Effects of finite size nuclei in relativistic four-component calculations of hyperfine structure

The effect of a finite size model for both the nuclear charge and magnetic moment distributions on calculated EPR hyperfine structure have been studied using a relativistic four-component method based on density functional theory. This approach employs a restricted kinetically balanced basis (mDKS-RKB) and includes spin-polarization using noncollinear spin-density exchange-correlation functionals in the unrestricted fashion. Benchmark calculations have been carried out for a number of small molecules containing Zn, Cd, Ag, and Hg. The present results are compared with those obtained at the Douglas-Kroll-Hess second order (DKH-2) method. The dependence of the results on the quality of the orbital and auxiliary basis sets has been studied. It was found that some basis sets contain irregularities that deteriorate the results. Especial care has to be taken also on the construction of the auxiliary basis for fitting the total electron and spin-densities.     

The effect of lipid oxidation on the water permeability of phospholipids bilayers

The effect of lipid oxidation on water permeability of phosphatidylcholine membranes was investigated by means of both scattering stopped flow experiments and atomistic molecular dynamics simulations. Formation of water pores followed by a significant enhancement of water permeability was observed. The molecules of oxidized phospholipids facilitate pore formation and subsequently stabilize water in the membrane interior. A wide range of oxidation ratios, from 15 to 100 mol%, was considered. The degree of oxidation was found to strongly influence the time needed for the opening of a pore. In simulations, the oxidation ratio of 75 mol% was found to be a threshold for spontaneous pore formation in the tens of nanosecond timescale, whereas 15 mol% of oxidation led to significant water permeation in the timescale of seconds. Once a pore was formed, the water permeability was found to be virtually independent of the oxidation ratio.     

Interaction of cephalosporins with outer membrane channels of Escherichia coli. Revealing binding by fluorescence quenching and ion conductance fluctuations

Outer membrane channels in gram-negative bacteria are implicated in the influx of the latest generation of cephalosporins. We have measured the interaction strengths of ceftriaxone, cefpirome and ceftazidime in the two most abundant outer membrane porins of Escherichia coli, OmpF and OmpC, by both ion current fluctuations through single protein channels and fluorescence quenching. Statistical analysis of individual antibiotic entry events in membrane-incorporated porins yielded the kinetic rates and the equilibrium binding constant of each antibiotic-porin pair. Affinity constants were independently obtained by measuring the static quenching of inherent tryptophan fluorescence in the porins in the presence of the antibiotics. Through an empirical inner filter effect correction we have succeeded in measuring the chemical interaction of these strongly absorbing antibiotics, and obtained a qualitative agreement with conductance measurements. The interaction of all three antibiotics is smaller for OmpC than OmpF, and in the case of each porin the interaction strength series ceftriaxone > cefpirome > ceftazidime is maintained.     

Fefferman–Stein inequalities for the dyadic-like maximal operators

The paper contains a transference theorem which allows to extend a large class of unweighted inequalities for the dyadic maximal operator to their weighted Fefferman–Stein counterparts on general probability spaces.

     

Broadband-cascaded four-wave mixing in a photonic crystal fiber around 1 μm

To our knowledge, efficient generation of broadband four-wave mixing cascades centered at 1 μm and spanning 600 nm is experimentally demonstrated for the first time. This frequency comb is generated from a two-tone seed with a maximum peak power of 25 W in a low-dispersion photonic crystal fiber. It consists of up to 44 new idler waves generated symmetrically around the seed.     

Quenching of the E1 strength in <Superscript>149</Superscript>Nd

Lifetime measurements of excited states in ¹⁴⁹Nd have been performed using the advanced time-delayed b \beta g \gamma g \gamma(t) method. Half-lives of 14 excited states in ¹⁴⁹Nd have been determined for the first time or measured with higher precision. Twelve new g \gamma -lines and 5 new levels have been introduced into the decay scheme of ¹⁴⁹Pr based on results of the g \gamma g \gamma coincidence measurements. Reduced transition probabilities have been determined for 40 g \gamma -transitions in ¹⁴⁹Nd . Configuration assignments for 6 rotational bands in ¹⁴⁹Nd are proposed. Enhanced E1 transitions indicate that the ground-state band and the band built on the 332.9keV level constitute a pair of the K^p = 5/2^±\ensuremath K^{\pi} = 5/2^{\pm} parity doublet bands. Potential energy surfaces on the (b₂,b₃)\ensuremath (\beta_{2},\beta_{3}) -plane have been calculated for the lowest single quasi-particle configurations in ¹⁴⁹Nd using the Strutinski method and the axially deformed Woods-Saxon potential. The predicted occurrence of the octupole-deformed K = 5/2 configuration is in agreement with experiment. Unexpectedly low |D₀|\ensuremath \vert D_0\vert values obtained for the K^p = 5/2^±\ensuremath K^{\pi} = 5/2^{\pm} parity doublet bands may result from cancellation between the proton and neutron shell correction contributions to |D₀|\ensuremath \vert D_0\vert .     

The first member of the eleven-vertex azadicarbaborane series, 1,6,9-NC2B8H13, and its N-alkyl derivatives

Reactions between closo-1,2-C(2)B(8)H(10) (1) and amines of general formulation R(1)R(2)NH (where R(1), R(2) = H, H; Me, H; t-Bu, H and Et, Et) resulted in a straightforward cluster expansion and formation of the 11-vertex arachno-azadicarbaboranes of the 1,1-R(1),R(2-)1,6,9-NC(2)B(8)H(11) (2) cluster constitution (where R(1), R(2) = H, H 2a; Me, H 2b; t-Bu, H 2c and Et, Et 2d) in yields 10-75%, depending on the nature of the amine used. The reactions are the first example of a direct closo to arachno transformation in the area of cluster-boron compounds. Compounds 2b and 2c were isolated in two isomeric forms anti- and syn- that differ in the positioning of the t-Bu substituent with respect to the bridging hydrogen site. Deprotonation of compounds 2 generally leads to removal of the bridging proton and formation of the [1,1-R(1),R(2-)1,6,9-NC(2)B(8)H(11)](-) (2-) anions that, in the case of the monoalkylated Me and t-Bu derivatives, adopt only an anti configuration. The structure of anti-2c was determined by X-ray diffraction analysis and the geometries of the parent compound and the corresponding syn and anti isomers were optimised at the RMP2/6-31G* level. The composition of all compounds is consistent with the results of mass spectrometry and multinuclear ((1)H and (11)B) spectroscopy complemented by two-dimensional [(11)B-(11)B]-COSY and (1)H{(11)B(selective)} NMR measurements. Experimental (11)B chemical shifts generally show acceptable agreement with theoretical values calculated by GIAO methods, in particular at GIAO-MP2/II, where possible.     

Diauxic behaviour for biological processes at various timescales

In the present paper, we provide the conditions guaranteeing the generalization of so-called diauxic behaviour of solutions of ordinary differential equations (ODEs). This behaviour was described by Monod in 1949 in the context of bacterial growth. Then, a similar behaviour was observed and described referring to dynamic of CDK1 protein activity during cell cycle. The diauxic behaviour is described in terms of inflection points.