Cyclic Groups as Autocommutator Groups

This article classifies the groups X whose autocommutator subgroup [X, Aut(X)] is isomorphic to ? and the finite groups X for which [X, Aut(X)] ? C _p has a prime number p of elements.     

Ultrafast exciton relaxation in microcrystalline pentacene films

The exciton dynamics in microcrystalline pentacene films is investigated by transient absorption measurements with 30 fs time resolution. It is found that the emission from photoexcited Frenkel excitons decays within 70 fs due to the ultrafast formation of an excitonic species with a strongly reduced transition dipole to the ground state and an absorption dipole in the plane of the film. We propose that an excimer exciton is formed and stabilized by changes of the local crystal structure. The subsequent dynamics is dominated by diffusion controlled annihilation and trapping.     

Trapping of Rb atoms by ac electric fields

We demonstrate trapping of an ultracold gas of neutral atoms in a macroscopic ac electric trap. Three-dimensional confinement is obtained by switching between two saddle-point configurations of the electric field. Stable trapping is observed in a narrow range of switching frequencies around 60 Hz. The dynamic confinement of the atoms is directly visualized at different phases of the ac switching cycle. We observe about 10(5) Rb atoms in the 1 mm3 large and several microkelvins deep trap with a lifetime of approximately 5 s.     

Amplitude point-spread function measurement of high-NA microscope objectives by digital holographic microscopy

We present here a three-dimensional evaluation of the amplitude point-spread function (APSF) of a microscope objective (MO), based on a single holographic acquisition of its pupil wavefront. The aberration function is extracted from this pupil measurements and then inserted in a scalar model of diffraction, allowing one to calculate the distribution of the complex wavefront propagated around the focal point. The accuracy of the results is compared with a direct measurement of the APSF with a second holographic system located in the image plane of the MO. Measurements on a 100 x 1.3 NA MO are presented.     

Combined quantum mechanical and molecular mechanical simulations of one- and two-electron reduction potentials of flavin cofactor in water, medium-chain acyl-CoA dehydrogenase, and cholesterol oxidase

Flavin adenine dinucleotide (FAD) is a common cofactor in redox proteins, and its reduction potentials are controlled by the protein environment. This regulation is mainly responsible for the versatile catalytic functions of flavoenzymes. In this article, we report computations of the reduction potentials of FAD in medium-chain acyl-CoA dehydrogenase (MCAD) and cholesterol oxidase (CHOX). In addition, the reduction potentials of lumiflavin in aqueous solution have also been computed. Using molecular dynamics and free-energy perturbation techniques, we obtained the free-energy changes for two-electron/two-proton as well as one-electron/one-proton addition steps. We employed a combined quantum mechanical and molecular mechanical (QM/MM) potential, in which the flavin ring was represented by the self-consistent-charge density functional tight-binding (SCC-DFTB) method, while the rest of the enzyme-solvent system was treated by classical force fields. The computed two-electron/two-proton reduction potentials for lumiflavin and the two enzyme-bound FADs are in reasonable agreement with experimental data. The calculations also yielded the pKa values for the one-electron reduced semiquinone (FH*) and the fully reduced hydroquinone (FH2) forms. The pKa of the FAD semiquinone in CHOX was found to be around 4, which is 4 units lower than that in the enzyme-free state and 2 units lower than that in MCAD; this supports the notion that oxidases have a greater ability than dehydrogenases to stabilize anionic semiquinones. In MCAD, the flavin ring interacts with four hydrophobic residues and has a significantly bent structure, even in the oxidized state. The present study shows that this bending of the flavin imparts a significant destabilization (approximately 5 kcal/mol) to the oxidized state. The reduction potential of lumiflavin was also computed using DFT (M06-L and B3LYP functionals with 6-31+G(d,p) basis set) with the SM6 continuum solvation model, and the results are in good agreement with results from explicit free-energy simulations, which supports the conclusion that the SCC-DFTB/MM computation is reasonably accurate for both 1e(-)/1H+ and 2e(-)/2H+ reduction processes. These results suggest that the first coupled electron-proton addition is stepwise for both the free and the two enzyme-bound flavins. In contrast, the second coupled electron-proton addition is also stepwise for the free flavin but is likely to be concerted when the flavin is bound to either the dehydrogenase or the oxidase enzyme.     

