Photophysics,Excited‐state Double‐Proton Transfer and Hydrogen‐bonding Properties of 5‐Deazaalloxazines

The photophysical properties of 5‐deazaalloxazine and 1,3‐dimethyl‐5‐deazaalloxazine were studied in different solvents. These compounds have higher values of fluorescence quantum yields and longer fluorescence lifetimes, compared to those obtained for their alloxazine analogs. Electronic structure and S₀–S_i transitions were investigated using the ab initio methods [MP2, CIS(D), EOM‐CCSD] with the correlation‐consistent basis sets. Also the time‐dependent density functional theory (TD‐DFT) has been employed. The lowest singlet excited states of 5‐deazaalloxazine and 1,3‐dimethyl‐5‐deazaalloxazine are predicted to have the π, π* character, whereas similar alloxazines have two close‐lying π, π* and n, π* transitions. Experimental steady‐state and time‐resolved spectral studies indicate formation of an isoalloxazinic excited state via excited‐state double‐proton transfer (ESDPT) catalyzed by an acetic acid molecule that forms a hydrogen bond complex with the 5‐deazaalloxazine molecule. Solvatochromism of both 5‐deazaalloxazine and its 1,3‐dimethyl substituted derivative was analyzed using the Kamlet–Taft scale and four‐parameter Catalán solvent scale. The most significant result of our studies is that the both scales show a strong influence of solvent acidity (hydrogen bond donating ability) on the emission properties of these compounds, indicating the importance of intermolecular solute–solvent hydrogen‐bonding interactions in their excited state.     

The intricacies of the stacking interaction in a pyrrole–pyrrole system

Extensive calculations of potential energy surfaces for parallel-displaced configurations of pyrrole–pyrrole systems have been carried out by the use of a dispersion-corrected density functional. System geometries associated with the energy minima have been found. The minimum interaction energy has been calculated as ?5.38 kcal/mol. However, bonding boundaries appeared to be relatively broad, and stacking interactions can be binding even for ring centroid distances larger than 6 Å. Though the contribution of the correlation energy to intermolecular interaction in pyrrole dimers appeared to be relatively small (around 1.6 smaller than it is in a benzene–benzene system), this system’s minimum interaction energy is lower than those calculated for benzene–benzene, benzene–pyridine and even pyridine–pyridine configurations. The calculation of the charges and energy decomposition analysis revealed that the specific charge distribution in a pyrrole molecule and its relatively high polarization are the significant source of the intermolecular interaction in pyrrole dimer systems.     

Luminescent cellulose fibers activated by Eu3+-doped nanoparticles

UV- active cellulose fibers were obtained by dry-wet method spinning an 8?% by weight α-cellulose solution in N-methylomorpholine-N-oxide (NMMO) modified by europium-doped gadolinium oxyfluoride Gd₄O₃F₆:Eu³⁺ containing 5?mol (%) of the dopant. Photoluminescent nanoparticles were introduced in the in powder form into a polymer matrix during the process of cellulose dissolution in NMMO. The dependencies of emission intensity on excitation energy and the concentration of Gd₄O₃F₆:Eu³⁺ nanoparticles in the final cellulosic products were examined by photoluminescence spectroscopy (excitation and emission). The fiber structure was studied by X-ray powder diffraction analysis. The size and dispersity of the nanoparticles in the polymer matrix were evaluated using scanning electron microscopy and X-ray microanalysis. The influence of different concentration particles (in the range from 0.5 to 5?% by weight) on the mechanical properties of the fibers, such as tenacity and elongation at break, were determined.     

Absolute configurations of C34 and C35 of antibiotic niphimycin A

The relative configurations of four stereogenic centers of the C33‐C42 fragment of niphimycin A were assigned as 2S*, 3R*, 4S* and 6S*, based upon ¹H NMR analysis with double‐quantum filtered COSY and nuclear Overhauser spectroscopy experiments. These data were then correlated with absolute configurations at C36 and C38 of niphimycin A, which were declared previously as 36S and 38S [3]. This allowed for the assignment of the absolute configurations at C34 and C35 of niphimycin A as 34S and 35R. Copyright © 2012 John Wiley & Sons, Ltd.     

Stabilité analytique et convergence locale de translatées en dynamique homogène S-arithmétique

We present the main result of Richard and Zamojski [14] concerning, in homogeneous dynamics, the general problem of the dynamics of sequences of translates of a certain measure in a space of S-arithmetic lattices.     

Embedding Banach spaces into the space of bounded functions with countable support

We prove that a WLD subspace of the space consisting of all bounded, countably supported functions on a set Γ embeds isomorphically into if and only if it does not contain isometric copies of . Moreover, a subspace of is constructed that has an unconditional basis, does not embed into , and whose every weakly compact subset is separable (in particular, it cannot contain any isomorphic copies of ).     

Erratum to: “Comparative studies of Pd, Ru, Ni, Cu/ZnAl2O4 catalysts for the water gas shift reaction”

The original version of the article was published in Cent. Eur. J. Chem. 11(6) (2013) pp. 912–919. Unfortunately, the original version of this article contains a mistake in the Acknowledgement section. It should be written as “Partially financed from grant number 0680/B/H03/2011/40 and gratefully acknowledged. Pawe? Mierczyński is a participant of START Programme.”     

Fractional electrical model for modified bismuth oxide

Modified bismuth oxide (Bi₂O₃) is of great importance to fuel cells and oxide varistors. The electrical parameters of Bi₂O₃ vary with its modifying components as well as with its aging temperature. This paper presents an analysis of impedance test results carried out to find an equivalent electric model and the relationship between the model's elements to various additives used to modify Bi₂O₃ and to changes in aging temperature. The proposed model was tested via computer simulation and the model parameters correlated to individual modifiers.     

Conformational Properties of the Phosphate Rings of Neutral Phosphoramidate Derivatives of Ribo- and 2′-Deoxyribonucleoside Cyclic 3′,5′-Monophosphates

Abstract

An investigation of the effects of changing the nature of X, nitrogen base (B), and amino substituent (R₂N) on the equilibrium 1?2 was carried out.

The influence of the above structural changes on the time-averaged coupling constants J_AP and J_BP, determined at 300 MHz, were used to follow changes in K_eq. With constant R₂N, small effects from variation of X and B were found. A large range in K_eq arose from changes in the steric size of R₂N. These results will be related to the question of the ease of chair to twist interconversion of the phosphate ring essential to the biological activities of the naturally occurring diesters, cAMP and cGMP.     

Aminophosphinic Acids in a Pyridine Series: Cleavage of Pyridine-2- and Pyridine-4-methyl(amino)phosphinic Acids in Acidic Solutions

The synthesis of a series of new pyridine aminomethylphosphinic acids is described. These compounds were obtained in the reaction of the corresponding pyridine aldehydes with primary amines and with ethyl phenylphosphinate, or methylphosphinate, in the presence of bromotrimethylsilane. In aqueous, strong acid solutions, pyridine aminophosphinic acids were split, forming the phenyl-, or methylphosphonic, acid and the corresponding secondary pyridyl-alkylamines. The kinetics of some observed cleavages were measured, and a mechanism of the cleavage has been proposed.