Copper cation interactions with biologically essential types of ligands: a computational DFT study

This work presents a systematic theoretical study on Cu(I) and Cu(II) cations in variable hydrogen sulfide-aqua-ammine ligand fields. These ligands model the biologically most common environment for Cu ions. Molecular structures of the complexes were optimized at the density functional theory (DFT) level. Subsequent thorough energy analyses revealed the following trends: (i) The ammine complexes are the most stable, followed by those containing the aqua and hydrogen sulfide ligands, which are characterized by similar stabilization energies. (ii) The most preferred Cu(I) coordination number is 2 in ammine or aqua ligand fields. A qualitatively different binding picture was obtained for complexes with H(2)S ligands where the 4-coordination is favored. (iii) The 4- and 5-coordinated structures belong to the most stable complexes for Cu(II), regardless of the ligand types. Vertical and adiabatic ionization potentials of Cu(I) complexes were calculated. Charge distribution (using the natural population analysis (NPA) method) and molecular orbital analyses were performed to elucidate the nature of bonding in the examined systems. The results provide in-depth insight into the Cu-binding properties and can be, among others, used for the calibration of bioinorganic force fields.     

Simulation Support to EPR-based Dentin Characterization

Treatment of dental caries as one of the most economically relevant human disease can rely only on the understanding of the caries progress through dentin. As it can be seen from the frequency of tooth decay among different animals, its existence and progress strongly depend on the mineral part arrangement, especially on the orientation of the hydroxyapatite (HA) crystals, which resist the mechanical and chemical stress very anisotropically. It is therefore not surprising that different attempts have been made to unravel the mystery of dentin growth and HA crystals arrangement. By dentin irradiation with gamma-rays, very stable CO₃ ^? radicals are generated within HA crystals which due to the anisotropic magnetic coupling enable detection of their orientational distribution via angular-dependent electron paramagnetic resonance spectroscopy. The latter can be significantly enhanced if the whole angular dependence can be fitted simultaneously within certain dentin structural models. As shown in this work, even subtle information like the orientation of the tubules relative to the pulp or the orientation of HA crystals relative to the tubules can be extracted. The sensitivity to different sample geometry is discussed to provide the best possible characterization.     

Generalized linear fractional programming under interval uncertainty

Data in many real-life engineering and economical problems suffer from inexactness. Herein we assume that we are given some intervals in which the data can simultaneously and independently perturb. We consider a generalized linear fractional programming problem with interval data and present an efficient method for computing the range of optimal values. The method reduces the problem to solving from two to four real-valued generalized linear fractional programs, which can be computed in polynomial time using an appropriate interior point method solver.     

On the favorable estimation for fitting heavy tailed data

Assessment of heavy tailed data and its compound sums has many applications in insurance, auditing and operational risk capital assessment among others. In this paper, we compare the classical estimators (maximum likelihood, QQ and moment estimators) with the recently introduced robust estimators of “generalized median”, “trimmed mean” and estimators based on t-score moments. We derive the exact distribution of the likelihood ratio tests of homogeneity and simple hypothesis on the tail index of a two-parameter Pareto model. Such exact tests support the assessment of the performance of estimators. In particular, we discuss some problems that one can encounter when misemploying the log-normal assumption based methods supported by the Basel II framework. Real data and simulated examples illustrate the methods.     

Automated contour detection in X-ray left ventricular angiograms using multiview active appearance models and dynamic programming

This paper describes a new approach to the automated segmentation of X-ray left ventricular (LV) angiograms, based on active appearance models (AAMs) and dynamic programming. A coupling of shape and texture information between the end-diastolic (ED) and end-systolic (ES) frame was achieved by constructing a multiview AAM. Over-constraining of the model was compensated for by employing dynamic programming, integrating both intensity and motion features in the cost function. Two applications are compared: a semi-automatic method with manual model initialization, and a fully automatic algorithm. The first proved to be highly robust and accurate, demonstrating high clinical relevance. Based on experiments involving 70 patient data sets, the algorithm's success rate was 100% for ED and 99% for ES, with average unsigned border positioning errors of 0.68 mm for ED and 1.45 mm for ES. Calculated volumes were accurate and unbiased. The fully automatic algorithm, with intrinsically less user interaction was less robust, but showed a high potential, mostly due to a controlled gradient descent in updating the model parameters. The success rate of the fully automatic method was 91% for ED and 83% for ES, with average unsigned border positioning errors of 0.79 mm for ED and 1.55 mm for ES.     

Theoretical study of the helio hydrogen cyanide dication HeCNH2+

The structure and stability of the helio hydrogen cyanide molecular ion, HeCNH²⁺, is investigated by standard quantum chemical methods. Single reference calculations are carried out using second-order perturbation theory (MP2), the coupled cluster expansion in the CCSD approximation, and the hybrid approach using a perturbative estimate of the triple excitation energy component designated CCSD(T). Multireference calculations using a complete active space (CASSCF) and a second-order perturbation theory estimate of correlation effects (CASPT2) are reported.     

An extremal problem for real algebraic polynomials

Let G _n be the set of all real algebraic polynomials of degree at most n, positive on the interval (?1, 1) and without zeros inside the unit circle (|z| < 1). In this paper an inequality for the polynomials from the set G _n is obtained. In one special case this inequality is reduced to the inequality given by B. Sendov [5] and in another special case it is reduced to an inequality between uniform norm and norm in the L ₂ space for the Jacobi weight.     

Crystallization behaviour of Ge17Sb23Se60 thin films

The crystallization behaviour of as-prepared and nucleated Ge₁₇Sb₂₃Se₆₀ thin films was studied by means of differential scanning calorimetry, X-ray diffraction analysis and scanning electron microscopy. Detailed analysis of the non-isothermal crystal growth kinetics was performed; the apparent activation energy, kinetic model and value of the pre-exponential factor were determined. The kinetic behaviour was found to be surprisingly close to the ideal Johnson–Mehl–Avrami nucleation-growth process, with the only non-ideality being the prolonged peak end tail (which may be a specificity associated with certain thicknesses of thin layers). This corresponds to the initiation of crystal growth in agreement with the classical nucleation theory, with the amount of mechanical defects and strains being negligible. The value of the kinetic parameter suggests two-dimensional crystal growth, which is consistent with the idea of macroscopic crystallites growing in a sterically restricted thin layer. A similar conclusion can be made on the basis of direct microscopic observation of the crystallites’ morphology.