Density functional calculation of the 2D potential surface and deuterium isotope effect on 13C chemical shifts in picolinic acid N-oxide. Comparison with experiment

2D free energy surfaces V = V(rOH, rO...O) for the intramolecular H-bond in the title compound were calculated by the DFT method and used in the calculation of primary and secondary chemical shifts of the compound dissolved in chloroform and acetonitrile. Solvent effects were accounted for by the SCRF/PCM method. The corresponding two-dimensional chemical shift surfaces with included solvent reaction field were obtained using the Continuous Set of Gauge Transformations approach at the B3LYP/6-311+G(2d,2p) level of theory. The chemical shifts were estimated as quantum averages along the two internal coordinates in the hydrogen bond and along several vibrational levels according to the Boltzmann distribution at room temperature. Fairly good agreement between the experimental and calculated isotope effects was obtained. 1D and 2D NMR spectra of solutions of picolinic acid N-oxide and its deuterated analogue were recorded and assigned.     

Synthesis and characterisation of Pd(II) complexes with a derivative of aminoazobenzene: Dynamic H-NMR study of cyclopalladation reactions in DMF

Three new Pd(II) complexes, i.e. [PdCl₂L]₂ (A), PdCl₂L₂ (B) and [Pd(μ-Cl)(L-H)]₂ (C), each with two diethyl [α-(4-benzenazoanilino)-2-hydroxybenzyl]phosphonates (L) bound to either one or two palladium atoms, are synthesized and characterized by elemental analysis, by IR, UV-vis and solid-state ¹³C-NMR spectra. Complexes B and C are additionally characterized by ¹H-, ¹³C- and ³¹P-NMR and electrospray mass spectrometry (ESMS) studies using dimethylformamide (DMF) as a solvent. In DMF solution adducts A and B undergo spontaneous rearrangement into the cyclopalladated complex C. Dynamic ¹H-NMR study of this rearrangement as well as of the reactions of L with PdCl₂ and Na₂PdCl₄ revealed a complex equilibrium in DMF solutions and enabled the formation mechanism of all involved species to be resolved. The complex A is immediately solvolyzed producing two molecules of intermediate M [PdCl₂(L)(DMF)]. Complex M was also the first intermediate in the reaction of L with PdCl₂. Once present in concentration above 10⁻⁵ mol dm⁻³M dimerizes very fast into chloro-bridged dimer [PdCl(μ-Cl)(L)]₂ (D) which undergoes cyclopalladation and converts into the complex C. The formation of C from the intermediate D is clearly demonstrated by the concentration dependence of the cyclopalladation reaction which has order greater than one. Chloride ions, released by cyclopalladation, react with D by splitting chloro-bridge and binding to metal atoms to produce byproduct [PdCl₃(L)]⁻ (T). The same species T are formed in the reaction of L with Na₂PdCl₄ whereby a chloride ion is replaced by the ligand L. The complex B undergoes similar, but slower, solvolytic reaction producing M and L while further reaction steps are identical as in the solvolysis of A.     

Conformational Properties of New Thiosemicarbazone and Thiocarbohydrazone Derivatives and Their Possible Targets

The structure assignment and conformational analysis of thiosemicarbazone KKI15 and thiocarbohydrazone KKI18 were performed through homonuclear and heteronuclear 2D Nuclear Magnetic Resonance (NMR) spectroscopy (2D-COSY, 2D-NOESY, 2D-HSQC, and 2D-HMBC) and quantum mechanics (QM) calculations using Functional Density Theory (DFT). After the structure identification of the compounds, various conformations of the two compounds were calculated using DFT. The two molecules showed the most energy-favorable values when their two double bonds adopted the E configuration. These configurations were compatible with the spatial correlations observed in the 2D-NOESY spectrum. In addition, due to the various isomers that occurred, the energy of the transition states from one isomer to another was calculated. Finally, molecular binding experiments were performed to detect potential targets for KKI15 and KKI18 derived from SwissAdme. In silico molecular binding experiments showed favorable binding energy values for all four enzymes studied. The strongest binding energy was observed in the enzyme butyrylcholinesterase. ADMET calculations using the preADMET and pKCSm software showed that the two molecules appear as possible drug leads.     

