Anion-templated supramolecular C3 assembly for efficient inclusion of charge-dispersed anions into hydrogen-bonded networks

The binding properties and conformational adaptability of a known nitrate/sulfate receptor N,N'-3-azapentane-1,5-bis[3-(1-aminoethylidene)-6-methyl-3H-pyran-2,4-dione] (L) toward various charge-dispersed monoanions (HSO(3)(-), ClO(4)(-), IO(4)(-), PF(6)(-), and SbF(6)(-)) are considered. These anions template the folding of three HL(+) species through a self-assembly process into a new hollow supramolecular trication. During the self-assembly, all strong hydrogen-bond donors of the podand become coordinatively saturated by interactions with the oxo functionalities from other HL(+) molecules. In that way, only the weak hydrogen-bond-donating groups in the exterior part of the receptor are accessible for anion binding. The investigated anions are accommodated in the hydrophobic pockets of the isomorphous hydrogen-bonded frameworks, which serve as a basis for selective crystallization from the highly competitive anion/solvent systems. This behavior is discussed in terms of size and geometry of the anions as well as the receptor's coordination capabilities to provide the most favorable surroundings for guest inclusion both in solution and in the solid state.     

Properties of surface dielectric barrier discharge plasma generator for fabrication of nanomaterials

This paper presents surface dielectric barrier discharge plasma generators as an efficient source of low-energy ions. Either positive or negative ions can be extracted from a plasma cloud with an external DC field created by the third electrode. Three different cross-section geometries of DBD generators were analyzed, simulated and fabricated. Currents of ions extracted from the plasma cloud were measured and the results were discussed. It was demonstrated that if the third electrode consists of liquid–gas interface, the presented arrangement can be used as a versatile reactor for nanomaterial synthesis (on the example of the synthesis of silver nanoparticles).     

Protonation and Anion Binding Properties of Aromatic Bis-Urea Derivatives—Comprehending the Proton Transfer

A series of aromatic bis-urea derivatives was prepared and their proton dissociation, as well as anion binding properties in DMSO were investigated. To this end, UV/Vis and ¹H NMR spectroscopies and computational methods were employed. The synthesized molecules differed in the relative position of the urea moieties (ortho- and meta-derivatives) and in the functional groups (−H, −CH₃, −OCH₃, −NO₂) in the para-position of the pendant phenyl groups. Remarkably high acidities of the compounds (logK₁^H≈14), were ascribed primarily to the stabilizing effect of the aromatic subunits. Quantum chemical calculations corroborated the conclusions drawn from experimental data and provided information from the structural point of view. Knowledge regarding protonation properties proved to be essential for reliable quantitative determination of anion binding affinities. Studied receptors were selective for acetate and dihydrogen phosphate among several anions. Formation of their complexes of 1:1 and 1:2 (ligand/anion) stoichiometries was quantitatively characterized. Proton transfer was taken into account in the course of data analysis, which was especially important in the case of AcO⁻. ortho-Receptors were proven to be more efficient acetate binders, achieving coordination with all four NH groups. The meta-analogues preferred dihydrogen phosphate, which acted as both hydrogen bond donor and acceptor. Cooperative binding was detected in the case of 1:2 H₂PO₄⁻ complexes, which was assigned to formation of interanionic hydrogen bonds.     

Combination Laws for Scaling Exponents and Relation to the Geometry of Renormalization Operators

Renormalization group has become a standard tool for describing universal properties of different routes to chaos—period-doubling in unimodal maps, quasiperiodic transitions in circle maps, dynamics on the boundaries of Siegel disks, destruction of invariant circles of area-preserving twist maps, and others. The universal scaling exponents for each route are related to the properties of the corresponding renormalization operators.     

Assessing publically financed metrology expenditure against economic parameters

The objective of this paper is to provide an economic perspective to those involved in public financing of the national metrology infrastructure. Whereas justifications for subsidising the national metrological activities are often historically biased, we raise the importance of economic considerations, which could be used during prioritisation. The expenditure in measurement and metrology infrastructure of European countries are compared to economic indicators for quality of life. Various proxies are used, such as measuring instruments sale (for measurement infrastructure) and data from the BIPM’s KCDB (as a proxy for national standards). As the EU Internal Market also holds for the provision of metrological services, the paper exposes possible trends regarding public financing to the sector.

UV-radiation-induced electron emission by hormones. Hypothesis for specific communication mechanisms

The highlights of recently observed electron emission from electronically excited sexual hormones (17β-estradiol, progesterone, testosterone) and the phytohormone genistein in polar media are briefly reviewed. The electron yield, Q(e_aq⁻), dependence from substrate concentration, hormone structure, polarity of solvent, absorbed energy and temperature are discussed. The hormones reactivity with e_aq⁻ and efficiency in electron transfer ensure them the ability to communicate with other biological systems in an organism. A hypothesis is presented for the explanation of the mechanisms of the distinct recognition of signals transmitted by electrons, originating from different types of hormones to receiving centres. Biological consequences of the electron emission in respect to cancer are mentioned.     

Transition metal complexes of N-1-tosylcytosine and N-1-mesylcytosine

The syntheses as well as chemical and X-ray structural characterization of dichlorobis[1-(p-toluenesulfonyl)cytosine]copper(II) (2), its solvated pseudopolymorph containing two methanol molecules (3), dichlorobis[1-(p-toluenesulfonyl)cytosine]cadmium(II) (4), 1-methanesulfonylcytosine (6) and its copper complex dichlorobis(1-methanesulfonylcytosine)copper(II) (7) are described. In addition, spectroscopic studies of dichlorobis[1-(p-toluenesulfonyl)cytosine]cobalt(II) (5), as well as of dichlorobis(1-mesylcytosine)cadmium(II) (8) are presented. Pseudopolymorphs 2 and 3, as well as their 1-mesylcytosine analog 7, reveal square-planar coordination spheres, almost ideal in the case of 2, but considerably distorted in the case of 3 and 7. In all cases, the Cu(II) ion is coordinated by two endocyclic N3 atoms from two ligand molecules and by two chlorine atoms. The analogous coordination sphere was found in complex 4, where Cd(II) lies in the center of a slightly distorted tetrahedron formed by two endocyclic N3 atoms and by two chlorine atoms.