 (R = Sc, Y, Lu), and discussed their physical properties. LeBail refinement of pXRD data confirms that all compounds crystallize in the hexagonal centrosymmetric MgZn2- type structure (P63/mmc, No. 194). The refined lattice parameters are a = b = 5.1791(1) Å and c = 8.4841(2) Å for ScOs2, a = b = 5.2571(3) Å and c = 8.6613(2) Å for LuOs2 and a =...
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Vibrational spectroscopic studies of N,N'-dimethylpropyleneurea-water system: Affected solvent spectra and factor analysis
PublicationZmierzono widma FT-IR układu N,N'-dimetylopropylenomocznik (DMPU) - woda w całym zakresie składów w zakresie 4000-500 cm-1 przy użyciu techniki całkowitego wewnętrznego odbicia (ATR). Hydratacja DMPU została dodatkowo zbadana przy pomocy transmisyjnej spektroskopii FT-IR izotopowo rozcieńczonej HDO w H2O. Widma zanalizowano przy użyciu ilościowej wersji metody widm różnicowych, prowadzącej do wyizolowania widma rozpuszczalnika...
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An unusual four-nuclear Pb(II)-pyrrole-2-carboxylato polymer: The effect of the lone pair and non-covalent interactions on the supramolecular assembly and fluorescence properties
PublicationThe reaction of Pb(NO3)2 with 1H-pyrrole-2-carboxylic acid (2prCOOH) leads to the formation of a new four-nuclear Pb(II) polymer, [Pb4(2prCOO)8(H2O)]n, which has been characterized by CHN, FT-IR, TG, PL and single-crystal X-ray diffraction methods. In view of the primary Pb–O bonds, Pb1 and Pb3 show hemidirected pentagonal pyramidal geometries, while Pb2 and Pb4 display hemidirected octahedral geometries. The topology of the strongest...
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Texture or Linker? Competitive Patterning of Receptor Assembly toward Ultra-Sensitive Impedimetric Detection of Viral Species at Gold-Nanotextured Titanium Surfaces
PublicationIn this work, we study the electrodes with a periodic matrix of gold particles pattered by titanium dimples and modified by 3-mercaptopropionic acid (MPA) followed by CD147 receptor grafting for specific impedimetric detection of SARS-CoV-2 viral spike proteins. The synergistic DFT and MM/MD modeling revealed that MPA adsorption geometries on the Au–Ti surface have preferential and stronger binding patterns through the carboxyl...
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Ultrasound-Assisted Dispersive Liquid-Liquid Microextraction Using Deep Eutectic Solvents (DESs) for Neutral Red Dye Spectrophotometric Determination
PublicationDeep eutectic solvents (DES), which have low toxicity and are low cost, biodegradable, and easily synthesized, were used for the extraction of neutral red (NR) dye before its spectrophotometric analysis. DES, containing choline chloride as a hydrogen bond acceptor and phenol as a hydrogen bond donor with a molar ratio of 1:2, was used for the extraction of NR dye from aqueous media. The possible interaction of different DESs with...
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Computational analysis of substituent effects on proton affinity and gas-phase basicity of TEMPO derivatives and their hydrogen bonding interactions with water molecules
PublicationThe study investigates the molecular structure of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) and its derivatives in the gas phase using B3LYP and M06-2X functional methods. Intermolecular interactions are analyzed using natural bond orbital (NBO) and atoms in molecules (AIM) techniques. NO2-substituted TEMPO displays high reactivity, less stability, and softer properties. The study reveals that the stability of TEMPO derivatives...
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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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Amides as models to study the hydration of proteins and peptides — spectroscopic and theoretical approach on hydration in various temperatures
PublicationInteractions with water are one of the key factors which determine protein stability and activity in aqueous solutions. However, the protein hydration is still insufficiently understood. N-methylacetamide (NMA) is regarded as a minimal part of the peptide backbone and the relative simplicity of its structure makes it a good model for studies on protein–water interactions. In this paper, the influence of NMA and N,N-dimethylacetamide...
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Geometry optimization of steroid sulfatase inhibitors - the influence on the free binding energy with STS
PublicationIn the paper we review the application of two techniques (molecular mechanics and quantum mechanics) to study the influence of geometry optimization of the steroid sulfatase inhibitors on the values of descriptors coded their chemical structure and their free binding energy with the STS protein. We selected 22 STS-inhibitors and compared their structures optimized with MM+, PM7 and DFT B3LYP/6–31++G* approaches considering separately...
