Hydroboration of Alkenes Catalysed by a Nickel N-Heterocyclic Carbene Complex: Reaction and Mechanistic Aspects

The pentamethylcyclopentadienyl N-heterocyclic carbene nickel complex [Ni(η⁵-C₅Me₅)Cl(IMes)] (IMes=1,3-dimesitylimidazol-2-ylidene) efficiently catalyses the anti-Markovnikov hydroboration of alkenes with catecholborane in the presence of a catalytic amount of potassium tert-butoxide, and joins the very exclusive club of nickel catalysts for this important transformation. Interestingly, the regioselectivity can be reversed in some cases by using pinacolborane instead of catecholborane. Mechanistic investigations involving control experiments, ¹H and ¹¹B NMR spectroscopy, cyclic voltammetry, piezometric measurements and DFT calculations suggest an initial reduction of the Ni^II precursor to a Ni^I active species with the concomitant release of H₂. The crucial role of the alkoxo-catecholato-borohydride species resulting from the reaction of potassium tert-butoxide with catecholborane in the formation of an intermediate nickel-hydride species that would then be reduced to the Ni^I active species, is highlighted.     

Cooperative Dehydrogenation of N‐Heterocycles Using a Carbon Nanotube–Rhodium Nanohybrid

Rhodium nanoparticles were anchored on carbon nanotubes and the resulting nanohybrid was studied as co‐catalyst, along with tert‐butylcatechol, for the dehydrogenation of various N‐heterocycles. The co‐catalytic system operates in high yields, under the mildest conditions reported so far, and can be applied to a wide variety of secondary amine‐containing scaffolds.     

Ultra-stable microwave generation with a diode-pumped solid-state laser in the 1.5-μm range

We demonstrate the first ultra-stable microwave generation based on a 1.5-μm diode-pumped solid-state laser (DPSSL) frequency comb. Our system relies on optical-to-microwave frequency division from a planar-waveguide external cavity laser referenced to an ultra-stable Fabry–Perot cavity. The evaluation of the microwave signal at ~10 GHz uses the transportable ultra-low-instability signal source ULISS^®, which employs a cryo-cooled sapphire oscillator. With the DPSSL comb, we measured ?125 dBc/Hz phase noise at 1 kHz offset frequency, likely limited by the photo-detection shot-noise or by the noise floor of the reference cryo-cooled sapphire oscillator. For comparison, we also generated low-noise microwave using a commercial Er:fiber comb stabilized in similar conditions and observed >20 dB lower phase noise in the microwave generated from the DPSSL comb. Our results confirm the high potential of the DPSSL technology for low-noise comb applications.     

Well‐defined copolymers based on poly(vinylidene fluoride): From preparation and phase separation to application

Poly(vinylidene fluoride) (PVDF) has reached the second largest production volume of fluoropolymers in recent years, and its popularity can be ascribed to high thermal stability and chemical inertness combined with its ferroelectric behavior. Copolymerization of vinylidene fluoride with other monomers leads to a wide variety of products with modified or improved properties. Besides commercially available fluorinated random copolymers, well‐defined block‐, graft, and alternating copolymers based on PVDF received more attention in recent years. PVDF‐containing block copolymers that may self‐assemble into well‐ordered morphologies are of particular interest, being potential precursors for functional nanostructured materials applicable in membranes and electronics. This Highlight provides an overview of the routes developed towards these materials via conventional and controlled polymerization techniques. In addition, it discusses their nanoscopic phase behavior and current and potential applications. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2861–2877     

Impedance Response of a Thin Film on an Electrode: Deciphering the Influence of the Double Layer Capacitance

The different contributions of the interfacial capacitance are identified in the case of passive materials or thin protective coatings deposited on the electrode surface. The method is based on a graphical analysis of the EIS results to determine both the passive-film capacitance in the high-frequency domain and the double-layer capacitance in the low-frequency domain. The proposed analysis is shown to be independent of the physicochemical origins of the frequency dispersion of the interfacial capacitances which results, from an analysis point of view of the experimental results, in the use of a constant-phase element However, for a correct evaluation of the thin-film properties such as its thickness, the high-frequency data must be corrected for the double-layer contribution. In particular, it is shown that if the double-layer capacitance gives a frequency-dispersed response, it is necessary to correct the high-frequency part for the double-layer constant-phase elements. This is first demonstrated on synthetic data and then used for the determination of the thickness of thin oxide film formed on Al in neutral pH solution.     

Irradiated UAmO2 transmutation discs analyses: from dissolution to isotopic analyses

Journal of Radioanalytical and Nuclear Chemistry - This paper details the different steps for the isotopic determination of UAmO2 discs from analytical irradiation. MARIOS and DIAMINO irradiations...     

Understanding the Reshaping of Fluorinated Polyester Vitrimers by Kinetic and DFT Studies of the Transesterification Reaction

Vitrimers are a third class of polymers gathering the mechanical properties and solvent resistance of 3D thermosets and the reprocessability of thermoplastics. This unique behaviour is due to the triggering of certain covalent exchange reactions that allow the network to rearrange upon application of a stimulus. The constitutive feature of vitrimers is the adoption of a glass-like viscosity during the rearrangement of the network, often due to an associative mechanism for the exchange reaction. Transesterification networks are one of the most studied type of vitrimers that usually require the incorporation of a catalyst, implying the associated drawbacks. Following up on a recent report on catalyst-free transesterification vitrimers in which the ester functions are particularly reactive thanks to the presence of fluorine atoms in α- or β-position, parallel DFT calculations and an experimental kinetic study on model molecules are presented in order to quantitatively assess the effect of neighbouring fluorinated groups on the transesterification reaction rate.     

Using Singular Spectrum Analysis to obtain staffing level requirements in emergency units

Many operational research (OR) techniques use historical data to populate model input parameters. Although the majority of these models take into account stochastic variation of the inputs, they do not necessarily take into account seasonal variations and other stochastic effects that might arise. One of the major applications of OR lies within healthcare, where ever increasing pressure on healthcare systems is having major implications on those who plan the provision of such services. Coping with growing demand for healthcare, as well as the volatile nature of the number of arrivals at a healthcare facility makes modelling healthcare provision one of the most challenging fields of OR. This paper proposes the use of a relatively modern time series technique, Singular Spectrum Analysis (SSA), to improve existing algorithms that give required staffing levels. The methodology is demonstrated using data from a large teaching hospital's emergency unit. Using time dependent queueing theory, as well as SSA, staffing levels are obtained. The performance of our technique is analysed using a weighted mean square error measure, introduced in this paper.