Computational study of the Zr4+ tetranuclear polymer, [Zr4(OH)8(H2O)16]8+

The Zr(4+) tetramer, [Zr(4)(OH)(8)(H(2)O)(16)](8+), is thought to be the major component of the Zr(4+) polymer system in aqueous solution, present as a dominant ionic cluster species compared to other Zr(4+) clusters under various experimental conditions. Despite widespread applications of zirconium, the structure and dynamics of the tetramer in aqueous solution are not well understood. We conducted a combination of ab initio molecular dynamics and quantum mechanical studies in the gas phase and aqueous solution and related our results to the available experimental data to provide atom-level information on the behavior of this species in aqueous solution. Our simulations indicate that the tetramer structure is stable on the picosecond time scale in an aqueous environment and that it is of a planar form, comprising eight-coordinated Zr(4+) ions with an antiprism/irregular dodecahedron ligand arrangement. In combination with our studies of Zr(4+) dimer and trimer clusters, our results provide detailed geometrical information on structural motifs for building zirconium polymers and suggest a possible polymerization path.     

A novel software tool for copolymer characterization by coupling of liquid chromatography with matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

The results of copolymer characterization by coupling of chromatography and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) techniques and subsequent calculation of copolymer composition using a novel software tool 'MassChrom2D' are presented. For high-resolution mass analysis copolymer samples were fractionated by means of liquid adsorption chromatography (LAC). These fractions were investigated off-line by MALDI-TOF MS. Various mono-n-butyl ethers of polyethylene oxide-polypropylene oxide copolymers (PEO-co-PPO) were investigated. As well as the copolymer composition presented in two-dimensional plots, the applied approach can give additional hints on specific structure-dependent separation conditions in chromatography.     

Non-Debye response for the structural relaxation in glass-forming liquids: test of the Avramov model

The experimentally observed characteristic features of the alpha-relaxation process in glass-forming liquids are the non-Arrhenius behavior of the structural relaxation times and the non-Debye character of the macroscopic relaxation function. The Avramov model in which relaxation is considered as an energy activation process of surmounting random barriers in liquid energy landscape was successfully applied to describe the temperature and pressure dependences of the macroscopic relaxation times or viscosity. In this paper, we consider the dielectric spectrum associated with Avramov model. The asymmetrical broadening of the loss spectra was found to be related directly to dispersion of the energy barrier distribution. However, it turns out that temperature dependence of the spectrum broadening as predicted by the Avromov model is at odds to experimental observation in glass-forming liquids.     

Self-assembled hydrogen-bonded coordination networks in two copper(II) carboxylates with 4-pyridylmethanol

The crystal and molecular structure of [Cu(nif)₂(4-PM)₂]·CH₃OH (1) and [Cu(2-Clbz)₂(4-PM)₂(H₂O)] (2), (where nif = niflumate anion, 2-Clbz = 2-chlorobenzoate anion and 4-PM is the 4-pyridylmethanol), have been determinated by X-ray crystallography. The Cu²⁺ cation in (1), is coordinated by two pairs of oxygen atoms from asymmetric bidentate niflumate anions and by a pair of pyridine nitrogen atoms from monodentate 4-pyridylmethanol ligands in trans position forming an extremely elongated bipyramid. The Cu²⁺ cation in (2), is coordinated by a pair of oxygen atoms from monodentate 2-chlorobenzoate anions, further by a pair of pyridine nitrogen atoms from monodentate 4-pyridylmethanol ligands and finally by a water oxygen atom forming a tetragonal-pyramidal coordination polyhedron. The molecules of both complexes in crystal structures are linked by O-H…O hydrogen bonds, which created a three-dimensional hydrogen-bonding networks. The Π-Π stacking interactions are also observed in crystal structures of complex 2. The spectral properties (IR and electronic spectra) of both complexes were also investigated.     

Time-resolved studies on the photoisomerization of a phenylene-silylene-vinylene type compound in its first singlet excited state

In femtosecond laser-flash photolysis experiments, the first singlet excited state of trans-ST, ((E,E)-{1,4-bis(2-dimethylphenylsilyl)ethenyl}benzene) showed a strong S1(π,π^?)-Sn absorption band at 540 nm in acetonitrile and at 550 nm in hexane. The lifetime of this state was determined to be 13.2±2.0 and 11.1±1.5 ps, respectively. Intersystem crossing was shown not to be a principal route for the deactivation of this S1 state of trans-ST. Evidence for this conclusion involved two complementary nanosecond laser-flash photolysis experiments. In one experiment involving direct excitation, no transient absorption spectrum was detected in the 350-650 nm spectral range. Yet, in the second experiment, on triplet sensitization, using xanthone, a transient absorption at 400 nm was tentatively assigned to the triplet state absorption of trans-ST. Photoisomerization was monitored in nanosecond time-resolved bleaching experiments. From these experiments the trans-cis photoisomerization quantum yield was determined to be 0.23 on direct trans-ST excitation. In a xanthone-sensitized stationary-state excitation experiment, the trans-cis isomerization quantum yield was determined to be 0.32. The main deactivation route of trans-ST in its S1 state is repopulation of the ground state directly through internal conversion or with the intermediacy of conformers with twisted geometry.