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Chiral and achiral crystals, charge-assisted hydrogen-bond patterns and self-organization of selected solid diaminium thiosulfates
PublicationAbstract A series of diaminium thiosulfates, derivatives of diamines: NH2CH2CH(CH3)NH2 (1) and NH2(CH2)nNH2, n = 3-6 (2-5 respectively)and thiosulfuric acid were prepared and their structures determined by crystal X-ray diffraction analysis. Compounds 1, 2 and 4 turned out to be hydrates. The crystal structure of 1,2-proylenediaminium thiosulfate is chiral and exhibits spontaneous resolution. Crystals for both enantiomers...
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TINKTEP: A fully self-consistent, mutually polarizable QM/MM approach based on the AMOEBA force field
PublicationWe present a novel quantum mechanical/molecular mechanics (QM/MM) approach in which a quantum subsystem is coupled to a classical subsystem described by the AMOEBA polarizable force field. Our approach permits mutual polarization between the QM and MM subsystems, effected through multipolar electrostatics. Self-consistency is achieved for both the QM and MM subsystems through a total energy minimization scheme. We provide an expression...
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The Reactivity of Phosphanylphosphinidene Complexes of Transition Metals Toward Terminal Dihaloalkanes
PublicationThe reactivities of phosphanylphosphinidene complexes [(DippN)2W(Cl)(η2-P−PtBu2)]− (1), [(pTol3P)2Pt(η2- P=PtBu2)] (2), and [(dppe)Pt(η2-P=PtBu2)] (3) toward dihaloalkanes and methyl iodide were investigated. The reactions of the anionic tungsten complex (1) with stochiometric Br(CH2)nBr (n = 3, 4, 6) led to the formation of neutral complexes with a tBu2PP(CH2)3Br ligand or neutral dinuclear complexes with unusual tetradentate...
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DMSO hydration redefined: Unraveling the hydrophobic hydration of solutes with a mixed hydrophilic–hydrophobic characteristic
PublicationHydrophobic hydration of solutes with a mixed hydrophilic--hydrophobic characteristics is still poorly understood. This is because both experimental and theoretical methods find it difficult to see the ice-like water structure around the nonpolar solute groups, unlike hydrogen bonds with the hydrophilic groups. In order to unravel this problem, we have investigated DMSO hydration by means of infrared spectroscopy and theoretical...
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Non-ergodic fragmentation upon collision-induced activation of cysteine–water cluster cations
PublicationCysteine–water cluster cations Cys(H2O)3,6 + and Cys(H2O)3,6H+ are assembled in He droplets and probed by tandem mass spectrometry with collision-induced activation. Benchmark experimental data for this biologically important system are complemented with theory to elucidate the details of the collisioninduced activation process. Experimental energy thresholds for successive release of water are compared to water dissociation energies...
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Impedimetric sensing of α-amino acids driven by micro-patterned 1,8-Diazafluoren-9-one into titania- boron- doped maze-like nanocarbons
PublicationThe development of impedimetric, non-faradaic label-free sensors for the detection of α-amino acids constitutes a trailblazing technology for the fast and inexpensive quantification of such biomarkers. Since α-amino acids, such as glycine and sarcosine, are basic constituents in biological processes, a variation in their concentration may be an indicator of cardiovascular diseases and metabolic disorders or neurological conditions....
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Effect of Aromatic System Expansion on Crystal Structures of 1,2,5-Thia- and 1,2,5-Selenadiazoles and Their Quaternary Salts: Synthesis, Structure, and Spectroscopic Properties
PublicationRational manipulation of secondary bonding interactions is a crucial factor in the construction of new chalcogenadiazole-based materials. This article reports detailed experimental studies on phenanthro[9,10-c][1,2,5]chalcogenadiazolium and 2,1,3-benzochalcogenadiazolium salts and their precursors. The compounds were synthesized, characterized employing NMR and UV-Vis spectroscopy. TD-DFT calculations were also performed. The influence...
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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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Optical and photocatalytic properties of rare earth metal-modified ZnO quantum dots
PublicationA series of novel ZnO quantum dots modified with rare earth metals was successfully prepared by a simple sol-gel approach. The effects of types (Eu, Er, Tb, Yb, Ho, La) and amounts (from 0.09 to 0.45 mmol) of lanthanides on the optical properties, structural characterization and photocatalytic activity of ZnO/RE QDs were systematically investigated. The X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Fourier transform...
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Direct determination of paraquat herbicide by square-wave voltammetry by two-step transfer mechanism at heterogeneous boron-doped carbon nanowall electrodes
PublicationBoron-doped carbon nanowalls (B:CNW) versus boron-doped diamond (BDD) materials were investigated for the effective electrochemical detection of highly toxic herbicide paraquat (PQ). Depending on the surface morphology and functional groups of BDD and B:CNWs, the electrochemical absorption and detection of the target analyte PQ revealed different detection mechanisms. The surface absorption mechanism was mainly observed for BDD,...
