New Rh derivatives of s-indacene active in dehydrogenative silylation of styrene

The mono- and bimetallic complexes [(2,6-diethyl-4,8-dimethyl-s-indacenide){Rh(COD)}] (1), anti-[(2,6-diethyl-4,8-dimethyl-s-indacenediide){Rh(COD)}₂] (2a), syn-[(2,6-diethyl-4,8-dimethyl-s-indacenediide){Rh(COD)}₂] (2b) were synthesized and characterized spectroscopically and in the case of complex 2b, by means of X-ray diffraction. The ¹³C and ¹⁰³Rh NMR studies suggest that the bonding mode of the indacenediide ligand can be described as intermediate between η³- and η⁵-coordination. This result was confirmed by the crystal structure of 2b as evidenced by the slippage of the rhodium atom towards the periphery of the ligand. Cyclic voltammetry studies revealed a strong intermetallic communication through the fused ring ligand. This property was further illustrated by higher activity and selectivity of binuclear complexes 2 for the catalytic dehydrogenative silylation of styrene.     

Staudinger ligation of peptides at non-glycyl residues

The Staudinger ligation provides a means to form an amide bond between a phosphinothioester and azide. This reaction holds promise for the ligation of peptides en route to the total chemical synthesis of proteins. (Diphenylphosphino)methanethiol is the most efficacious of known reagents for mediating the Staudinger ligation of peptides, providing high (> 90%) isolated yields for equimolar couplings in which a glycine residue is at the nascent junction. Surprisingly, the yields are lower (< 50%) for non-glycyl couplings due to an aza-Wittig reaction that diverts the reaction toward a phosphonamide byproduct. Here, the partitioning of the reaction toward Staudinger ligation (and away from the aza-Wittig reaction) is shown to increase with increasing electron density on phosphorus. This electron density can be tuned either by installing functional groups on the phenyl substituents of (diphenylphosphino)methanethiol or by changing the polarity of the solvent. Installing p-methoxy groups and using a solvent of low polarity (such as toluene or dioxane) provide especially high (> 80%) isolated yields for the ligation of two non-glycyl residues. These conditions retain the high chemoselectivity of the reaction and do not lead to a substantial change in reaction rate. The traceless Staudinger ligation is now poised to enable the iterative ligation of peptides with little regard for their sequence, as well as the synthesis of amide bonds for other purposes.     

Ferromagnetic heteronuclear {Fe(4)(Er,Lu)(2)} cyclic coordination clusters based on ferric wheels

A new family of hexanuclear ferric-lanthanide [Fe(III)(4)Ln(III)(2)(Htea)(4)(Piv)(6)(N(3))(4)] clusters, where Ln(III) = Er(1) and Lu(2) is reported. Variable temperature solid-state magnetic susceptibility studies of 1 and 2 reveal the presence of ferromagnetic (1) or competing anti- and ferromagnetic exchange interactions (2) between the constituent Fe(III) ions.     

Polycationic chitosan-conjugated photosensitizer for antibacterial photodynamic therapy

The complex nature of bacterial cell membrane and structure of biofilm has challenged the efficacy of antimicrobial photodynamic therapy. This study was aimed to synthesize a polycationic chitosan-conjugated rose bengal (CSRB) photosensitizer and test its antibiofilm efficacy on Enterococcus faecalis (gram positive) and Pseudomonas aeruginosa (gram negative) using photodynamic therapy. During experiments, CSRB was tested along with an anionic photosensitizer rose bengal (RB) and a cationic photosensitizer methylene blue (MB) for uptake and killing efficacy on 7-day-old E. faecalis and P. aeruginosa biofilms. Microbiological culture based analysis was used to analyze the cell viability, while laser scanning confocal microscopy (LSCM) was used to examine the structure of biofilm. The synthesized CSRB showed absorbance spectrum similar to the RB. The concentration of CSRB uptaken by both the bacterial biofilms was significantly higher than that of RB and MB (P < 0.05). Photoactivation resulted in significantly higher elimination of both bacterial biofilms sensitized with CSRB than RB and MB. The structure of biofilm under LSCM was found to be disrupted following CSRB treatment. The present study highlighted the importance of inherent cell membrane permeabilizing effect of chitosan and increased cell/biofilm uptake of conjugated photosensitizer to produce significant antibiofilm efficacy during photodynamic therapy.     

