Separation of amino acids. Possibilities offered by optimized associations of low-voltage electrophoresis and chromatography on finely textured paper and on cellulose thin-layers

Summary Three optimized small-scale methods for amino acid separation are described and compared. Two dimensional separations are based on paper or cellulose thin-layer ionophoresis and chromatography with simple and inexpensive apparatus. The influence of experimental conditions on resolution and amount required for amino acids possessing almost identical mobilities, is studied. The quickest procedure based on the coupling of 200×200×0.25 mm thin-layer, low-voltage electrophoresis (20 V/cm) with chromatography, and the system: cellulose −1.04 mol dm⁻³ formic acid — tertbutanol/methanol/pyridine/formic acid/water (33∶43∶9.6∶0.4∶20), provides very reproducible results with high separating power for small samples (2–10 nmoles).     

A new catalytic route for the epoxidation of styrene with sodium hypochlorite activated by transition metal complexes

Preliminary results on the transition metal catalyzed expoxidation of styrene and cyclohexene with sodium hypochlorite solution and phase-transfer reagent are described.     

The “strange term” in the periodic homogenization for multivalued Leray–Lions operators in perforated domains

Using the periodic unfolding method of Cioranescu, Damlamian and Griso, we study the homogenization for equations of the form

$-{\rm div}\,\,d_\varepsilon=f,\,\,{\rm with}\,\,\left(\nabla u_{\varepsilon , \delta }(x),d_{\varepsilon , \delta }(x)\right) \in A_\varepsilon(x)$

in a perforated domain with holes of size \({\varepsilon \delta }\) periodically distributed in the domain, where \({A_\varepsilon }\) is a function whose values are maximal monotone graphs (on R ^N ). Two different unfolding operators are involved in such a geometric situation. Under appropriate growth and coercivity assumptions, if the corresponding two sequences of unfolded maximal monotone graphs converge in the graph sense to the maximal monotone graphs A(x, y) and A ₀(x, z) for almost every \({(x,y,z)\in \Omega \times Y \times {\rm {\bf R}}^N}\), as \({\varepsilon \to 0}\), then every cluster point (u ₀, d ₀) of the sequence \({(u_{\varepsilon , \delta }, d_{\varepsilon , \delta } )}\) for the weak topology in the naturally associated Sobolev space is a solution of the homogenized problem which is expressed in terms of u ₀ alone. This result applies to the case where \({A_{\varepsilon}(x)}\) is of the form \({B(x/\varepsilon)}\) where B(y) is periodic and continuous at y = 0, and, in particular, to the oscillating p-Laplacian.

     

Comparative measurements of loudspeakers in a listening situation

Comparison of loudspeakers is a major concern during design or product selection. There are several standards for the measurement of loudspeaker characteristics, but none of them provides hints for a rigorous comparison between devices. In this study, different ways of evaluating acoustical dissimilarity between loudspeakers were compared. Several methods of signal analysis were used, and for each method a metric evaluating the dissimilarity between two signals was defined. The correlation between the different dissimilarity evaluations over a significant panel of loudspeakers led to identified classes of measurements. A specific aspect of this work is that measurements were performed in a standard listening environment, rather than in an anechoic or reverberant one. It allowed the use of the recorded signals for a simple listening test, providing a perceptual metric which was compared to the acoustical ones. It also allowed the introduction of auditory models in the computation of some acoustical metrics, so defining a new class of measurements which gave results close to the perceptual ones.     

