Capillary zone electrophoresis in non-aqueous solutions: pH of the background electrolyte

Although the establishment of a pH scale and the determination of the pH in water is not problematic, it is not a straightforward task in non-aqueous solvents. As capillary zone electrophoresis (CZE) in organic solvents has gained increasing interest, it seems to be valuable to re-discuss the concept of the pH in such media, especially pointing to those aspects, which make pH measurement uncertain in non-aqueous solvents. In this review, the relevant aspects when dealing with primary standard (PS) and secondary standard (SS) as recommended by the International Union of Pure and Applied Chemistry (IUPAC), and the usage of the operational pH are discussed with special emphasis to non-aqueous solvents. Here, different liquid junction potentials, incomplete dissociation of the electrolytes (especially in solvents with low or moderate relative permittivity) and the occurrence of homo- and heteroconjugation must be taken into account. Problems arising in capillary zone electrophoresis practice are addressed, e.g. when the background electrolyte (BGE) consists of organic solvents, but the measuring electrode (normally the glass electrode) is calibrated with aqueous buffers, and the liquid junction potentials between the solvents do not cancel each other. The alternative concept of establishing a certain pH is described, using mixtures of reference acids or bases with known pKa in the organic solvent, and their respective salts, at a certain concentration ratio, relying to the Henderson-Hasselbalch equation. Special discussion is directed to those organic solvents most common in capillary zone electrophoresis, methanol (MeOH) and acetonitrile (ACN), but other solvents are included as well. The potential significance of small amounts of water present in the organic solvent on changes in pKa values, and thus on the pH of the buffering components is pointed out.     

Plasma Chemical Functionalisation of a Cameroonian Kaolinite Clay for a Greater Hydrophilicity

A Cameroonian kaolinite powder was treated with gliding arc plasma in order to increase the amount of hydroxyl functional groups present on its external surfaces. The functional changes that occurred were monitored by Fourier transform infrared spectroscopy. The crystalline changes were followed by the X-ray diffraction. The ionisation effect, acid effect, and water solubility of the treated samples were also evaluated. Results showed that there is breaking of the bonds in the Si–O–Si and Si–O–Al groups, followed by the formation of new aluminol (Al–OH) and silanol (Si–OH) groups at the external surface of kaolinite after exposing the clay to the gliding arc plasma. The increase in hydroxyl groups on the surface of kaolinite leads to the increase of its hydrophilicity. Moreover, new charges appear on its surfaces and no significant change in crystallinity has occurred. This study shows that clays in powder form being can effectively be functionalised by gliding arc plasma in spatial post discharge processing mode. Knowing that the treatment in spatial post discharge offers the possibility to process large amounts of clay, this work is of great interest to the industry.     

Thermally Induced Synthesis of Anthracene-, Pyrene- and Naphthalene-Fused Porphyrins

The synthesis of π-extended porphyrins containing anthracenyl moieties still represents an important challenge. Here, we report on the synthesis of a series of unsubstituted naphthyl-, pyrenyl- and anthracenyl-fused zinc porphyrin derivatives. To this aim, meso-substitued porphyrins are synthesized and the fusion of the PAHs (Polycyclic Aromatic Hydrocarbon) on the β-positions are performed through thermally induced dehydro-aromatization. The fused zinc-porphyrin derivatives are fully characterized and their optical absorption and photoluminescence properties are reported. We also demonstrate that zinc can be removed from the porphyrin core, giving rise to pure C, H, N materials. This work constitutes the first step towards the synthesis of the fully-fused tetra-anthracenylporphyrin.     

Peak dispersion and contributions to plate height in nonaqueous capillary electrophoresis at high electric field strengths: propanol as background electrolyte solvent

