Regulation of the retention factor for weak acids in micellar electrokinetic chromatography with cationic surfactant via variation of the chloride concentration

For tetradecyltrimethylammonium bromide in boric acid/borate or acetic acid/acetate buffer and NaCl or CaCl? as the added salt, it is investigated whether the retention behaviour of weak acids in MEKC with cationic surfactant can be modelled by assuming for the deprotonated species predominantly electrostatic interaction with the micelles acting as a pseudostationary ion-exchanger. The retention of (partially) charged solutes by oppositely charged micelles is analyzed by applying the classical theory of IEC (plotting lg k against lg(c(Cl?)) assuming a fixed concentration of ion-exchange sites. When plotting the absolute slopes of the regression lines against the absolute effective charge numbers of the analytes, correlation coefficients of 0.968-0.998 were obtained. It is shown that the dependence of the retention factor on the concentration of chloride (the competing ion) in the separation electrolyte and on the degree of dissociation of the analyte corresponds to what would be expected for mixed-mode retention (hydrophobic and ion-exchange interaction) on a pseudostationary ion-exchanger.     

Influence of the nature of the absorption band on the potential performance of high molar extinction coefficient ruthenium(II) polypyridinic complexes as dyes for sensitized solar cells

When tested in solar cells, ruthenium polypyridinic dyes with extended π systems show an enhanced light-harvesting capacity that is not necessarily reflected by a high (collected electrons)/(absorbed photons) ratio. Provided that metal-to-ligand charge transfer bands, MLCT, are more effective, due to their directionality, than intraligand (IL) π-π* bands for the electron injection process in the solar cell, it seems important to explore and clarify the nature of the absorption bands present in these types of dyes. This article aims to elucidate if all the absorbed photons of these dyes are potentially useful in the generation of electric current. In other words, their potentiality as dyes must also be analyzed from the point of view of their contribution to the generation of excited states potentially useful for direct injection. Focusing on the assignment of the absorption bands and the nature of the emitting state, a systematic study for a series of ruthenium complexes with 4,4'-distyryl-2,2'-dipyridine (LH) and 4,4'-bis[p-(dimethylamino)-α-styryl]-2,2'-bipyridine (LNMe(2)) "chromophoric" ligands was undertaken. The observed experimental results were complemented with TDDFT calculations to elucidate the nature of the absorption bands, and a theoretical model was proposed to predict the available energy that could be injected from a singlet or a triplet excited state. For the series studied, the results indicate that the percentage of MLCT character to the anchored ligand for the lower energy absorption band follows the order [Ru(deebpy)(2)(LNMe(2))](PF(6))(2) > [Ru(deebpy)(2)(LH)](PF(6))(2) > [Ru(deebpy)(LH)(2)](PF(6))(2), where deebpy is 4,4'-bis(ethoxycarbonyl)-2,2'-bipyridine, predicting that, at least from this point of view, their efficiency as dyes should follow the same trend.     

Studying the interaction between triazines and humic substances--a new approach using open tubular capillary electrochromatography

The strength of the interaction between a pesticide and the soil organic matter is a key parameter to assess the risk of it reaching to groundwater with potentially harmful effects to human health. In this work, a new approach that allows measuring such interactions in a few minutes using a purified fraction of the soil organic matter (humic substances) is detailed. The strength of sorption is assessed via the normalised difference of elution (retention factor, k′) between the chemical of interest and a neutral marker transported via electroosmotic flow through an open tubular column supporting the immobilised humic substances (open tubular capillary electrochromatography). The immobilisation was achieved by incubating a capillary, pre-coated with a monolayer of humic acid, with an acidic solution of humic substances. This induces the formation of a supramolecular structure of humic substances as it occurs in soils. This aggregate can easily be removed using alkaline solutions, and a new structure assembled using other humic substances (HS) or different incubations conditions. The whole procedure takes 2 h. This approach has been tested using five triazines and three types of humic substances. The order of the strength of sorption of the triazines as expected from relevant literature and the relative standard deviation of k′ was between 1 and 6%. Good repeatability was also observed after long period of wash, between re-coating and repeating of the full coating with a new capillary.     