On-Surface Synthesis and Characterization of Acene-Based Nanoribbons Incorporating Four-Membered Rings

A bottom up method for the synthesis of unique tetracene-based nanoribbons, which incorporate cyclobutadiene moieties as linkers between the acene segments, is reported. These structures were achieved through the formal [2+2] cycloaddition reaction of ortho-functionalized tetracene precursor monomers. The formation mechanism and the electronic and magnetic properties of these nanoribbons were comprehensively studied by means of a multitechnique approach. Ultra-high vacuum scanning tunneling microscopy showed the occurrence of metal-coordinated nanostructures at room temperature and their evolution into nanoribbons through formal [2+2] cycloaddition at 475 K. Frequency-shift non-contact atomic force microscopy images clearly proved the presence of bridging cyclobutadiene moieties upon covalent coupling of activated tetracene molecules. Insight into the electronic and vibrational properties of the so-formed ribbons was obtained by scanning tunneling microscopy, Raman spectroscopy, and theoretical calculations. Magnetic properties were addressed from a computational point of view, allowing us to propose promising candidates to magnetic acene-based ribbons incorporating four-membered rings. The reported findings will increase the understanding and availability of new graphene-based nanoribbons with high potential in future spintronics.     

“Through-space” P spin-spin couplings in ferrocenyl tetraphosphine coordination complexes: Improvement in the determination of the distance dependence of JPP constants

From the analysis of several nickel and palladium halide complexes of a constrained ferrocenyl tetraphosphine, the existence in solution phase of unique ³¹P-³¹P “through-space” nuclear spin-spin coupling constants (J_PP) had been previously evidenced. Due to the blocked conformation of the species in solution, and based on the NMR spectra obtained for the complexes and their corresponding solid state X-ray structures, these J_PP constants had been shown to clearly depend on the mutual spatial position of the corresponding phosphorus atoms. Herein, the quantitative correlation disclosed at that time (P?P distance dependence of coupling constants) is remarkably confirmed, and mathematically refined owing to the study of a new palladium dibromide tetraphosphine complex, for which the synthesis and the solution NMR and solid state X-ray characterizations are reported.     

Platinated copper(3-clip-phen) complexes as effective DNA-cleaving and cytotoxic agents

The synthesis and biological activity of three heteronuclear platinum-copper complexes based on 3-Clip-Phen are reported. These rigid complexes have been designed to alter the intrinsic mechanism of action of both the platinum moiety and the Cu(3-Clip-Phen) unit. The platinum centers of two of these complexes are coordinated to a 3-Clip-Phen moiety, an ammine ligand and two chlorides, which are either cis or trans to each other. The third complex comprises two 3-Clip-Phen units and two chloride ligands bound in a trans fashion to the platinum ion. DNA-cleavage experiments show that the complexes are highly efficient nuclease agents. In addition, a markedly difference in their aptitude to perform direct double-strand cleavage is observed, which appears to be strongly related to the ability of the platinum unit to coordinate to DNA. Indeed, complex 6 is unable to coordinate to DNA, which is reflected by its incapability to carry out double-strand breaks. Nonetheless, this complex exhibits efficient DNA-cleavage activity, and its cytotoxicity is high for several cell lines. Complex 6 shows better antiproliferate activity than both cisplatin and Cu(3-Clip-Phen) toward most cancer cell lines. Furthermore, the cytotoxicity observed for 1 is for most cell lines close to that of cisplatin, or even better. Cu(3-Clip-Phen) induces very low cytotoxic effects, but a marked migratory activity. Complex 6 presents DNA-cleavage properties comparable to the one of Cu(3-Clip-Phen), but it does not show any migratory activity. Interestingly, both Cu(3-Clip-Phen) and 6 induces vacuolisation processes in the cell in contrast to complex 1 and cisplatin. Thus, the four complexes cisplatin tested, Cu(3-Clip-Phen), 1 and 6 stimulate different cellular responses.     

Electron transport in open systems from finite-size calculations: Examination of the principal layer method applied to linear gold chains

We describe the occurrence of computational artifacts when the principal layer method is used in combination with the cluster approximation for the calculation of electronic transport properties of nanostructures. For a one-dimensional gold chain, we observe an unphysical band in the band structure. The artificial band persists for large principal layers and for large buffer sizes. We demonstrate that the assumption of equality between Hamiltonian elements of neighboring layers is no longer valid and that a discontinuity is introduced in the potential at the layer transition. The effect depends on the basis set. When periodic boundary conditions are imposed and the k-space sampling is converged, the discontinuity disappears and the principal layer method can be correctly applied by using a linear combination of atomic orbitals as basis set.