Peak dispersion effects in nonaqueous capillary electrophoretic separations of aromatic anionic analytes were investigated in a propanolic background electrolyte solution. Poly(glycidylmethacrylate-co-N-vinylpyrrolidone) coating was applied to the capillary to suppress the electroosmotic flow and to improve the repeatability of the migration times. Electrical field strengths up to 2000 Vcm(-1) were applied in separations and the separation efficiencies were compared with theoretical values calculated on the basis of plate height theory. The contributions to the total plate height were calculated for injection plug length, diffusion, Joule heating, electromigration dispersion, analyte adsorption to the capillary wall, and detector slit aperture length. Analyte diffusion coefficients were measured by Taylor dispersion method, while distribution constants were measured chromatographically. Agreement between the calculated and empirical results was fairly good even though some approximations were required. In most cases the longitudinal diffusion contribution governed the total plate height, while the contribution of Joule heating was insignificant even at exceptionally high field strengths used. The relatively long detection slit aperture was found to influence the separation efficiency strongly, while the other dispersion sources that were investigated were of minor importance, except for adsorption in the case of one analyte. With all analytes, the dispersive effect of longitudinal diffusion was reduced as the field strength was increased, leading to enhanced migration velocities and faster separations.     

Band-pass filtered velocity statistics in decaying turbulent box

For homogeneous isotropic turbulence study, the acquisition of band-pass filtered velocity increments (FVI) in a non-forced turbulent box is still a challenge both experimentally and numerically. Turbulence and associated physical processes, at a given instant, are permanently contaminated by a forcing process which can seldom be universal. The situation tends to be the origin of intermittency and the non-Gaussian probability density distribution for acceleration and velocity gradients. To reveal implied mechanism, grid turbulence is adapted to observe non-perturbed homogeneous isotropic turbulence. The velocity increments (VI) can be obtained following Comte-Bellot and Corrsin (GCBC) by means of two point-two time shifted velocity measurements. It is difficult to obtain decaying turbulence (DT) at large turbulent Reynolds number without pollution coming from walls. Nevertheless it is also significant to investigate DT in low Reynolds number regimes to determine non-polluted tendencies. The similarity of DT between particle image velocimetry (PIV) and hot wire anemometry measurements by GCBC are presented. Here we focus our tendency on VI and FVI probability density function (PDF) shapes in this letter. In conclusion, the tendency to Gaussian shape in inertial zone wavenumbers, demonstrates that there will be no intermittency if turbulent cascade is not perturbed.     

Multivariate Gaussian criteria in SMAA

We consider stochastic multicriteria decision-making problems with multiple decision makers. In such problems, the uncertainty or inaccuracy of the criteria measurements and the partial or missing preference information can be represented through probability distributions. In many real-life problems the uncertainties of criteria measurements may be dependent. However, it is often difficult to quantify these dependencies. Also, most of the existing methods are unable to handle such dependency information.In this paper, we develop a method for handling dependent uncertainties in stochastic multicriteria group decision-making problems. We measure the criteria, their uncertainties and dependencies using a stochastic simulation model. The model is based on decision variables and stochastic parameters with given distributions. Based on the simulation results, we determine for the criteria measurements a joint probability distribution that quantifies the uncertainties and their dependencies. We then use the SMAA-2 stochastic multicriteria acceptability analysis method for comparing the alternatives based on the criteria distributions. We demonstrate the use of the method in the context of a strategic decision support model for a retailer operating in the liberated European electricity market.     

Stabilization of the Cauchy problem for integro-differential equations

In the present paper, we obtain a criterion for the stabilization of the Cauchy problem for an integro-differential equation in the class of functions of polynomial growth γ ≥ 0. Published in Ukrains’kyi Matematychnyi Zhurnal, Vol. 57, No. 11, pp. 1571–1576, November, 2005.     

Stability of relative equilibria. Part I: The reduced energy-momentum method

Communicated by P.Holmes     

Carbon-13 spectral analysis,tautomeric structures and conformations of four two-ring methylene-bridged phloroglucinol derivatives

The ¹³C NMR spectra of phloropyron BB, desaspidin BB, albaspidin BB and margaspidin BB were recorded and the structures of the compounds investigated with the aid of chemical shifts and CH coupling constants. The filicinic acid ring of the first three compounds appeared to have a monoketonic structure with the carbonyl group in position 2 (acyl group in position 3). The pyronone ring of phloropyron BB also has a monoketonic structure, with the carbonyl function adjacent to the ring oxygen. The two rings of the first three compounds attain a conformation where a stabilizing hydrogen bond(s) is (are) formed between the two rings, as shown by the observed CH couplings to some of the hydroxyl protons. The spectrum of margaspidin BB, whichconsists of two aromatic acyl phloroglucinol rings, indicates less inter-ring hydrogen bonding interactions.