Note on the number of zeros of $$\zeta ^{(k)}(s)$$ ζ ( k ) ( s )

The Ramanujan Journal - Assuming the Riemann hypothesis, we prove that $$\begin{aligned} N_k(T) = \frac{T}{2\pi }\log \frac{T}{4\pi e} + O_k\bigg (\frac{\log T}{\log \log T}\bigg ), \end{aligned}$$...     

Assessment of the indoor-to-outdoor ratio of dose rates in and around the historic objects in Bosnia and Herzegovina

Journal of Radioanalytical and Nuclear Chemistry - This paper deals with the first study of the indoor to outdoor ambient dose equivalent rates ratio measured in and around the historic objects at...     

Surface and mechanical analysis of metallized poly(dimethylsiloxane) gel for varifocal micromirrors

Varifocal micromirrors are alternative and miniaturized mirror systems that are used for imaging procedures in biomedical diagnostics, mirror-based tunable lenses, or the correction of spherical aberration. In this study, we demonstrate a new concept for focal length variation by electrostatic mirror deformation of a compact and integrated electroactive polymer actuator based on metallized poly(dimethylsiloxane) (PDMS) gel thin films. The varifocal micromirrors have a lateral size of 70 × 70 μm² and are capable of deforming in either convex or concave direction, depending on a defined surface treatment by O₂-plasma or UV/ozone of the PDMS prior to metallization by physical vapor deposition (PVD). Surface and interface analysis by wetting experiments, sputter depth-profiling X-ray photoelectron spectroscopy (XPS) combined with scanning electron microscopy (SEM) on cross-sections processed with focused ion beam (FIB) as well as polymer and metal surfaces are used to understand and to improve the metal film growth and quality with respect to high reflectivity and conductivity. In addition to the high quality of the metallic mirror layer, the mirror displacement is important and inevitably depends on the gel stiffness of the actuator. Therefore, we investigate the gel mechanics and the performance of the actuator with rheology, confocal microscopy, and image formation on the electrically deformed mirrors. Our concept of varifocal micromirrors offers a wide range of applications for tunable mirror-based optics due to their simple and compact design.     

Probing solubilization sites in block copolymer micelles using fluorescence quenching

The solubilization sites provided by micelles formed by a diblock copolymer with one neutral hydrophobic block, polystyrene, and one charged hydrophilic block, poly(acrylic acid) or poly(methacrylic acid), have been studied by fluorescence quenching of pyrene by polar and nonpolar quenchers. Pyrene solubilized into these micelles is distributed between the inner corona and the micelle core. The fraction of pyrene residing in the inner corona is almost unity for star micelles, where the corona-forming blocks are larger than the core-forming blocks, and around 0.5 for crew-cut micelles where the opposite situation prevails. The kinetics of the quenching process depends on the pyrene location, i.e. is static in the micelle core, and largely dynamic in the inner corona at low quencher concentration. The rate constants for fluorescence quenching by nitromethane are shown to increase with increasing pH.     

Phase Space Tunneling in Multistate Scattering

We prove exponentially small estimates on the off-diagonal terms of the scattering matrix associated to two-state semiclassical Schrödinger Hamiltonians. Our method is based on phase space tunneling estimates and a splitting of the operator by means of Toeplitz-type phase space cutoff operators.     

A contraction of the Lucas polygon

The celebrated Gauss-Lucas theorem states that all the roots of the derivative of a complex non-constant polynomial lie in the convex hull of the roots of , called the Lucas polygon of . We improve the Gauss-Lucas theorem by proving that all the nontrivial roots of lie in a smaller convex polygon which is obtained by a strict contraction of the Lucas polygon of .