Rhodium(II)-Catalyzed Selective C(sp3)−H Amination of Alkanes

The development of an efficient catalytic system enabling the conversion of alkanes to valuable nitrogen-containing building blocks is reported. Light alkanes can be selectively functionalized by an intermolecular C(sp³)−H amination reaction that proceeds at room temperature in the presence of only 1 mol % of a dirhodium(II) complex. Selective amination of tertiary C(sp³)−H within acyclic or cyclic alkanes used as limiting components leads to the corresponding amides isolated with yields in the 51–96 % range. The reaction, that can be performed on a gram-scale, applies with equal levels of efficiency and selectivity to more complex hydrocarbons.     

Neuronal devices: understanding neuronal cultures through percolation helps prepare for the next step

Cultures of dissociated neurons are an invaluable experimental tool in studying neuronal networks at an intermediate scale in an in vitro controlled physico-chemical environment. Moreover, current micro-fabrication techniques allow the design of a custom connectivity between subpopulations, which could make it possible to carry out computations with devices involving living cells. The quorum percolation (QP) model has been designed in the context of neurobiology to describe bursts of activity occurring in neuronal cultures from the point of view of collective phenomena rather than from a dynamical synchronization approach. Such a model is well suited to describe triggered activity in neuronal devices, and its generic character points at the necessity of heavily structured devices to go beyond collective bursting. We derive a continuous extension of the QP model, seen as information propagation on a non-metric directed graph, and discuss how its critical behavior might give insight on the connectivity of neuronal networks. The link with metric graphs, embedded in a two-dimensional space, is tackled by the introduction of a geometrical model based upon a random walk, where axon growth is constrained by obstacles such as walls and channels. This provides a starting point for the construction of neuronal devices in vitro capable of more complex behaviors. Lastly, we show how simulations of bursts with a dynamical adaptive integrate-and-fire model can be interpreted in terms of QP, confirming the robustness of this synchronized behavior.     

Synthesis,Aromaticity, and Application of peri-Pentacenopentacene: Localized Representation of Benzenoid Aromatic Compounds

We report the synthesis and optoelectronic properties of TIPS-peri-pentacenopentacene ( TIPS-PPP ), a vertical extension of TIPS-pentacene ( TIPS-PEN ) and a low-band-gap material with remarkable stability. We found the synthetic conditions to avoid the competition between 1,2- and 1,4-addition of lithium acetylide on the large aromatic dione. The high stability of TIPS-PPP is due to the peri-fusion which increases the aromaticity by generating two localized aromatic sextets that are flanked with 2 diene fragments, similar to two fused-anthracenes. Like TIPS-PEN , TIPS-PPP shows the archetypal 2D brickwall motif in crystals with a larger transfer integral and smaller reorganization energy. The high mobility of up to 1 cm² V^?1 s^?1 was obtained in an organic field-effect transistor fabricated by a wet process. Also, TIPS-PPP was used as a near-infrared (NIR) emitter for NIR organic-light-emitting-diode devices resulting in a high external quantum efficiency at 800 nm.     

Overspeed burst of elastoviscoplastic rotating disks – Part I: Analytical and numerical stability analyses

Burst of rotating disks in case of overspeed is investigated. The certification of turbo-engines requires to demonstrate the integrity of disks at higher rotation speeds than the maximum rotation speed reachable in service. The determination of the burst speed by analysis can help to reduce the number of tests required for the certification. This prediction can be established by non-linear stability analyses of finite element simulations. Non-linearities originate from (i) the material behaviour described by elastoviscoplastic constitutive equations, (ii) geometric changes accounted for by the finite strain formulation. In this work, loss of uniqueness and loss of stability criteria from [Hill, R., 1958. A general theory of uniqueness and stability in elastic-plastic solids. J. Mech. Phys. Solids 6, 236–249] are applied. The loss of stability criterion is restricted to the case of rotating disks and compared to several simple widely used material based failure criteria. 3D simulations of rotating metal disks are performed for a given elastoviscoplastic behaviour and the stability criteria are evaluated. The sensitivity of disk stability to material parameters, such as yield criterion, hardening and viscosity is evaluated in the case of a nickel based superalloy.     

