O-Nucleoside, S-nucleoside, and N-nucleoside probes of lumazine synthase and riboflavin synthase

Lumazine synthase catalyzes the penultimate step in the biosynthesis of riboflavin, while riboflavin synthase catalyzes the last step. O-Nucleoside, S-nucleoside, and N-nucleoside analogues of hypothetical lumazine biosynthetic intermediates have been synthesized in order to obtain structure and mechanism probes of these two enzymes, as well as inhibitors of potential value as antibiotics. Methods were devised for the selective cleavage of benzyl protecting groups in the presence of other easily reduced functionality by controlled hydrogenolysis over Lindlar catalyst. The deprotection reaction was performed in the presence of other reactive functionality including nitro groups, alkenes, and halogens. The target compounds were tested as inhibitors of lumazine synthase and riboflavin synthase obtained from a variety of microorganisms. In general, the S-nucleosides and N-nucleosides were more potent than the corresponding O-nucleosides as lumazine synthase and riboflavin synthase inhibitors, while the C-nucleosides were the least potent. A series of molecular dynamics simulations followed by free energy calculations using the Poisson-Boltzmann/surface area (MM-PBSA) method were carried out in order to rationalize the results of ligand binding to lumazine synthase, and the results provide insight into the dynamics of ligand binding as well as the molecular forces stabilizing the intermediates in the enzyme-catalyzed reaction.     

Complete 1H and 13C NMR data assignment of new constituents from Severinia buxifolia

Phytochemical analysis of different organs of the rutaceaeous plant Severinia buxifolia led to the isolation of a new limonoid, a new acridone alkaloid, and a new flavone. Structure elucidation and signal assignment were achieved by the extensive use of 1D and 2D NMR experiments (selective 1D NOE, COSY, NOESY, HSQC, HMBC). Copyright © 2009 John Wiley & Sons, Ltd.     

The mother of all pair potentials

This paper presents a computer simulation study of the exponentially repulsive pair potential system. The simulations show that the system has strong virial potential energy correlations in a large part of its thermodynamic phase diagram. Consequences of this are briefly discussed; these include the existence of isomorphs and predictions for general simple liquids and solids.     

Spin–spin interaction in magnetic semiconductor quantum dots

Self-assembled Cd(Mn)Se/Zn(Mn)Se quantum dots have been investigated by means of spatially and time-resolved magneto-optical spectroscopy. In such quasi zero-dimensional diluted magnetic semiconductors, the exchange interaction couples the spins of optically generated charge carriers with localized magnetic ion spins. We demonstrate that this can be used on the one hand to monitor nanoscale magnetization with a resolution of <100 μ_B by a purely optical technique and on the other hand to optically manipulate the magnetization in a semiconductor quantum dot.     

Interwell exciton relaxation in semimagnetic asymmetric double quantum wells

The possibility of magnetic field control of the spectral and polarization characteristics of exciton recombination is examined in Cd(Mg, Mn) Te-based asymmetric double quantum wells. At low fields, the exciton transition in a semimagnetic well is higher in energy than that in a nonmagnetic well and the interwell exciton relaxation is fast. In contrast, when the energy order of the exciton transitions reverses at high fields, unexpectedly slow relaxation of σ⁻ polarized excitons from the nonmagnetic well to the σ⁺-polarized ground state in the semimagnetic well is observed. Strong dependence of the total circular polarization degree on the heavy-light hole splitting Δ _hh-lh in the nonmagnetic well is found and attributed to the spin dependent interwell tunneling controlled by exciton spin relaxation. Such a slowing down of the relaxation allows separation of oppositely spin-polarized excitons in adjacent wells. The text was submitted by the authors in English.     

Fluorescent cellulose aerogels containing covalently immobilized (ZnS)x(CuInS2)1−x/ZnS (core/shell) quantum dots

Photoluminiscent (PL) cellulose aerogels of variable shape containing homogeneously dispersed and surface-immobilized alloyed (ZnS)_x(CuInS₂)_1?x/ZnS (core/shell) quantum dots (QD) have been obtained by (1) dissolution of hardwood prehydrolysis kraft pulp in the ionic liquid 1-hexyl-3-methyl-1H-imidazolium chloride, (2) addition of a homogenous dispersion of quantum dots in the same solvent, (3) molding, (4) coagulation of cellulose using ethanol as antisolvent, and (5) scCO₂ drying of the resulting composite aerogels. Both compatibilization with the cellulose solvent and covalent attachment of the quantum dots onto the cellulose surface was achieved through replacement of 1-mercaptododecyl ligands typically used in synthesis of (ZnS)_x(CuInS₂)_1?x/ZnS (core–shell) QDs by 1-mercapto-3-(trimethoxysilyl)-propyl ligands. The obtained cellulose—quantum dot hybrid aerogels have apparent densities of 37.9–57.2 mg cm^?3. Their BET surface areas range from 296 to 686 m² g^?1 comparable with non-luminiscent cellulose aerogels obtained via the NMMO, TBAF/DMSO or Ca(SCN)₂ route. Depending mainly on the ratio of QD core constituents and to a minor extent on the cellulose/QD ratio, the emission wavelength of the novel aerogels can be controlled within a wide range of the visible light spectrum. Whereas higher QD contents lead to bathochromic PL shifts, hypsochromism is observed when increasing the amount of cellulose at constant QD content. Reinforcement of the cellulose aerogels and hence significantly reduced shrinkage during scCO₂ drying is a beneficial side effect when using α-mercapto-ω-(trialkoxysilyl) alkyl ligands for QD capping and covalent QD immobilization onto the cellulose surface.     

Towards an identification of chemically different flavin radicals by means of theirg-tensor

Theg-tensors of two chemically different flavin mononucleotide (FMN) radicals, one of which is covalently bound via N(5) of its 7,8-dimethyl isoalloxazine moiety, and the other one non-covalently bound to mutant LOV domains of the blue-light receptor phototropin, LOV1 C57M and LOV2 C450A, respectively, have been determined by very high microwave frequency and high magnetic field electron paramagnetic resonance (EPR) performed at 360 GHz and 12.8 T. Due to the high spectral resolution of the frozen-solution continuous-wave EPR spectra, the anisotropy of theg-tensors could be fully resolved. By least-squares fittings of spectral simulations to expermental data, the principal values ofg have been established:g _X=2.00554(5),g _Y=2.00391(5), andg _Z=2.00247(7) for the N(5)-alkyl-chain-linked FMN radical in LOV1 C57M-675, andg _X=2.00427(5),g _Y=2.00360(5), andg _Z=2.00220(7) for the noncovalently bound FMN radical in LOV2 C450A-605. By a comparison of these values to the ones from the flavin adenine dinucleotide radicals in two photolyases, the radical in LOV2 C450A-605 could be clearly identified as a neutral FMN radical, FMNH. In contrast, LOV1 C57M-675 exhibits significantly shifted principal components ofg, the differences being caused by spin-orbit coupling of the nearby sulfur from the reactive methionine residue, and the modified chemical structure due to the covalent attachment at N(5) of the radical to the apoprotein. The results clearly show the potential of using theg-tensor as probe of the global electronic and chemical structure of protein-bound flavin radicals.