Reversibility of Conjugacies for Nonautonomous Equations

We establish a reversible version of the Grobman–Hartman theorem for nonautonomous differential equations in Banach spaces. Namely, we show that if the differential equation is reversible, then the topological conjugacies in the Grobman–Hartman theorem also commute with the symmetries. The result is illustrated with an example.     

Towards nanoscale composite particles of dual complexity

The fabrication of heteroaggregates comprising inorganic and organic nanoparticles of different sizes is reported. Control over the assembly of nanoscale functional building units is of great significance to many practical applications. Joining together different spherical nanoparticles in a defined manner allows control over the shape of the composites. If two types of constituents are chosen that differ in size, the surfaces of the composites exhibit two specific radii of curvature, yielding aggregates of dual surface roughness. Moreover, if the constituents consist of different materials, the resulting heteroaggregates feature both compositional and interfacial anisotropy, offering unprecedented perspectives for custom-tailored colloids. This study describes a two-step approach towards such designer particles. At first, amine-modified polystyrene particles with 154 nm diameter were assembled into clusters of well-defined configurations. Onto these, oppositely charged inorganic particles with diameters of only a few nanometres were deposited by direct uptake from solution, resulting in numerous functional entities all over the surface of the polymer clusters. Despite the fact that oppositely charged constituents are brought together, charge reversal by uptake of nanoparticles allows for stable suspensions of heterocomposites. Hence, the possibility to assemble particles into nanoscale heterocomposites with full control over shape, composition, and surface roughness is demonstrated.     

Molecular aspects of the interaction between plants sterols and DPPC bilayers: an experimental and theoretical approach

The effect of sterols composition in a lipid bilayer was investigated on membranes of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) and mixtures with the plant sterols β-sitosterol and stigmasterol. Differential scanning calorimetry, 1,6-diphenyl-1,3,5-hexatriene (DPH) fluorescence polarization and infrared spectroscopy studies showed that both sterols changed the packing of the membrane and the hydration of the polar headgroup of the phospholipids, disordering the gel phase and, vice versa, ordering the membrane in the liquid crystalline phase. In all cases some differences among β-sitosterol and stigmasterol could be observed, being β-sitosterol slightly more efficient than stigmasterol in ordering a fluid membrane, bringing the membrane to a more packed liquid ordered phase. Molecular dynamic simulations were carried out to better characterize the distinct behavior of both sterols in a DPPC-membrane. The calculated parameters agreed quite well with the experimental results and a molecular model is proposed to explain differences in the sterols molecules and their effect on the DPPC-bilayer.     

Linear and nonlinear optical properties of cationic bipyridyl iridium(III) complexes: tunable and photoswitchable?

A series of cationic Ir(III) substituted bipyridyl ()(N(∧)N (N(∧)N-bpy) complexes incorporating electron-donor and -acceptor substituents, [Ir(C(∧)N-ppy-R')(2)(N(∧)N-bpy-CH═CH-C(6)H(4)-R)][X] (X(-) = PF(6)(-) or C(12)H(25)SO(3)(-)), 2 (a, R = NEt(2) and R' = Me; b, R = O-Oct and R' = Me; c, R = NO(2) and R' = C(6)H(13); C(∧)N-ppy = cyclometalated 2-phenylpyridine, [Ir(C(∧)N-ppy-Me)(2)(N(∧)N-bpy-CH═CH-thienyl-Me)][PF(6)], 2d, and the dithienylethene (DTE)-containing complex 2e have been synthesized and characterized, and their absorption, luminescence, and quadratic nonlinear optical (NLO) properties are reported. Density functional theory (DFT) and time-dependent-DFT (TD-DFT) calculations on the complexes facilitate a detailed assignment of the excited states involved in the absorption and emission processes. All five complexes are luminescent in a rigid glass at 77 K, displaying vibronically structured spectra with long lifetimes (14-90 μs), attributed to triplet states localized on the styryl-appended bipyridines. The second-order NLO properties of 2a-d and related complexes 1a-d with 1,10-phenanthrolines have been investigated by both electric field induced second harmonic generation (EFISH) and harmonic light scattering (HLS) techniques. They are characterized by high negative EFISH μβ values which decrease when the ion pair strength between the cation and the counterion (PF(6)(-), C(12)H(25)SO(3)(-)) increases. The EFISH response is mainly controlled by metal-to-ligand charge-transfer/ligand-to-ligand charge-transfer (MLCT/L'LCT) processes. A combination of HLS and EFISH techniques is used to evaluate both the dipolar and octupolar contributions to the total quadratic hyperpolarizability, demonstrating that the major contribution is controlled by the octupolar part. The incorporation of a photochromic DTE unit into the N(∧)N-bpy ligand (complex 2e) allows the luminescence to be switched ON or OFF. The photocyclisation of the DTE unit can be triggered by using either UV (365 nm) or visible light (430 nm), leading to an efficient quenching of the ligand-based 77 K luminescence, which can be restored upon irradiation of the closed form at 715 nm. In contrast, no significant modification of the EFISH μβ value is observed upon photocyclization, suggesting that the quadratic NLO response is dominated by the MLCT/L'LCT processes, rather than by the intraligand excited states localized on the substituted bipyridine ligand.     

