A dithienylethene-tethered beta-cyclodextrin dimer as a photoswitchable host

The binding of TSPP by a dithienylethene-tethered beta-cyclodextrin dimer can be altered reversibly by irradiation with light.     

A note on the coefficients of inverse polynomials

We describe some relations on the coefficients of a polynomial in terms of the map that induces and use them to characterize the coefficients of the inverse polynomials of some special classes of permutation polynomials.     

Natural radioactivity and radiation hazards assessment of soil samples from the area of Tuzla and Lukavac,Bosnia and Herzegovina

The results of activity concentration measurements of natural occurring radioactive nuclides ²³⁸U, ²³⁵U, ²³²Th, ²²⁶Ra, and ⁴⁰K in surface soil samples collected in the area of cities Tuzla and Lukavac, northeast region of Bosnia and Herzegovina were presented. Soil sampling was conducted at the localities that are situated in the vicinity of industrial zones of these cities. The measured activity was in the range from (8?±?4) to (95?±?28) Bq kg^–1 for ²³⁸U, from (0.41?±?0.06) to (4.6?±?0.7) Bq kg^–1 for ²³⁵U, from (7?±?1) to (66?±?7) Bq kg^–1 for ²³²Th, from (6?±?1) to (55?±?6) Bq kg^–1 for ²²⁶Ra, and from (83?±?12) to (546?±?55) Bq kg^–1 for ⁴⁰K. In order to evaluate the radiological hazard of the natural radioactivity for people living near industrial zones, the absorbed dose rate, the annual effective dose and the radium equivalent activity have been calculated and compared with the internationally approved values.     

Photocontrolled release and uptake of a porphyrin guest by dithienylethene-tethered beta-cyclodextrin host dimers

Two photoswitchable dithienylethene-tethered beta-cyclodextrin dimers were synthesized to function as host molecules with an externally controllable binding affinity. The cyclodextrin cavities of these dimers are linked through their secondary sides by a photochromic dithienylethene unit that is connected to the secondary rim either directly (4) or through propyl spacers (9). Irradiation with light switches these dimers between a relatively flexible (open) and a rigid (closed) form. The binding properties of the dimers depend on the configuration of the dithienylethene spacer, as is shown by microcalorimetry performed with tetrakis-sulfonatophenyl porphyrin (TSPP) as a guest molecule. The differences in binding properties are most pronounced for the more rigid dimer 4, which binds TSPP 35 times more strongly in the open form (4 a) than in the closed form (4 b). The values found for the enthalpy of binding (deltaH degrees ) indicate that this difference in binding is due to the loss of cooperativity between the two beta-cyclodextrin cavities in the closed form. Molecular modeling shows that 4 b is not able to bind TSPP effectively in both cyclodextrin cavities. The open and closed forms of the more flexible dimer 9 show no substantial difference in their binding of TSPP. Thermodynamic values indicative of strong binding of TSPP by two beta-cyclodextrin cavities were measured for both forms of the dimer, and molecular modeling confirms that both are flexible enough to tightly bind TSPP. The binding differences between the forms of dimer 4 allow the photocontrolled release and uptake of TSPP, which renders control of the ratio of complexed to free TSPP in solution possible.     

Bis(phenylthienyl)ethene-tethered beta-cyclodextrin dimers as photoswitchable hosts

Two beta-cyclodextrin dimers tethered by photoswitchable bis(phenylthienyl)ethene moieties were synthesized as potentially tunable receptor molecules. The cyclodextrin cavities of these dimers were linked via their secondary sides, with the photochromic bis(phenylthienyl)ethene unit either directly connected to the secondary rim (7) or via propyl spacers (10). By irradiation with light the dimers were reversibly switched between a relatively flexible (open) form and a rigid (closed) form. The photostationary states for both dimers consisted of 92% of the open and 8% of the closed form, enabling the nearly complete conversion between the two forms. The binding properties of the open and closed forms of dimers 7 and 10 were assessed by complexation studies with meso-tetrakis(4-sulfonatophenyl)porphyrin (TSPP) using isothermal titration calorimetry. For the rigidly tethered dimer 7, a factor 8 difference in binding affinity between the open and closed form of the dimer was found. This difference in binding affinity reflects the difference in enthalpy of binding for the two dimers, indicating that the beta-cyclodextrin cavities of the closed dimer 7b are spaced too far apart from each other by the rigid closed bis(phenylthienyl)ethene tether to cooperatively bind TSPP. The difference in binding affinity was sufficient to enable the phototriggered release of TSPP from dimer. The thermodynamic parameters obtained for dimer 10 suggested that the closed tether substantially contributes to the binding of TSPP. The open and closed form of dimer 10 bound TSPP with similar association constants, although the enthalpy of binding for the complexation of TSPP by the closed form of dimer 10 was more favorable than that found for the open form of the dimer.     

On coefficients of polynomials over finite fields

In this paper we study the relation between coefficients of a polynomial over finite field Fq and the moved elements by the mapping that induces the polynomial. The relation is established by a special system of linear equations. Using this relation we give the lower bound on the number of nonzero coefficients of polynomial that depends on the number m of moved elements. Moreover we show that there exist permutation polynomials of special form that achieve this bound when m|q−1. In the other direction, we show that if the number of moved elements is small then there is an recurrence relation among these coefficients. Using these recurrence relations, we improve the lower bound of nonzero coefficients when m?q−1 and . As a byproduct, we show that the moved elements must satisfy certain polynomial equations if the mapping induces a polynomial such that there are only two nonzero coefficients out of 2m consecutive coefficients. Finally we provide an algorithm to compute the coefficients of the polynomial induced by a given mapping with O(q3/2) operations.     

Electrochemical Reduction of N2 to NH3 at Low Potential by a Molecular Aluminum Complex

Electrochemical generation of ammonia (NH₃) from nitrogen (N₂) using renewable electricity is a desirable alternative to current NH₃ production methods, which consume roughly 1 % of the world's total energy use. The use of catalysts to manipulate the required electron and proton transfer reactions with low energy input is also a chemical challenge that requires development of fundamental reaction pathways. This work presents an approach to the electrochemical reduction of N₂ into NH₃ using a coordination complex of aluminum(III), which facilitates NH₃ production at −1.16 V vs. SCE. Reactions performed under ¹⁵N₂ liberate ¹⁵NH₃. Electron paramagnetic resonance spectroscopic characterization of a reduced intermediate and investigations of product inhibition, which limit the reaction to sub-stoichiometric, are also presented.     

From Mesomorphic Phosphine Oxide to Clustomesogens Containing Molybdenum and Tungsten Octahedral Cluster Cores

New clustomesogens (i.e., metal atom clusters containing liquid crystalline (LC) materials) have been obtained by grafting neutral cyanobiphenyl (CB)‐ or cholesteryl‐containing tailor‐made dendritic mesomorphic triphenylphosphine oxide ligands on luminescent (M₆Clⁱ₈)⁴⁺ octahedral cluster cores (M=Mo, W). The LC properties were studied by a combination of polarizing optical microscopy (POM), differential scanning calorimetry (DSC), and X‐ray powder diffraction analyses. While the organic ligands showed various mesophase types ranging from nematic, SmA columnar (SmA_Col), SmA, and SmC phases, it turned out that the corresponding clustomesogens formed layered phases (SmA) over a wide range of temperatures that depend on the nature and density of mesogenic groups employed. Intrinsic luminescence properties of the cluster precursors are preserved over the entire range of LC phase existence.