Multiple Reaction Pathways in Rhodium‐Catalyzed Hydrosilylations of Ketones

A detailed density functional theory (DFT) computational study (using the BP86/SV(P) and B3LYP/TZVP//BP86/SV(P) level of theory) of the rhodium‐catalyzed hydrosilylation of ketones has shown three mechanistic pathways to be viable. They all involve the generation of a cationic complex [L_nRh^I]⁺ stabilized by the coordination of two ketone molecules and the subsequent oxidative addition of the silane, which results in the Rh–silyl intermediates [L_nRh^III(H)SiHMe₂]⁺. However, they differ in the following reaction steps: in two of them, insertion of the ketone into the Rh? Si bond occurs, as previously proposed by Ojima et al., or into the Si? H bond, as proposed by Chan et al. for dihydrosilanes. The latter in particular is characterized by a very high activation barrier associated with the insertion of the ketone into the Si? H bond, thereby making a new, third mechanistic pathway that involves the formation of a silylene intermediate more likely. This “silylene mechanism” was found to have the lowest activation barrier for the rate‐determining step, the migration of a rhodium‐bonded hydride to the ketone that is coordinated to the silylene ligand. This explains the previously reported rate enhancement for R₂SiH₂ compared to R₃SiH as well as the inverse kinetic isotope effect (KIE) observed experimentally for the overall catalytic cycle because deuterium prefers to be located in the stronger bond, that is, C? D versus M? D.     

Polymerization kinetic pathways of epoxidized linseed oil with aliphatic bio-based dicarboxylic acids

The curing of epoxidized linseed oil (ELO) with three different bio-based dicarboxylic acids (sebacic acid, suberic acid, and succinic acid) has been investigated. No accelerators or catalysts were used and the resulting thermosets are 100% bio-based. Structural investigations of the three crosslinked ELO resins were made using FTIR spectroscopy and TMA, that is, tensile tests, TGA, and DMA. As evidenced by FTIR measurements ELO and dicarboxylic acids reacts but no major differences can be distinguished between the dicarboxylic acids. Non-isothermal curing has been conducted by rheological and DSC measurements. Advanced isoconversional analysis applied to DSC data in association with the complex viscosity variations gives new insights into the polymerization mechanism. The length of dicarboxylic acid carbon chain modifies the reaction rate. Then, a correlation between reaction rate, activation energy, pre-exponential factors, polymerization mechanism, and change in rate-limiting step was shown. DMA and tensile tests highlight the relationship between the carbon chain length, reactivity, and thermomechanical properties. The use of succinic acid allows reaching a higher T_g and thermal stability.     

A 2D reversed-phase × ion-pair reversed-phase HPLC-MALDI TOF/TOF-MS approach for shotgun proteome analysis

The separation of complex peptide mixtures in shotgun proteome analysis using a 2D separation scheme encompassing reversed-phase × ion-pair reversed-phase (IP-RP) liquid chromatography coupled online to electrospray ion trap mass spectrometry (MS) has been shown earlier to be superior in terms of separation efficiency and technical robustness compared to the classically used separation scheme encompassing strong cation exchange × IP-RP-chromatography in shotgun proteome analysis. In the present study, this novel separation scheme was coupled offline to matrix-assisted laser desorption/ionization (MALDI) time-of-flight (TOF)/TOF-MS for the analysis of the same sample, a tryptic digest of the cytosolic proteome of the bacterium Corynebacterium glutamicum. Compared to the earlier study, the MALDI-based platform led to a significantly increased number of peptides (7,416 vs. 2,709) and proteins (1,208 vs. 468, without single peptide-based identifications), respectively. This represents the majority of all predicted cytosolic proteins in C. glutamicum. The high proteome coverage, as well as the large number of low-abundant proteins identified with this improved analytical platform, pave the way for new biological studies. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Global divergence of spatial coalescents

We study several fundamental properties of a class of stochastic processes called spatial Λ-coalescents. In these models, a number of particles perform independent random walks on some underlying graph G. In addition, particles on the same vertex merge randomly according to a given coalescing mechanism. A remarkable property of mean-field coalescent processes is that they may come down from infinity, meaning that, starting with an infinite number of particles, only a finite number remains after any positive amount of time, almost surely. We show here however that, in the spatial setting, on any infinite and bounded-degree graph, the total number of particles will always remain infinite at all times, almost surely. Moreover, if ${G\,=\,\mathbb{Z}^d}$ , and the coalescing mechanism is Kingman’s coalescent, then starting with N particles at the origin, the total number of particles remaining is of order (log* N) ^d at any fixed positive time (where log* is the inverse tower function). At sufficiently large times the total number of particles is of order (log* N) ^d-2, when d?>?2. We provide parallel results in the recurrent case d?=?2. The spatial Beta-coalescents behave similarly, where log log N is replacing log* N.     