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Taurine as a water structure breaker and protein stabilizer
PublicationThe enhancing effect on the water structure has been confirmed for most of the osmolytes exhibiting both stabilizing and destabilizing properties in regard to proteins. The presented work concerns osmolytes, which should be classified as “structure breaking” solutes: taurine and N,N,N-trimethyltaurine (TMT). Here, we combine FTIR spectroscopy, DSC calorimetry and DFT calculations to gain an insight into the interactions between...
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The new diphosphanylphosphido complexes of tungsten(VI) and molybdenum(VI). Their synthesis, structures and properties
PublicationWe report on the reactivity of R2P–P(Li)–PR’2 (R = tBu, iPr, R’ = NEt2, iPr) towards diimido complexes [(dippN)2MCl2·dme] (M = Mo, W and dipp = 2,6-iPr2C6H3). A series of new complexes with diphosphanylphosphido ligands R2P–P–PR’2 were isolated. The solid-state structures of [(dippN)2M(Cl)(1,2-η-iPr2P–P– PiPr2)] (2Mo and 2W) and [(dippN)2M(Cl){1,2-η-tBu2P–P–P(NEt2)2}] (3Mo and 3W) were established by single-crystal X-ray diffraction...
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Compressive Sensing Approach to Harmonics Detection in the Ship Electrical Network
PublicationThe contribution of this paper is to show the opportunities for using the compressive sensing (CS) technique for detecting harmonics in a frequency sparse signal. The signal in a ship’s electrical network, polluted by harmonic distortions, can be modeled as a superposition of a small number of sinusoids and the discrete Fourier transform (DFT) basis forms its sparse domain. According to the theory of CS, a signal may be reconstructed...
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Homoleptic mono-, di-, and tetra-iron complexes featuring phosphido ligands: a synthetic, structural, and spectroscopic study
PublicationWe report the first series of homoleptic phosphido iron complexes synthesized by treating either the β-diketiminato complex [(Dippnacnac)FeCl2Li(dme)2] (Dippnacnac = HC[(CMe)N(C6H3-2,6-iPr2)]2) or [FeBr2(thf )2] with an excess of phosphides R2PLi (R = tBu, tBuPh, Cy, iPr). Reaction outcomes depend strongly on the bulkiness of the phosphido ligands. The use of tBu2PLi precursor led to an anionic diiron complex 1 encompassing a planar...
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Structural and spectroscopic analysis of a new family of monomeric diphosphinoboranes
PublicationWe present a series of amino- and aryl(diphosphino)boranes R2PB(R’’)PR’2, where R2P, R’2P = tBu2P, tBuPhP, Ph2P, Cy2P, and R’’ = iPr2N, Ph, which were obtained via the metathesis reaction of iPr2NBBr2 or PhBBr2 with selected lithium phosphides. The structures of isolated diphosphinoboranes were characterized in the solid state and in solution by means of X-ray diffraction and NMR spectroscopy, respectively. The utility of these...
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Photocatalytic degradation and pollutant-oriented structure-activity analysis of carbamazepine, ibuprofen and acetaminophen over faceted TiO2
PublicationPhotocatalytic degradation of carbamazepine, ibuprofen, acetaminophen and phenol was studied in the presence of anatase photocatalyst, exposing three different crystal facets in the majority of {0 0 1}, {1 0 0} or {1 0 1}. It was found that octahedral anatase particles exposing {1 0 1} facets allow to achieve the best degradation and mineralization of all persistent organic pollutants. This confirms that the previous findings,...
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Removal of diphenols using pine biochar. Kinetics, equilibrium, thermodynamics, and mechanism of uptake
PublicationThermal pyrolysis synthesized activated biochar from the Pinus elliottii sawdust (PS) at 600° C. The obtained activated biochar (PB600) was used for the removal of three diphenols, catechol (CAT), resorcinol (RES), and hydroquinone (HYD), which are utilized mainly in different industries. The PB600 was characterized by several analytical techniques. The BET surface area of 1473 m2.g−1 and a total pore volume of 0.707 cm3 g−1 was...
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Two complementary approaches for the synthesis and isolation of stable phosphanylphosphaalkenes
PublicationPhospha-Wittig (phosphanylphosphinidene titanium(IV) complex) and phospha-Peterson (lithiated diphosphane) reactions were used to obtain phosphanylphosphaalkenes with the general formula XYC=P-PtBu2 (X = alkyl, aryl group or H; Y = alkyl or aryl group). Therefore, two series of reactions with different ketones and aldehydes were performed. An examination revealed that the two methods are complementary. For smaller carbonyl compounds,...
