Shape-responsive host-guest chemistry: metal-free tetracationic porphyrin nonplanarity promoted by clay mineral interactions assessed by theoretical simulations.

Distortions in the porphyrin core from planarity can trigger a unique structure-property relationship, imparting its basicity, chemical stability, redox potential, and excited-state energetics, among other properties. The colour change promoted by such distortion is signed by red shifts in its electronic absorption spectra. The adsorption of guest -substituted free-base porphyrin species onto inorganic hosts, such as clay minerals (layered aluminium or magnesium silicates), is known to further promote colour changes.

Pressure-Induced Phase Transformations of Quasi-2D SrHfO.

We present an abinitio study of the quasi-2D layered perovskite SrHfO compound, performed within the framework of the density functional theory and lattice dynamics analysis. At high temperatures, this compound takes a centrosymmetric structure (S.G.

Correlation of Interface Interdiffusion and Skyrmionic Phases.

Magnetic skyrmions are prime candidates for the next generation of spintronic devices. Skyrmions and other topological magnetic structures are known to be stabilized by the Dzyaloshinskii-Moriya interaction (DMI) that occurs when the inversion symmetry is broken in thin films. Here, we show by first-principles calculations and atomistic spin dynamics simulations that metastable skyrmionic states can also be found in nominally symmetric multilayered systems.

Folic acid and sodium folate salts: Thermal behavior and spectroscopic (IR, Raman, and solid-state C NMR) characterization.

Folic acid (FA; vitamin B9) and its associated sodium salts, strongly relevant for many scientific and technological applications - from nutrition to pharmacology and nanomedicine, suffer from a lack of characterization combining experimental and theoretical. In this work, a spectroscopic investigation of FA and its synthesized sodium salts in the form of dianion (NaHFol) or trianion (NaFol) was scrutinized in their solid state. The spectroscopic (infrared, Raman, and solid state C-nuclear magnetic resonance) data interpretation was supported by theoretical calculations using the Density Functional Theory (DFT).

Group Theory Analysis to Study Phase Transitions of Quasi-2D SrHfO.

We present an study performed in the framework of density functional theory, group-subgroup symmetry analysis and lattice dynamics, to probe the octahedral distortions, which occur during the structural phase transitions of the quasi-2D layered perovskite SrHfO compound. Such a system is characterized by a high-temperature centrosymmetric structure and a ground-state ferroelectric phase. We have probed potential candidate polymorphs that may form the → transition pathways, namely , , and .

Heterobinuclear copper(II)‑platinum(II) complexes with oxindolimine ligands: Interactions with DNA, and inhibition of kinase and alkaline phosphatase proteins.

Two mononuclear copper(II) compounds, [Cu(isad)(HO)Cl]Cl 1 and [Cu(isah)(HO)Cl]Cl 2, and its corresponding heterobinuclear species containing also platinum(II), [CuCl(isad)Pt(NH)Cl] 3 and [CuCl(isah)Pt(NH)Cl] 4 (where isad and isah are oxindolimine ligands, (E)-3-(2-(3-aminopropylamino)ethylimino)indolin-2-one, and (E)-3-(3-amino-2-hydroxypropylimino)indolin-2-one, respectively), have been previously synthesized and characterized by different spectroscopic techniques in our laboratory. Cytotoxicity assays performed with B16F10 murine cancer cells, and MES-SA human uterine sarcoma cells, showed IC values lower or in the same order of cisplatin. Herein, in order to better elucidate their probable modes of action, possible interaction and damage to DNA, as well as their effect on the activity of crucial proteins were verified.

Theoretical UV-Vis spectra of tetracationic porphyrin: effects of environment on electronic spectral properties.

Electronic and spectroscopic properties of tetracationic 5,10,15,20-tetrakis(1-methyl-4-pyridyl)-21H,23H-porphyrin (TMPyP) were investigated in the framework of the density functional theory (DFT). Modeling of implicit solvent, charge effects, and medium acidity were performed and compared with experimental results. Various hybrid exchange correlation functionals in the Kohn-Sham Scheme of the DFT were employed and various porphyrin models were constructed, simulating different environmental conditions.

Noncollinear magnetism of Mn nanowires on Fe(1 1 0).

Magnetic properties of Mn linear nanochains on a bcc Fe(1 1 0) surface have been studied using the first-principles real space-linear muffin-tin orbital atomic sphere approximation (RS-LMTO-ASA) method. We have considered up to nine Mn atoms deposited on bcc Fe(1 1 0). Our ab initio calculations reveal the competition between the antiferromagnetic Mn-Mn and Mn-Fe couplings, presenting a behavior which is very different from Mn nanowires on Fe(0 0 1), as shown in a previous publication.