Spin label EPR-based characterization of biosystem complexity

Following the widely spread EPR spin-label applications for biosystem characterization, a novel approach is proposed for EPR-based characterization of biosystem complexity. Hereto a computational method based on a hybrid evolutionary optimization (HEO) is introduced. The enormous volume of information obtained from multiple HEO runs is reduced with a novel so-called GHOST condensation method for automatic detection of the degree of system complexity through the construction of two-dimensional solution distributions. The GHOST method shows the ability of automatic quantitative characterization of groups of solutions, e.g. the determination of average spectral parameters and group contributions. The application of the GHOST condensation algorithm is demonstrated on four synthetic examples of different complexity and applied to two physiologically relevant examples--the determination of domains in biomembranes (lateral heterogeneity) and the study of the low-resolution structure of membrane proteins.     

Über die Trennung von gasgemischen in laminarer Strömung

Summary The separation effect in a gas mixture laminary and hydrodynamically flowing through a cylindrical pipe with constant wall temperature is calculated.     

Potentiometric discrimination of neutral forms of nitrophenol isomers by liquid membrane electrodes incorporated with corroles

The results of studies on the use of corrole derivatives as a host ligand in the PVC liquid membrane electrodes and their ability for the potentiometric high-throughput discrimination of nitrophenol guests have been presented. The significance of parameters which govern the mechanism of generation of potentiometric signals such as the attachment of substituents in the corrole structure, acidity and lipophilicity of the guests, and pH of the aqueous solutions has been discussed in details. Supramolecular recognition processes between corroles and para-nitrophenol molecules have been confirmed by independent NMR measurements.     

Extended Global Convergence Framework for Unconstrained Optimization

An extension of the global convergence framework for unconstrained derivative-free optimization methods is presented. The extension makes it possible for the framework to include optimization methods with varying cardinality of the ordered direction set. Grid-based search methods are shown to be a special case of the more general extended global convergence framework. Furthermore,the required properties of the sequence of ordered direction sets listed in the definition of grid-based methods are relaxed and simplified by removing the requirement of structural equivalence.     

Diversity of TiO<Subscript>2</Subscript> nanopowders’ characteristics relevant to toxicity testing

In this study, the physicochemical properties of several commercial ultrafine TiO₂ powders and their behaviour in the as-received form and colloidal suspensions were analysed. Besides the particle size, the morphology and agglomeration state of the dry powders, dispersibility, ζ-potential and sedimentation in water and in phosphate-buffered saline (PBS) were studied. Also, leaching of ions from the powders during ageing in physiological solution and the ability of the photoactivated powders to decompose organic substances were evaluated. The examined TiO₂ powders revealed diversified characteristics when dispersed in water. In general, while in dry conditions the particle size appeared in the nano-range (down to 32 nm), the particles were agglomerated in aqueous suspensions at pH ~7 and only a minor amount showed dimensions below 200 nm, but none below 100 nm. The inherent pH of the 3 % suspensions varies from 3.7 to 7.5 and the surface charge at these pH values varied from highly positive to highly negative values. In PBS, the surface charge is negative and relatively low for all the samples, which resulted in agglomeration. Five out of six powders exhibited significant photocatalytic activity when exposed to UV irradiation. This also includes one cosmetic-grade powder. Furthermore, during the immersion in aqueous media at physiological temperature, the powders released foreign ions, which might also contribute to the results of cytotoxicity tests. The results revealed the major role of the particle surface charge and its impact on particle dispersion or agglomeration. Due to the high ionic strength in the liquids relevant for cell-surface interaction tests, for all the examined titania powders the nanoparticulate character was lost. However, the presence of impurities and photocatalysis might further contribute to the results of cytotoxicity tests.