The effect of aromatic interactions on the elasticity of bituminous binders

In this paper, experimental support is provided showing the importance of polyaromaticity on the elastic properties of bituminous binders. Especially the size of the polyaromatic structures seems to play a crucial role. The observations indicate that larger conjugated aromatic structures provide stronger interactions and relate to the elastic behaviour at longer loading times or up to higher temperatures, while smaller aromatic structures determine more the elastic behaviour at short loading times or at low temperatures. In addition to aromatic interactions, natural wax can, upon crystallization, also induce increased elastic effects, especially at low frequencies. A large variety of binders was investigated: bitumen from straight distillation, visbreaking, solvent deasphalting and oxidation were included in the sample set. Average levels of aromaticity were determined by Fourier transform infrared (FT-IR) spectroscopy and by refractive index measurements. Chromatography combined with UV-visible absorption spectroscopy was used as an indicator of the average size of the aromatic structures. Rheological properties were determined using a dynamic shear rheometer, in a temperature range from 0 up to 90 °C. Good relations were observed between the phase angle measurements, at specific test conditions of frequency and temperature, and UV-vis absorption levels at specific wavelengths.     

Sharp constant for the Bergman projection onto the minimal Möbius invariant space

We consider the minimal Möbius invariant space of the unit disk with norm defined in terms of the second derivative. We obtain the best constant for the Bergman projection in this setting. We also show how this result generalizes to Bergman projections with respect to standard weights and beyond.     

Nickel superoxide dismutase reaction mechanism studied by hybrid density functional methods

The reaction mechanism for the disproportionation of the toxic superoxide radical to molecular oxygen and hydrogen peroxide by the nickel-dependent superoxide dismutase (NiSOD) has been studied using the B3LYP hybrid DFT method. Based on the recent X-ray structures of the enzyme in the resting oxidized Ni(III) and X-ray-reduced Ni(II) states, the model investigated includes the backbone spacer of six residues (sequence numbers 1-6) as a structural framework. The side chains of residues His1, Cys2, and Cys6, which are essential for nickel binding and catalysis, were modeled explicitly. The catalytic cycle consists of two half-reactions, each initiated by the successive substrate approach to the metal center. The two protons necessary for the dismutation are postulated to be delivered concertedly with the superoxide radical anions. The first (reductive) phase involves Ni(III) reduction to Ni(II), and the second (oxidative) phase involves the metal reoxidation back to its resting state. The Cys2 thiolate sulfur serves as a transient protonation site in the interim between the two half-reactions, allowing for the dioxygen and hydrogen peroxide molecules to be released in the reductive and oxidative phases, respectively. The His1 side chain nitrogen and backbone amides of the active site channel are shown to be less favorable transient proton locations, as compared to the Cys2 sulfur. Comparisons are made to the Cu- and Zn-dependent SOD, studied previously using similar models.     

A dispersed fluorescence and ab initio investigation of the X2B1 and A2A1 electronic states of the PH2 molecule

In this work, the X2B1 and A2A1 electronic states of the phosphino (PH2) free radical have been studied by dispersed fluorescence and ab initio methods. PH2 molecules were produced in a molecular free-jet apparatus by laser vaporizing a silicon rod in the presence of phosphine (PH3) gas diluted in helium. The laser-induced fluorescence, from the excited A2A1 electronic state down to the ground electronic state, was dispersed and analyzed. Ten (upsilon1upsilon2upsilon3) vibrationally excited levels of the ground electronic state, with upsilon1 < or = 2, upsilon2 < or = 6, and upsilon3 = 0, have been observed. Ab initio potential-energy surfaces for the X2B1 and A2A1 electronic states have been calculated at 210 points. These two states correlate with a 2Pi(u) state at linearity and they interact by the Renner-Teller coupling and spin-orbit coupling. Using the ab initio potential-energy surfaces with our RENNER computer program system, the vibronic structure and relative intensities of the A2A1 --> X2B1 emission band system have been calculated in order to corroborate the experimental assignments.     

Urine profiling using capillary electrophoresis-mass spectrometry and multivariate data analysis

This work presents the development of a general and fast method for metabolic profiling of urine, using capillary electrophoresis-electrospray ionisation mass spectrometry (CE-ESIMS) and multivariate data analysis (DA). Human urine samples collected before and after ingestion of paracetamol were analysed at acidic and basic CE conditions, using both positive and negative ESI-MS detection. Analysis of the entire resulting data set, with no prior knowledge of the target compounds, using pair-wise 'fuzzy' correlation and eigenvalue analysis enabled the samples to be discriminated between on the basis of blank urine and urine collected after drug intake. By generating two-dimensional loadings plots, it was also possible to identify the m/z values of the substances responsible for the differentiation between control and dosed samples.     

