Stability and structure of mixed-ligand metal ion complexes that contain Ni2+, Cu2+, or Zn2+, and Histamine, as well as adenosine 5'-triphosphate (ATP4-) or uridine 5'-triphosphate (UTP(4-): an intricate network of equilibria

With a view on protein–nucleic acid interactions in the presence of metal ions we studied the “simple” mixed‐ligand model systems containing histamine (Ha), the metal ions Ni²⁺, Cu²⁺, or Zn²⁺ (M²⁺), and the nucleotides adenosine 5′‐triphosphate (ATP^4?) or uridine 5′‐triphosphate (UTP^4?), which will both be referred to as nucleoside 5′‐triphosphate (NTP^4?) . The stability constants of the ternary M(NTP)(Ha)^2? complexes were determined in aqueous solution by potentiometric pH titrations. We show for both ternary‐complex types, M(ATP)(Ha)^2? and M(UTP)(Ha)^2?, that intramolecular stacking between the nucleobase and the imidazole residue occurs and that the stacking intensity is approximately the same for a given M²⁺ in both types of complexes: The formation degree of the intramolecular stacks is estimated to be 20 to 50 %. Consequently, in protein–nucleic acid interactions imidazole–nucleobase stacks may well be of relevance. Furthermore, the well‐known formation of macrochelates in binary M²⁺ complexes of purine nucleotides, that is, the phosphate‐coordinated M²⁺ interacts with N7, is confirmed for the M(ATP)^2? complexes. It is concluded that upon formation of the mixed‐ligand complexes the M²⁺? N7 bond is broken and the energy needed for this process corresponds to the stability differences determined for the M(UTP)(Ha)^2? and M(ATP)(Ha)^2? complexes. It is, therefore, possible to calculate from these stability differences of the ternary complexes the formation degrees of the binary macrochelates: The closed forms amount to (65±10) %, (75±8) %, and (31±14) % for Ni(ATP)^2?, Cu(ATP)^2?, and Zn(ATP)^2?, respectively, and these percentages agree excellently with previous results obtained by different methods, confirming thus the internal validity of the data and the arguments used in the evaluation processes. Based on the overall results it is suggested that M(ATP)^2? species, when bound to an enzyme, may exist in a closed macrochelated form only, if no enzyme groups coordinate directly to the metal ion.     

Comparison of silica gel modified with three different functional groups with C-18 and styrene-divinylbenzene adsorbents for the analysis of selected volatile flavor compounds

A comparison of SPE cartridges produced in authors laboratory containing silica modified by addition of three functional moieties with standard C-18 and SDVB cartridges was made in terms of their applicability for the isolation of flavor compounds. Compounds found in wine and grapes were used for model mixture, which was spiked into a grape juice. Functionalized phases for SPE were prepared modifying silica gel with alkoxysilanes with different functional groups: (3-(phenylamino)-propyltrimethoxysilane, octyltriethoxysilane and octadecyl-silane. The functionalization was carried out by the dry method, which resulted 5, 10 and 20 weight parts of initial support. Functionalized phases were characterized using FT-IR, elemental analysis and NMR.Performance for new phases compared to “standard” ones (C-18 and SDVB (styrene–divinylbenzene) varied, depending on the group or type of analyzed compound. They were more efficient in extraction of methyl anthranilate and vanilins. For extraction of terpenes, C-6 alcohols, isoprenoids, benzene derivatives and phenols their efficiency was comparable to that of C-18.Functionalized laboratory-made mixed phases are suitable for extraction of flavor compounds from grape juice. They are suitable for extraction of compounds belonging to different chemical classes with the efficiency comparable to C-18 and SDVB phases. The production of such functionalized phases can be easily performed in the laboratory, at a very low cost, comparing to C-18 or SDVB cartridges. This makes the proposed functionalized phases an interesting alternative, in sample preparation for analysis and particularly in preparative/flash chromatography.     

The -Cys-Cys- motif in Helicobacter pylori's Hpn and HspA proteins is an essential anchoring site for metal ions

The Hpn and HspA proteins from H. pylori are significant for nickel homeostasis and protect the cells from higher concentrations of external metal ions. Both proteins have a unique histidine- and cysteine-rich domain at the C terminus. The interactions of Ni(2+), Bi(3+), Zn(2+) and Cd(2+) ions with C-terminal Ac-CCSTSDSHHQ-NH(2) and Ac-EEGCCHGHHE-NH(2) fragments from Hpn and the Ac-GSCCHTGNHD-NH(2) sequence from HspA were studied by potentiometry, mass spectrometry, circular dichroism and UV-Vis spectroscopy. Ac-CC-NH(2) was used as a reference peptide. The studies have shown that nickel ions form planar complexes with a {2S(-),N(-)} binding mode. The thiol sulfurs of the -Cys-Cys- motif are also the anchoring sites for Bi(3+), Zn(2+) and Cd(2+) ions. The studied protein fragments have the highest affinity for Bi(3+) ions. The thermodynamic stability of Ni(2+) is much higher then that of Zn(2+).     