Jarník’s convex lattice n-gon for non-symmetric norms

What is the minimum perimeter of a convex lattice n-gon? This question was answered by Jarník in 1926. We solve the same question, and prove a limit shape result, in the case when perimeter is measured by a (not necessarily symmetric) norm.     

Survival of Near-Critical Branching Brownian Motion

Consider a system of particles performing branching Brownian motion with negative drift \(\mu= \sqrt{2 - \varepsilon}\) and killed upon hitting zero. Initially there is one particle at x>0. Kesten (Stoch. Process. Appl. 7:9–47, 1978) showed that the process survives with positive probability if and only if ε>0. Here we are interested in the asymptotics as ε→0 of the survival probability Q _μ (x). It is proved that if \(L=\pi/\sqrt{\varepsilon}\) then for all x∈?, lim? _ε→0 Q _μ (L+x)=θ(x)∈(0,1) exists and is a traveling wave solution of the Fisher-KPP equation. Furthermore, we obtain sharp asymptotics of the survival probability when x<L and L?x→∞. The proofs rely on probabilistic methods developed by the authors in (Berestycki et al. in arXiv:1001.2337, 2010). This completes earlier work by Harris, Harris and Kyprianou (Ann. Inst. Henri Poincaré Probab. Stat. 42:125–145, 2006) and confirms predictions made by Derrida and Simon (Europhys. Lett. 78:60006, 2007), which were obtained using nonrigorous PDE methods.     

Direct measurement of the nitrogen content by XPS in self‐passivated TaNx thin films

The nitrogen content in tantalum nitride (TaN_x) thin films, where x indicates that TaN_x is not generally stoechiometric, can be measured directly by XPS. This is the purpose of the present study. However, the XPS spectra of TaN_x present electron energy loss spectroscopy (EELS) peaks that lead to a complex peak fitting, particularly for self‐passivated thin films. A complete peak fitting procedure based upon Tougaard's background, the Doniach‐Sunjic Function and EELS peaks, is presented. It is applied to two self‐passivated TaN_x thin films elaborated by reactive sputtering and presenting a different nitrogen content. The physical properties of these surfaces are interpreted in terms of Ta 4f_7/2 chemical states directly dependent on the nitrogen content. The main results are discussed and improvements are proposed to the method. Copyright © 2008 John Wiley & Sons, Ltd.     

Spectra of large diluted but bushy random graphs

We compute an asymptotic expansion in of the limit in of the empirical spectral measure of the adjacency matrix of an Erd?s‐Rényi random graph with vertices and parameter . We present two different methods, one of which is valid for the more general setting of locally tree‐like graphs. © 2015 Wiley Periodicals, Inc. Random Struct. Alg., 49, 160–184, 2016     

On-line solid-phase extraction high-performance liquid chromatography-tandem mass spectrometry for the quantitative analysis of tacrolimus in whole blood hemolyzate

Tacrolimus is an immunosuppressive drug essential for preventing organ rejection after transplantation. Since tacrolimus strongly binds to erythrocytes, therapeutic monitoring requires its quantification in whole blood lyzate, representing one of the most difficult to analyze biological fluids due to its high protein load. In this communication, we report on the successful combination of whole blood hemolysis employing ionic liquids, followed by sample preparation by means of on-line solid phase extraction (SPE) using restricted access materials (RAM), which permitted the efficient removal of hemoglobin and other large biomolecules. Among six different tested RAM columns, highest hemoglobin depletion and analyte extraction efficiency was obtained with a polymer-based, glycoprotein-coated RAM stationary phase (Biotrap 500 MS) operated at an alkaline pH of 10.7. Analyte quantification was performed by high-performance liquid chromatography-selected reaction monitoring tandem mass spectrometry (HPLC-SRM-MS/MS). The ability to quantify tacrolimus in therapeutically relevant concentrations in whole blood hemolyzates was demonstrated via external calibration with lower limits of detection and quantification of 2.00 and 7.23 ng mL(-1), respectively. Moreover, the investigation of heparin-pretreated blood samples during blood sampling led to an increase in sensitivity for the analyte, while the method appeared to be more robust with ethylenediaminetetraacetic acid as anticoagulant.     

Metal Silylenes Generated by Double Silicon–Hydrogen Activation: Key Intermediates in the Rhodium‐Catalyzed Hydrosilylation of Ketones

Rhodium silylenes , which are generated by double Si–H activation at the metal, are involved in a low‐activation‐barrier mechanism of the hydrosilylation of ketones with R₂SiH₂. A DFT‐based study of reaction mechanisms accounts for the experimental observations, notably the rate enhancement for R₂SiH₂ over R₃SiH and an inverse kinetic isotope effect.