Delivery system for mefenamic acid based on the nanocarrier layered double hydroxide: Physicochemical characterization and evaluation of anti-inflammatory and antinociceptive potential.

Purpose: The anionic form of the drug mefenamic acid intercalated into the nanocarrier layered double hydroxide (LDH-Mef) was evaluated by anti-inflammatory and antinociceptive assays.

Methods: The LDH-Mef material was characterized by a set of physicochemical techniques, which was supported by Density Functional Theory calculations. The pharmacological effects of LDH-Mef (40 wt% of drug) were evaluated by hemolytic, anti-inflammatory activity and antinociceptive assays.

Inhibition of cyclin-dependent kinase CDK1 by oxindolimine ligands and corresponding copper and zinc complexes.

Oxindolimine-copper(II) and zinc(II) complexes that previously have shown to induce apoptosis, with DNA and mitochondria as main targets, exhibit here significant inhibition of kinase CDK1/cyclin B protein. Copper species are more active than the corresponding zinc, and the free ligand shows to be less active, indicating a major influence of coordination in the process, and a further modulation by the coordinated ligand. Molecular docking and classical molecular dynamics provide a better understanding of the effectiveness and kinase inhibition mechanism by these compounds, showing that the metal complex provides a stronger interaction than the free ligand with the ATP-binding site.

Metal coordination study at Ag and Cd sites in crown thioether complexes through DFT calculations and hyperfine parameters.

Structural and electronic properties of [C12H24S6X], [C13H26S6OX], and [C14H28S6OX] (X: Ag(+), Cd(2+)) crown thioether complexes were investigated within the framework of the density functional theory (DFT) using the projector augmented wave (PAW) method. The theoretical results were compared with time-differential perturbed γ-γ angular correlations (TDPAC) experiments reported in the literature using the (111)Ag→(111)Cd probe. In the case of X=Ag(+), a refinement of the structure was performed and the predicted equilibrium structures compared with available X-ray diffraction experimental data.

Cd hyperfine interactions in DNA bases and DNA of mouse strains infected with Trypanosoma cruzi investigated by perturbed angular correlation spectroscopy and ab initio calculations.

In this work, perturbed angular correlation (PAC) spectroscopy is used to study differences in the nuclear quadrupole interactions of Cd probes in DNA molecules of mice infected with the Y-strain of Trypanosoma cruzi. The possibility of investigating the local genetic alterations in DNA, which occur along generations of mice infected with T. cruzi, using hyperfine interactions obtained from PAC measurements and density functional theory (DFT) calculations in DNA bases is discussed.

Magnetic properties of Fe(x)Co(1-x) nanochains on Pt(1 1 1) surfaces.

The magnetic properties of FexCo1-x nanochains on Pt(1 1 1) were studied using the first-principles real-space linear muffin-tin orbital-atomic sphere approximation (RS-LMTO-ASA) method within the density functional theory. The relative amounts of Fe and Co atoms in a chosen nanochain were varied and several possible arrangements of the atomic species were taken into account. The results of the exchange interaction demonstrates ferromagnetic coupling for the nanowires.

Mefenamic acid anti-inflammatory drug: probing its polymorphs by vibrational (IR and Raman) and solid-state NMR spectroscopies.

This work deals with the spectroscopic (supported by quantum chemistry calculations), structural, and morphological characterization of mefenamic acid (2-[(2,3-(dimethylphenyl)amino] benzoic acid) polymorphs, known as forms I and II. Polymorph I was obtained by recrystallization in ethanol, while form II was reached by heating form I up to 175 °C, to promote the solid phase transition. Experimental and theoretical vibrational band assignments were performed considering the presence of centrosymmetric dimers.

Industrial Scale Isolation, Structural and Spectroscopic Characterization of Epiisopiloturine from Pilocarpus microphyllus Stapf Leaves: A Promising Alkaloid against Schistosomiasis.

This paper presents an industrial scale process for extraction, purification, and isolation of epiisopiloturine (EPI) (2(3H)-Furanone,dihydro-3-(hydroxyphenylmethyl)-4-[(1-methyl-1H-imidazol-4-yl)methyl]-, [3S-[3a(R*),4b]]), which is an alkaloid from jaborandi leaves (Pilocarpus microphyllus Stapf). Additionally for the first time a set of structural and spectroscopic techniques were used to characterize this alkaloid. EPI has shown schistomicidal activity against adults and young forms, as well as the reduction of the egg laying adult worms and low toxicity to mammalian cells (in vitro).

Peculiar reactivity of a di-imine copper(II) complex regarding its binding to albumin protein.