Molecular recognition of ADP over ATP in aqueous solution by a polyammonium receptor containing a pyrimidine residue

The synergistic action of the different binding groups of the polyfunctional HL receptor leads to the recognition of ADP over ATP in water, with a selectivity coefficient of up to 116, a phenomenon which is unprecedented in the context of synthetic receptors in water. The recognition is mostly due to the good matching between H(3)L(2+) and the protonated forms of ADP.     

Surface-enhanced Raman scattering and DFT investigation of Eriochrome Black T metal chelating compound

The surface-enhanced Raman scattering (SERS) spectra of Eriochrome Black T (EBT) and its Cu(II), Fe(III), Mn(II) and Pb(II) complexes were recorded using a hydroxylamine reduced silver colloid. Molecular geometry optimization, molecular electrostatic potential (MEP) distribution and vibrational frequencies calculation were performed at B3LYP/6-31G(d) level of theory for the EBT molecule and its Cu(EBT), Fe(EBT) and Mn(EBT) metal complexes. Differentiation between EBT complexes of Cu(II), Fe(III), Mn(II) and Pb(II) is shown by the SERS spectral features of each complex.     

Absence of quenching by [Fe(CN)6]4- is not proof of DNA intercalation

The quenching of the (3)MLCT emission of three Ru(II) complexes of known DNA binding mode is compared. This work shows that relative binding constants dictate whether quenching is observed in the presence of DNA rather than protection of the probe by intercalation, as has been commonly stated.     

Conformational studies of the robust 2-Cys peroxiredoxin Salmonella typhimurium AhpC by solution phase hydrogen/deuterium (H/D) exchange monitored by electrospray ionization mass spectrometry

This is the first comprehensive HX-MS study of a "robust" 2-Cys peroxiredoxin (Prx), namely Salmonella typhimurium AhpC (StAhpC). Prx proteins control intracellular peroxide levels and are abundant antioxidant proteins in eukaryotes, archaea and bacteria. Crystal structural analyses and structure/activity studies of several bacterial and mammalian 2-Cys Prxs have revealed that the activity of 2-Cys Prxs is regulated by redox-dependent oligmerization and a sensitivity of the active site cysteine residue to overoxidation. The propensity to overoxidation is linked to the conformational flexibility of the peroxidatic active site loop. The HX-MS results emphasize the modulation of the conformational motility of the active site loop by disulfide formation. To obtain information on the conformational impact of decamer formation on the active site loop motility, mutants with Thr77 substituted by Ile, a decamer-disrupting mutation or by Val, a decamer-stabilizing mutation, were studied. For the isoleucine mutant, enhanced mobility was observed for regions encompassing the α4 helix located in the dimer-dimer interface and regions surrounding the peroxidatic loop. In contrast, the T77V mutation resulted in an increase in conformational stability in most regions of the protein except for the active site loop and the region encompassing the resolving cysteine.     

Radon hydrides: structure and bonding

Quantum chemical calculations, using gradient-correct density functional at the BP86 level in conjunction with TZ2P basis sets, have been carried out for the radon hydrides HRnY (with Y = F, Cl, Br, I, CCH, CN, and NC). The bonding in HRnY is studied using different bond ruptures, establishing the role of those stabilizing (and destabilizing) factors that prevent these species to be dissociated. Although all HRnY systems studied here are bound equilibrium structures, they are metastable species with respect to the HRnY → Rn + HY decomposition channel. However, the HRnY → H + Rn + Y reaction is endothermic. So, these results indicate the possibility to identify the radon hydrides in noble-gas matrices.