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Photoresponsive Amide-Based Derivatives of Azobenzene-4,4′-Dicarboxylic Acid—Experimental and Theoretical Studies
PublicationAzobenzene derivatives are one of the most important molecular switches for biological and material science applications. Although these systems represent a well-known group of compounds, there remains a need to identify the factors influencing their photochemical properties in order to design azobenzene-based technologies in a rational way. In this contribution, we describe the synthesis and characterization of two novel amides...
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Synthesis of Cyano-Benzylidene Xanthene Synthons Using a Diprotic Brønsted Acid Catalyst, and Their Application as Efficient Inhibitors of Aluminum Corrosion in Alkaline Solutions
PublicationNovel cyano-benzylidene xanthene derivatives were synthesized using one-pot and condensation reactions. A diprotic Brønsted acid (i.e., oxalic acid) was used as an effective catalyst for the promotion of the synthesis process of the new starting xanthene–aldehyde compound. Different xanthene concentrations (ca. 0.1–2.0 mM) were applied as corrosion inhibitors to control the alkaline uniform corrosion of aluminum. Measurements were...
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Magnetic deep eutectic solvents as efficient media for extraction of furfural and 5-hydroxymethylfurfural from aqueous samples
PublicationThe extraction of furfural (FF) and 5-hydroxymethylfurfural (HMF) from hydrolysates is currently one of the main challenges in bio-refinery. In this work, the separation of FF and HMF from the aqueous phase was carried out using a new type of green solvents – Magnetic Deep Eutectic Solvents (MDES). A conductor-like screening model for realistic solvents (COSMO-RS) was used for the preselection of 400 MDES. MDES which exhibit the...
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Engineering boron and nitrogen codoped carbon nanoarchitectures to tailor molecularly imprinted polymers for PFOS determination
PublicationPer- and polyfluoroalkyl substances (PFAS) have gained significant attention as emerging contaminants due to their persistence, abundance, and adverse health effects. Consequently, the urgent need for ubiquitous and effective sensors capable of detecting and quantifying PFAS in complex environmental samples has become a priority. In this study, we present the development of an ultrasensitive molecularly imprinted polymer (MIP)...
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Formation of chlorinated breakdown products during degradation of sunscreen agent, 2-ethylhexyl-4-methoxycinnamate in the presence of sodium hypochlorite
PublicationIn this study, a new degradation path of sunscreen active ingredient, 2-ethylhexyl-4-methoxycinnamate (EHMC) and 4-methoxycinnamic acid (MCA) in the presence of sodium hypochlorite (NaOCl), was discussed. The reaction products were detected using gas chromatography–mass spectrometry (GC-MS). Since HOCl treatment leads to more polar products than EHMC, application of polar extracting agents, dichloromethane and ethyl acetate/n-hexane...
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The Metal-Free Regioselective Deuteration of 2-Methylquinolin-8-ol and 2,5-Dimethylquinolin-8-ol, Spectroscopic and Computational Studies
PublicationAbstract: Aim and Background: Introducing deuterium to a molecule is of interest to a wide variety of research, including investigation of reaction mechanisms or kinetics, analysis of drug metabolism, structural elucidation of molecules, and syntheses of isotopically labeled materials used for NMR spectroscopy and medicinal research. Objective: The transition-metal-free regioselective deuteration of 2-methylquinolin-8-ol...
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Solvent influence on the crystal structures of new cadmium tri-tert -butoxysilanethiolate complexes with 1,4-bis(3-aminopropyl)piperazine: luminescence and antifungal activity
PublicationMonocrystals of dinuclear -1,4-bis(3-aminopropyl)piperazine-4N1,N10:N4,N40-bis[bis(tri-tert-butoxysilanethiolato-S)cadmium(II)], [Cd2(C12H27O3SSi)4(C10-H24N4)] or [Cd2{SSi(OtBu)3}4(-BAPP)], 1, and polynuclear catena-poly[[bis-(tri-tert-butoxysilanethiolato-S)cadmium(II)]--1,4-bis(3-aminopropyl)piperazine-2N10:N40], [Cd(C12H27O3SSi)2(C10H24N4)]n or [Cd{SSi(OtBu)3}2(-BAPP)]n,2, with 1,4-bis(3-aminopropyl)piperazine (BAPP)...
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Synthesis, physicochemical and theoretical studies on new rhodium and ruthenium dimers. Relationship between structure and cytotoxic activity
PublicationTwo dimeric compounds of the general formulae (Et3NH)2[Rh2(μ2-L)4Cl2] (1) (where L = thiophene-2-carboxylate) and [((η6-p-cymene)Ru)2(μ-Cl)3]PF6 (2) have been synthesized using a new method. The unique anionic complex 1 (space group P bca) has octahedral coordination in which the equatorial positions are occupied by the oxygen atoms of four thiophene-2-carboxylates in a paddle wheel fashion. In complex 2 (space group ), each Ru(II)...