Coordination ability of trans-cyclohexane-1,2-diamine-N,N,N',N'-tetrakis(methylenephosphonic acid) towards lanthanide(III) ions

The proton and metal complex equilibria of trans-cyclohexane-1,2-diamine-N,N,N',N'-tetrakis(methylenephosphonic acid) (CDTP) with lanthanide(iii) ions, where Ln(III) = La(III), Nd(III), Sm(III), Eu(III), Gd(III), Tb(III), Ho(III) and Lu(III) were studied. The stoichiometry, protonation and complex formation constants were determined by potentiometric titration at 25.0 degrees C and ionic strength of 0.1 mol dm(-3) (KCl). All metal ions form several species: [LnH4L]-, [LnH3L](2-), [LnH2L](3-), [LnHL](4-), [LnL](5-), [LnH(-1)L](6-) and [LnH(-2)L](7-) in the pH range between 2 and 11. The stability constants log beta(LnL) were found to be between 14.7 and 16.7. The studied complexes were also characterized by spectroscopic methods (31P NMR, UV-Vis absorption and emission spectroscopy). These studies allowed to reveal a distinct structural change of the Ln(III)-CDTP complex which occurs between protonated and hydroxy species in solutions at pH around 7.5. The major change is caused by the involvement of both nitrogen donors in the metal ion coordination occurring in ML species. The data obtained from UV-Vis spectroscopy allowed to draw conclusions about complex symmetry and to estimate a number of coordinated water molecules. The hydration number or more precisely the number of two OH oscillators was found to be approximately one in all species formed over the pH range between 5 and 10. The structure of the major hydroxy complex was supported by X-ray crystallographic data. The crystal structures of the Eu(III) and Tb(III) complexes clearly show that the CDTP ligand is coordinated to the Ln(III) ion by two nitrogen and four oxygen atoms in such a way that only one oxygen atom from each phosphonic group is placed in the lanthanide inner sphere. The monomeric complex anion is connected to a symmetry related ion through short hydrogen bonds formed by two hydroxy ions and one water molecule. In this way the two neighbouring anions form a quasi-dimer in which one of the Ln(III) ion is seven-coordinate (two N atoms, four O atoms and one hydroxy ion) and the other is eight-coordinate (two N atoms, four O atoms, one hydroxy ion and one water molecule).     

Laser spectroscopy of Nd and Dy ions in lead borate glasses

The spectroscopic and laser properties of Nd³⁺ and Dy³⁺ ions in lead borate glass were studied. Luminescence spectra recorded in the near-infrared and visible ranges correspond to ⁴F_3/2-⁴I_J/2 (J=9, 11, 13) transitions of Nd³⁺ and ⁴F_9/2-⁶H_J/2 (J=11, 13, 15) transitions of Dy³⁺, respectively. Luminescence decay curves were analyzed as a function of activator concentration. Luminescence quenching is observed, which is due to Ln-Ln interaction increasing. Several spectroscopic parameters relevant to laser potential of Ln³⁺ ions (Ln=Nd, Dy) in lead borate glass were determined. The relatively large values of the quantum efficiency and the room-temperature emission cross-section for the ⁴F_3/2-⁴I_11/2 transition of Nd³⁺ at 1061 nm and the ⁴F_9/2-⁶H_13/2 transition of Dy³⁺ at 573 nm imply that Ln-doped lead borate glasses can be considered as promising solid-state materials for laser applications.     

Adsorption and structural properties of soft-templated mesoporous carbons obtained by carbonization at different temperatures and KOH activation

Two series of phenolic resin-based mesoporous carbons were prepared by soft-templating strategy, which involves the formation of thermosetting carbon precursor by polymerization of phloroglucinol and formaldehyde in hydrophilic mesodomains of a thermally decomposable triblock copolymer used as a soft-template. It was shown that the volumes of mesopores and micropores in the resulting carbons can be tuned by varying carbonization temperature of phenolic resins in the range from 400 to 1000 °C followed by the post-synthesis KOH activation at 700 °C. The highly microporous carbons were obtained by KOH activation of phenolic resins pyrolyzed at lower temperature (∼500 °C), while high temperature KOH activation (∼800 °C) afforded microporous carbons with preserved mesoporosity.     