Sensitivity of risk measures with respect to the normal approximation of total claim distributions

A simple and commonly used method to approximate the total claim distribution of a (possibly weakly dependent) insurance collective is the normal approximation. In this article, we investigate the error made when the normal approximation is plugged in a fairly general distribution-invariant risk measure. We focus on the rate of convergence of the error relative to the number of clients, we specify the relative error’s asymptotic distribution, and we illustrate our results by means of a numerical example. Regarding the risk measure, we take into account distortion risk measures as well as distribution-invariant coherent risk measures.     

Effects of dynamical couplings in IR spectra of the hydrogen bond in N-phenylacrylamide crystals

This article presents the investigation results of the polarized IR spectra of the hydrogen bond in N-phenylacrylamide crystals measured in the frequency range of the proton and deuteron, ν(N-H) and ν(N-D), stretching vibration bands. The basic spectral properties of the crystals were interpreted quantitatively in terms of the "strong-coupling" theory. The proposed model of the centrosymmetric dimer of hydrogen bonds facilitated the explanation of the well-developed, two-branch structure of the ν(N-H) and ν(N-D) bands as well as the isotopic dilution effects in the spectra. The vibronic mechanism of the generation of the long-wave branch of the ν(N-H) band ascribed to the excitation of the totally symmetric proton vibration was elucidated. The complex fine structure pattern of ν(N-H) and ν(N-D) bands in N-phenylacrylamide spectra in comparison with the spectra of other secondary amide crystals (e.g., N-methylacetamide and acetanilide) can be accounted for in terms of the vibronic model for the forbidden transition breaking in the dimers. On the basis of the linear dichroic and temperature effects in the polarized IR spectra of N-phenylacrylamide crystals, the H/D isotopic "self-organization" effects were revealed.     

Electron-induced phase transition in hydrogen-bonded solid-state 2-pyridone

This paper presents the results of experimental studies of hydrogen-bonded 2-pyridone crystal IR spectra. Spectral studies have demonstrated the existence of two anhydrous solid-state phases of each compound, namely the α and the β phases. Hydrogen bonds in the high-temperature α phase of these crystals have been estimated to be 40% stronger than the hydrogen bonds in the β phase, which are stable at room temperature. The mechanism of the phase transition in the solid-state 2-pyridone is proposed on the basis of the IR spectral data. This was possible by taking into account small changes in the geometry of heterocyclic molecular skeletons, which accompany the electron density redistribution in the hydrogen bonds occurring during the transition. The phase transition is connected with a partial change in the hydrogen bond nature from the N(+)-H···O(-) in the α phase, to the N-H···O hydrogen bonds in the β phase crystals.     

Complete assignment of the vibrational modes of C60 by inelastic neutron scattering spectroscopy and periodic-DFT

In this paper we exploit the complementarity of inelastic neutron scattering (INS), infrared and Raman spectroscopies with ab initio calculations to generate an updated assignment of the vibrational modes of C(60). We have carried out periodic-DFT calculations of the high temperature face centred cubic phase modelled as the standard structure and also of the low temperature simple cubic phase, the latter for the first time. Our assignment differs from all previous work, however, it is the only one that is able to successfully reproduce the INS spectrum in terms of both transition energies and intensities. In addition to the INS spectrum we are also able to quantitatively simulate the major features of the infrared and Raman spectra in the high temperature phase and the infrared spectrum in the low temperature phase.     

The curse of dimensionality for the class of monotone functions and for the class of convex functions

We study the integration and approximation problems for monotone or convex bounded functions that depend on $d$ variables, where $d$ can be arbitrarily large. We consider the worst case error for algorithms that use finitely many function values. We prove that these problems suffer from the curse of dimensionality. That is, one needs exponentially many (in $d$) function values to achieve an error $\epsilon$.     

Geometric properties of F-normed Orlicz spaces

Aequationes mathematicae - The paper deals with F-normed functions and sequence spaces. First, some general results on such spaces are presented. But most of the results in this paper concern...