Reactivity of a N-Coordinated Germylene-Borane Complex: From Ge→B to Ge→Ga Coordination

Reactivity studies of the Ge^II→B complex L(Cl)Ge⋅BH₃ ( 1 ; L=2-Et₂NCH₂-4,6-tBu₂-C₆H₂) were performed to determine the effect on the Ge^II→B donation. N-coordinated compounds L(OtBu)Ge⋅BH₃ ( 2 ) and [LGe⋅BH₃]₂ ( 3 ) were prepared. The possible tuning of the Ge^II→B interaction was proved experimentally, yielding compounds 1-PPh₂-8-(LGe)-C₁₀H₆ ( 4 ) and L(Cl)Ge⋅GaCl₃ ( 5 ) without a Ge^II→B interaction. In 5 , an unprecedented Ge^II→Ga coordination was revealed. The experimental results were complemented by a theoretical study focusing on the bonding in 1 − 5 . The different strength of the Ge^II→E (E=B, Ga) donation was evaluated by using energy decomposition analysis. The basicity of different L(X)Ge groups through proton affinity is also assessed.     

Catalytic Nitrene Transfer by an FeIV-Imido Complex Generated by a Comproportionation Process

Nitrene transfer reactions have emerged as one of the most powerful and versatile ways to insert an amine function to various kinds of hydrocarbon substrates. However, the mechanisms of nitrene generation have not been studied in depth albeit their formation is taken for granted in most cases without definitive evidence of their occurrence. In the present work, we compare the generation of tosylimido iron species and NTs transfer from Fe^II and Fe^III precursors where the metal is embedded in a tetracarbene macrocycle. Catalytic nitrene transfer to reference substrates (thioanisole, styrene, ethylbenzene and cyclohexane) revealed that the same active species was at play, irrespective of the ferrous versus ferric nature of the precursor. Through combination of spectroscopic (UV-visible, Mössbauer), ESI-MS and DFT studies, an Fe^IV tosylimido species was identified as the catalytically active species and was characterized spectroscopically and computationally. Whereas its formation from the Fe^II precursor was expected by a two-electron oxidative addition, its formation from an Fe^III precursor was unprecedented. Thanks to a combination of spectroscopic (UV-visible, EPR, Hyscore and Mössbauer), ESI-MS and DFT studies, we found that, when starting from the Fe^III precursor, an Fe^III tosyliodinane adduct was formed and decomposed into an Fe^V tosylimido species which generated the catalytically active Fe^IV tosylimide through a comproportionation process with the Fe^III precursor.     

On-line Method for Montelukast Determination in Bile Salt Medium with Multivariate Optimization and Fluorescent Detection

Journal of Analytical Chemistry - The present development involved a flow injection strategy using a mini-column of multiwalled carbon nanotubes and fluorescent detection (λex of 283 nm,...     

Analysis of stepwise charging limits and its implementation for efficiency improvement in switched capacitor DC–DC converters

In this work we analysed the stepwise charging technique to find the limits from which it is beneficial in terms of load capacitance and charge–discharge frequency. We included in the analysis practical limitations such as the consumption of auxiliary logic needed to implement the technique and the minimum size of auxiliary switches imposed by the technology. We proposed an ultra-low-power logic block to push these limits and to obtain benefits from this technique in small capacitances. Finally, we proposed to use a stepwise driver in the driving of the gate capacitance of power switches in switched-capacitor (SC) DC–DC converters. We designed and manufactured, in a 130 nm process, a SC DC–DC converter and measured a 29% energy reduction in the gate-drive losses of the converter. This accounts for an improvement of 4% (from 69 to 73%) in the overall converter efficiency.

     

A methodology to select suppliers to increase sustainability within supply chains

Central European Journal of Operations Research - Sustainability practice within supply chains remains in an early development phase. Enterprises still need tools that support the integration of...     

Efficient Design of Pruned Convolutional Neural Networks on FPGA

Journal of Signal Processing Systems - Convolutional Neural Networks (CNNs) have improved several computer vision applications, like object detection and classification, when compared to other...     

An interval branch and bound method for global Robust optimization

In this paper, we design a Branch and Bound algorithm based on interval arithmetic to address nonconvex robust optimization problems. This algorithm provides the exact global solution of such difficult problems arising in many real life applications. A code was developed in MatLab and was used to solve some robust nonconvex problems with few variables. This first numerical study shows the interest of this approach providing the global solution of such difficult robust nonconvex optimization problems.

     

Superquantiles at Work: Machine Learning Applications and Efficient Subgradient Computation

Set-Valued and Variational Analysis - R. Tyrell Rockafellar and his collaborators introduced, in a series of works, new regression modeling methods based on the notion of superquantile (or...     

k-Hankel Gabor Transform and Its Applications to the Theory of Localization Operators

Analysis Mathematica - We introduce and study the k-Hankel Gabor transform. We investigate the localization operators for this transform. In particular, we study their trace class properties and we...