Solid-phase synthesis of a library of C-terminal agmatine dipeptides using a backbone amide linker (BAL) strategy

In this Letter, we report a novel solid-phase strategy using a backbone amide linker (BAL) attached to a polystyrene support for the synthesis of C-terminal agmatine dipeptides. Our method eliminates the need to purify intermediates by column chromatography and enables us to build rapidly an 18-member library of C-terminal agmatine dipeptides which are subsequently screened for inhibitory activity against a viral enzyme.     

Radial orthogonality and Lebesgue constants on the disk

In polynomial interpolation, the choice of the polynomial basis and the location of the interpolation points play an important role numerically, even more so in the multivariate case. We explore the concept of spherical orthogonality for multivariate polynomials in more detail on the disk. We focus on two items: on the one hand the construction of a fully orthogonal cartesian basis for the space of multivariate polynomials starting from this sequence of spherical orthogonal polynomials, and on the other hand the connection between these orthogonal polynomials and the Lebesgue constant in multivariate polynomial interpolation on the disk. We point out the many links of the two topics under discussion with the existing literature. The new results are illustrated with an example of polynomial interpolation and approximation on the unit disk. The numerical example is also compared with the popular radial basis function interpolation.     

Multiscale experimental investigations about the cyclic behavior of the 304L SS

This work follows a series of experiments carried out earlier at INSA of Rouen (Hassan, T., Taleb, L., Krishna, S., 2008. Influence of non-proportional loading paths on ratcheting responses and simulations by two recent cyclic plasticity models. Int. J. Plast. 24, 1863–1889). It investigates the elastoplastic cyclic behavior of a 304L stainless steel at room temperature. In a first step the cross path effect on ratcheting is confirmed, as well as the crucial role of the loading path non-proportionality. Strain controlled tests are also conducted for different strain amplitudes and loading paths. Cross-hardening effect appears more important when the shearing sequence is followed by the axial one. Moreover for alternating axial and shearing cycles, this phenomenon occurs after each crossing sequence leading to a very significant strain hardening, at least of the same order as the one obtained after a circular strain path. Yet, the magnitude of the observed over hardening does not necessarily seem a function of the cumulated plastic strain.     

Rational approximation of vertical segments

In many applications, observations are prone to imprecise measurements. When constructing a model based on such data, an approximation rather than an interpolation approach is needed. Very often a least squares approximation is used. Here we follow a different approach. A natural way for dealing with uncertainty in the data is by means of an uncertainty interval. We assume that the uncertainty in the independent variables is negligible and that for each observation an uncertainty interval can be given which contains the (unknown) exact value. To approximate such data we look for functions which intersect all uncertainty intervals. In the past this problem has been studied for polynomials, or more generally for functions which are linear in the unknown coefficients. Here we study the problem for a particular class of functions which are nonlinear in the unknown coefficients, namely rational functions. We show how to reduce the problem to a quadratic programming problem with a strictly convex objective function, yielding a unique rational function which intersects all uncertainty intervals and satisfies some additional properties. Compared to rational least squares approximation which reduces to a nonlinear optimization problem where the objective function may have many local minima, this makes the new approach attractive.     

Evidence of different stoichiometries for the limiting carbonate complexes across the lanthanide(III) series: a capillary electrophoresis-mass spectrometry study

The electrophoretic mobilities (mu ep,Ln) of twelve lanthanides (not Ce, Pr and Yb) were measured by CE-ICP-MS in 0.15 and 0.5 mol L(-1) Alk2 CO3 aqueous solutions for Alk+ = Li+, Na+, K+ and Cs+. In 0.5 mol L(-1) solutions, two different mu ep,Ln values were found for the light (La to Nd) and the heavy (Dy to Tm) lanthanides, which suggests two different stoichiometries for the carbonate limiting complexes. These results are consistent with a solubility study that attests the Ln(CO3)3(3-) and Ln(CO3)4(5-) stoichiometries for the heavy (small) and the light (big) lanthanides, respectively. The Alk+ counterions influence the mu ep,Ln Alk2 CO3 values, but not the overall shape of the mu ep,Ln Alk2 CO3 plots as a function of the lanthanide atomic numbers: the counterions do not modify the stoichiometries of the inner sphere complexes. The influence of the Alk+ counterions decreases in the Li+ > Na+ > K+ > Cs+ series. The K3,Ln stepwise formation constants of the Ln(CO3)3(3-) complexes slightly increase with the atomic numbers of the lanthanides while K4,Ln, the stepwise formation constants of Ln(CO3)4(5-) complexes, slightly decrease from La to Tb, and is no longer measurable for heavier lanthanides.