On some equation for set-valued functions

In his paper Smajdor (Aequat. Math. 75 149–162, 2008) showed that the equation H + tH ² = (I + tH) ○ H, t ≥ 0 is a necessary and sufficient condition under which the family {F ^t , t ≥ 0} of set-valued functions ${F^t(x):=\sum_{n=0}^{\infty} \frac{t^n}{n!}H^n(x), x \in K}$ is an iteration semigroup. We present a simple proof of a generalization of this result, independent of the coefficients of the series.     

Edge flames stabilized in a non-premixed microcombustor

The dynamics of an edge flame confined in a non-premixed microcombustor model is studied numerically within the context of a diffusive-thermal model. Fuel and oxidizer, separated upstream by a thin plate, flow through a channel with a prescribed velocity. At the tip of the plate, the fuel and oxidizer mix and, when ignited, an edge flame is sustained at some distance from the plate. The objective in this work is to consider the effects of confinement, differential diffusion, and heat loss on the dynamics of an edge flame in a narrow channel. We consider a wide range of channel widths and allow for changing Lewis numbers, and both adiabatic conditions and heat losses along the channel walls. The results illustrate how the flame shape and standoff distance are affected by the channel width, by mixture composition through variations in Lewis numbers and by heat losses. Conditions for flame stabilization, flame oscillations and flame extinction or blowoff are predicted.     

Smectic polymorphism of 4-decyloxybenzylidene- 4′-alkyloxyanilines and their mixtures with polar standards of mesophases

This article describes liquid crystalline properties of the homologous series of 4-decyloxybenzylidene-4′-alkyloxyanilines. Based on the polarization microscopy (POM and TOA methods) and the calorimetric (DSC) measurements a rich polymorphism has been detected. Investigated compounds exhibit nematic, smectic A, smectic C, smectic B, smectic I and G (smectic G) mesophases with their characteristic configurations. The presence of these mesophases was confirmed by the miscibility method, using 4-heptyloxybenxylidene-4′-pentylaniline as a mesophase reference. Nine other smectic standards with different polarity have been applied in order to investigate their influence on the mesophase stability.     

Designing and scaling up an innovation in abstract algebra

In this paper, we describe the process of designing and scaling up the TAAFU group theory curriculum. This work unfolded in three overlapping stages of research and design. The initial designs emerged along with local instructional theories as the result of small-scale design experiments conducted with pairs of students. A second stage of the research and design process focused on generalizing from the initial laboratory design context to an authentic classroom setting. The third (ongoing) stage involves generalizing to instructors (mathematicians) who were not involved in the design process. We describe each of these stages, and our efforts to investigate the efficacy of the resulting curriculum, in order to provide an illustrative example of the process of scaling up an innovation.     

Stereocontrolled Synthesis of Chiral Heteroaromatic Propellers with Small Optical Bandgaps

Chiral heteroaromatic propellers based on radially π‐extended hexapyrrolohexaazacoronenes were obtained in a concise synthesis from suitably functionalized donor–acceptor monopyrroles. To overcome steric hindrance, a new cyclodehydrogenation method was developed, and it uses bromine electrophiles as oxidative coupling agents instead of the commonly employed high‐potential oxidants. The new reaction offers high yields of propeller‐shaped targets, even for electron‐deficient precursors, and shows electrophile‐dependent stereoselectivity, with N‐bromosuccinimide and dibromine yielding, respectively D₆‐ and C₂‐symmetric products. The propeller azacoronenes are chiral and can be separated into configurationally stable enantiomers. In addition to providing steric bulk, peripheral functionalization considerably affects the electronic properties of the propellers, which exhibit reduced optical and electrochemical band gaps, and a more clearly defined electroreduction behavior.