Globotriose- and oligo(ethylene glycol)-terminated self-assembled monolayers: surface forces, wetting, and surfactant adsorption

A set of oligo(ethylene glycol)-terminated and globotriose-terminated self-assembled monolayers (SAMs) has been prepared on gold substrates. Such model surfaces are well defined and have good stability due to the strong binding of thiols and disulfides to the gold substrate. They are thus very suitable for addressing questions related to effects of surface composition on wetting properties, surface interactions, and surfactant adsorption. These issues are addressed in this report. Accurate wetting tension measurements have been performed as a function of temperature using the Wilhelmy plate technique. The results show that the nonpolar character of oligo(ethylene glycol)-terminated SAMs increases slightly but significantly with temperature in the range 20-55 degrees C. On the other hand, globotriose-terminated SAMs are fully wetted by water at room temperature. Surface forces measurements have been performed and demonstrated that the interactions between oligo(ethylene glycol)-terminated SAMs are purely repulsive and similar to those determined between adsorbed surfactant layers with the same terminal headgroup. On the other hand, the interactions between globotriose-terminated SAMs include a short-range attractive force component that is strongly affected by the packing density in the layer. In some cases it is found that the attractive force component increases with contact time. Both these observations are rationalized by an orientation- and conformation-dependent interaction between globotriose headgroups, and it is suggested that hydrogen-bond formation, directly or via bridging water molecules, is the molecular origin of these effects.     

Monte Carlo simulations of cross-linked polyelectrolyte gels with oppositely charged macroions

The volume and structural changes upon replacement of oppositely charged network counterions for oppositely charged macroions in cross-linked polyelectrolyte gels have been investigated by Monte Carlo simulations using a coarse-grained model. Initially, the gel deswells, but after an approximately equivalent amount of macroions, the gel starts to swell again. The deswelling effect is greatest for small and highly charged macroions. The role of different network properties on the deswelling has also been examined. The initial deswelling is understood in terms of a replacement of confined counterions with macroions, thereby reducing the osmotic pressure originating from the counterions. At these conditions, macroions are located near network nodes with various degrees of network chains wrapping them. At charge equivalence, a profound change in the network structure has appeared. At these conditions, the cohesive electrostatic interaction and the excluded volume effect of the macroions strongly influence the equilibrium volume of the gel. Our model system reproduces many characteristic experimental observations of polyelectrolyte gels containing oppositely charged surfactants.     

Monitoring substrate and products in a bioprocess with FTIR spectroscopy coupled to artificial neural networks enhanced with a genetic-algorithm-based method for wavelength selection

An experiment was developed as a simple alternative to existing analytical methods for the simultaneous quantitation of glucose (substrate) and glucuronic acid (main product) in the bioprocesses Kombucha by using FTIR spectroscopy coupled to multivariate calibration (partial least-squares, PLS-1 and artificial neural networks, ANNs). Wavelength selection through a novel ranked regions genetic algorithm (RRGA) was used to enhance the predictive ability of the chemometric models. Acceptable results were obtained by using the ANNs models considering the complexity of the sample and the speediness and simplicity of the method. The accuracy on the glucuronic acid determination was calculated by analysing spiked real fermentation samples (recoveries ca. 115%).     

Effect of alkali metal hydroxides on the enantioseparation of amines using di-O-isopropylidene-keto-L-gulonic acid as the selector in NACE

The present work demonstrates the importance of the ionic composition in the BGE for enantioseparation. (-)-2,3:4,6-di-O-Isopropylidene-2-keto-L-gulonic acid ((-)-DIKGA) has been used as the chiral selector in methanolic and ethanolic BGEs. The influence of added alkali metal hydroxides on the EOF and the chiral separation of amines (atenolol, isoprenaline, pindolol and propranolol) have been studied. The ion-pair formation constants in ethanol were determined by precision conductometry for the enantiomers of pindolol with (-)-DIKGA, for Li(+), Na(+) and Cs(+) with (-)-DIKGA, and also for the corresponding alkali metal hydroxides. The effective mobilities and the enantiomeric mobility differences were affected by the type of alkali metal hydroxide (LiOH, NaOH, KOH, RbOH or CsOH) added to the BGE. The effective mobility and mobility difference were increased with decrease in solvated radius of the alkali metal cation. These differences could partly be correlated to the ion-pair formation constants of the alkali metal cations with the chiral selector, affecting the equilibrium concentration of the free selector. The electroosmosis was also affected by the alkali metal hydroxide added to the BGE. The cathodic electroosmosis decreased with decreasing solvated radius of the alkali metal cation added to the BGE. Interestingly, the cathodic EOF was even reversed, i.e. became anodic in the ethanolic BGEs containing KOH, RbOH or CsOH and the methanolic ones with RbOH and CsOH.