A set of four di-imine copper(II) complexes containing pyridine, pyrazine and/or imidazole moieties, [Cu(apyhist)H2O](2+) 1 (apyhist = 2-(1H-imidazol-4-yl)-N-(1-(pyridin-2-yl)ethylidene)ethanamine), [Cu(apzhist)OH](+) 2 (apzhist = 2-(1H-imidazol-4-yl)-N-(1-(pyrazin-2-yl)ethylidene)ethanamine), [Cu(apyepy)OH](+) 3 (apyepy = 2-(pyridin-2-yl)-N-(1-(pyridin-2-yl)ethylidene)ethanamine), and [Cu(apzepy)H2O](2+) 4 (apzepy = N-(1-(pyrazin-2-yl)ethylidene)-2-(pyridin-2-yl)ethanamine), were investigated regarding their capability of interacting with serum albumin (human, HSA and bovine, BSA), by using spectroscopic techniques, CD, UV/Vis and EPR. Like other similar di-imine copper(II) complexes, most of them showed an expected preferential insertion of the metal ion at the primary N-terminal site of the protein, very selective for copper and characterized by a CD band at 560 nm. Further insertion of the copper ion at a secondary site is expected when using an excess of the metal.

Electric field gradients in (111)In-doped (Hf/Zr)3Al2 and (Hf/Zr)4Al3 mixed compounds: ab initio calculations, perturbed angular correlation measurements and site preference.

The quadrupolar hyperfine interactions of in-diffused (111)In --> (111)Cd probes in polycrystalline isostructural Zr(4)Al(3) and Hf(4)Al(3) samples containing small admixtures of the phases (Zr/Hf)(3)Al(2) were investigated. A strong preference of (111)In solutes for the contaminant (Zr/Hf)(3)Al(2) minority phases was observed. Detailed calculations of the electric field gradient (EFG) at the Cd nucleus using the full-potential augmented plane wave + local orbital formalism allowed us to assign the observed EFG fractions to the various lattice sites in the (Zr/Hf)(3)Al(2) compounds and to understand the preferential site occupation of the minority phases by the (111)In atoms.

Hyperfine and magnetic properties of Fe-Cu clusters and Fe precipitates embedded in a Cu matrix.

Using the first-principles real-space linear muffin-tin orbital method within the atomic sphere approximation (RS-LMTO-ASA) we study hyperfine and local magnetic properties of substituted pure Fe and Fe-Cu clusters in an fcc Cu matrix. Spin and orbital contributions to magnetic moments, hyperfine fields and the Mössbauer isomer shifts at the Fe sites in Fe precipitates and Fe-Cu alloy clusters of sizes up to 60 Fe atoms embedded in the Cu matrix are calculated and the influence of the local environment on these properties is discussed.

Oxindole-Schiff base copper(II) complexes interactions with human serum albumin: spectroscopic, oxidative damage, and computational studies.

CD and EPR were used to characterize interactions of oxindole-Schiff base copper(II) complexes with human serum albumin (HSA). These imine ligands form very stable complexes with copper, and can efficiently compete for this metal ion towards the specific N-terminal binding site of the protein, consisting of the amino acid sequence Asp-Ala-His. Relative stability constants for the corresponding complexes were estimated from CD data, using the protein as competitive ligand, with values of log K(CuL) in the range 15.

Hyperfine interaction studies with (181)Ta and (111)Cd probes in the compound Ti(2)Ag.

By using the time-differential perturbed angular correlation technique, the electric field gradients (EFG) at (181)Hf/(181)Ta and (111)In/(111)Cd probe sites in the MoSi(2)-type compound Ti(2)Ag have been measured as a function of temperature in the range from 24 to 1073 K. Ab initio EFG calculations have been performed within the framework of density functional theory using the full-potential augmented plane wave+local orbitals method as implemented in the WIEN2k package. These calculations allowed assignments of the probe lattice sites.

Application of standard DFT theory for nonbonded interactions in soft matter: prototype study of poly-para-phenylene.

We present a detailed analysis of the application of density functional theory (DFT) methods to the study of structural properties of molecular and supramolecular systems, using as a paradigmatic example three para-phenylene-based systems: isolated biphenyl, single chain poly-para-phenylene, and crystalline biphenyl. We use different functionals for the exchange correlation potential, the local density (LDA), and generalized gradient approximations (GGA), and also different basis sets expansions, localized, plane waves (PW), and mixed (localized plus PW), within the reciprocal space formulation for the hamiltonian. We find that regardless of the choice of basis functions, the GGA calculations yield larger interring distances and torsion angles than LDA.

Nitrogen binding to the FeMo-cofactor of nitrogenase.

Density functional calculations are presented to unravel the first steps of nitrogen fixation of nitrogenase. The individual steps leading from the resting state to nitrogen binding at the FeMo-cofactor with a central nitrogen ligand are characterized. The calculations indicate that the Fe-Mo cage opens as dinitrogen binds to the cluster.