A yield function for single crystals containing voids

A yield function for single crystals containing voids has been developed based on a variational approach. This first yield function is phenomenologically extended by modifying the dependence on the mean stress and introducing three adjustable parameters. Unit cell finite element calculations are performed for various stress triaxiality ratios, main loading directions and porosity levels in the case of a perfectly plastic FCC single crystal. The three model parameters are adjusted on the unit cell calculations so that a very good agreement between simulation results and the proposed model is obtained.     

Synthesis and Properties of Benzo‐Fused Indeno[2,1‐c]fluorenes

A set of fully‐conjugated indenofluorenes has been synthesized and confirmed by solid‐state structure analysis. The indeno[2,1‐c]fluorenes and their benzo‐fused analogues all contain the antiaromatic as‐indacene core. The molecules possess high electron affinities and show a broad absorption that reaches into the near‐IR region of the electromagnetic spectrum. All of the featured compounds reversibly accept up to two electrons as revealed by cyclic voltammetry. Analysis of molecule tropicity using NICS‐XY scan calculations shows that, while the as‐indacene core is less paratropic than s‐indacene, benz[a]‐annulation further reduces the antiaromaticity of the core. Antiaromatic strength of the as‐indacene core can also be tuned by the position of fusion of additional arenes on the outer rings.     

Protein NMR Resonance Assignment without Spectral Analysis: 5D SOlid‐State Automated Projection SpectroscopY (SO‐APSY)

Narrow proton signals, high sensitivity, and efficient coherence transfers provided by fast magic‐angle spinning at high magnetic fields make automated projection spectroscopy feasible for the solid‐state NMR analysis of proteins. We present the first ultrahigh dimensional implementation of this approach, where 5D peak lists are reconstructed from a number of 2D projections for protein samples of different molecular sizes and aggregation states, which show limited dispersion of chemical shifts or inhomogeneous broadenings. The resulting datasets are particularly suitable to automated analysis and yield rapid and unbiased assignments of backbone resonances.     

The high pressure synthesis of the graphitic form of C3N4

Abstract

Basing on “ab-initio” calculations, C₃N₄ was claimed to be an ultra-hard material with a bulk-modulus close to that of diamond. Five different structural varieties were announced: the graphitic form, the zinc blende structure, the α and β forms of Si₃N₄ and another form, isostructural with the high pressure variety of Zn₂Si0₄.

Using the same strategy as that developed for diamond or c-BN synthesis, it appears that the graphitic form could be an appropriate precursor for preparing the 3D varieties. Two main problems characterize the C₃N₄ synthesis: (-) the temperature should be reduced in order to prevent nitrogen loss, (-) the reactivity of the precursors should be improved.

Consequently, we have developed a new process using the solvothermal decomposition of organic precursors containing carbon and nitrogen in the presence of a nitriding solvent. The resulting material, with a composition close to C₃N₄, has been characterized by different physico-chemical techniques.     

Production of [11C]Carbon Labelled Flumazenil and L-Deprenyl Using the iMiDEV™ Automated Microfluidic Radiosynthesizer

In the last decade, microfluidic techniques have been explored in radiochemistry, and some of them have been implemented in preclinical production. However, these are not suitable and reliable for preparing different types of radiotracers or dose-on-demand production. A fully automated iMiDEV™ microfluidic radiosynthesizer has been introduced and this study is aimed at using of the iMiDEV™ radiosynthesizer with a microfluidic cassette to produce [¹¹C]flumazenil and [¹¹C]L-deprenyl. These two are known PET radioligands for benzodiazepine receptors and monoamine oxidase-B (MAO-B), respectively. Methods were successfully developed to produce [¹¹C]flumazenil and [¹¹C]L-deprenyl using [¹¹C]methyl iodide and [¹¹C]methyl triflate, respectively. The final products 1644 ± 504 MBq (n = 7) and 533 ± 20 MBq (n = 3) of [¹¹C]flumazenil and [¹¹C]L-deprenyl were produced with radiochemical purities were over 98% and the molar activity for [¹¹C]flumazenil and [¹¹C]L-deprenyl was 1912 ± 552 GBq/µmol, and 1463 ± 439 GBq/µmol, respectively, at the end of synthesis. All the QC tests complied with the European Pharmacopeia. Different parameters, such as solvents, bases, methylating agents, precursor concentration, and different batches of cassettes, were explored to increase the radiochemical yield. Synthesis methods were developed using 3–5 times less precursor than conventional methods. The fully automated iMiDEV™ microfluidic radiosynthesizer was successfully applied to prepare [¹¹C]flumazenil and [¹¹C]L-deprenyl.