Highly Efficient Transition Metal Nanoparticle Catalysts in Aqueous Solutions

A ligand design is proposed for transition metal nanoparticle (TMNP) catalysts in aqueous solution. Thus, a tris(triazolyl)‐polyethylene glycol (tris‐trz‐PEG) amphiphilic ligand, 2 , is used for the synthesis of very small TMNPs with Fe, Co, Ni, Cu, Ru, Pd, Ag, Pt, and Au. These TMNP‐ 2 catalysts were evaluated and compared for the model 4‐nitrophenol reduction, and proved to be extremely efficient. High catalytic efficiencies involving the use of only a few ppm metal of PdNPs, RuNPs, and CuNPs were also exemplified in Suzuki–Miyaura, transfer hydrogenation, and click reactions, respectively.     

A new indicator to measure the noise impact around airports: The Real Estate Tolerance Level (RETL) – Case study around Charles de Gaulle Airport

The Community Tolerance Level (CTL) is a new indicator which characterizes the impact of aircraft noise around local airport. It corresponds to the exposure sound level (DENL or DNL) where 50% of the population is highly annoyed. Inspired by this indicator, this paper aims at calculating the Real Estate Tolerance Level (RETL) which corresponds to the exposure sound level where a property price is 50% depreciated compared to the price of the same property which would be situated in an area whose DENL is below 50 dB(A). The use of a notarial database analyzed with the Hedonic Price Model (HPM) made it possible to calculate the percentage of property price depreciation around CDG airport, with 1-dB steps of DENL, and so far to calculate the RETL. 19,891 house transactions and 23,264 apartments have been localized with a Geographic Information Systems (GIS) and crossed with the Sound Environment Curves provided by Airport of Paris. The RETL value for single houses and for apartments around CDG is 75.8 dB. It is comparable to the mean CTL value which has been estimated to 73.3 dB from the DNL data of 43 airports over the world (about 73.9 dB from DENL data). The RETL is predictable without field survey and could characterize the impact of aircraft noise around local airports. It could be a good indicator to follow the evolution of population tolerance over the years.     

Stochastic EM algorithms for parametric and semiparametric mixture models for right-censored lifetime data

Mixture models in reliability bring a useful compromise between parametric and nonparametric models, when several failure modes are suspected. The classical methods for estimation in mixture models rarely handle the additional difficulty coming from the fact that lifetime data are often censored, in a deterministic or random way. We present in this paper several iterative methods based on EM and Stochastic EM methodologies, that allow us to estimate parametric or semiparametric mixture models for randomly right censored lifetime data, provided they are identifiable. We consider different levels of completion for the (incomplete) observed data, and provide genuine or EM-like algorithms for several situations. In particular, we show that simulating the missing data coming from the mixture allows to plug a standard R package for survival data analysis in an EM algorithm’s M-step. Moreover, in censored semiparametric situations, a stochastic step is the only practical solution allowing computation of nonparametric estimates of the unknown survival function. The effectiveness of the new proposed algorithms are demonstrated in simulation studies and an actual dataset example from aeronautic industry.     

New Insights into the Reactivity of Cisplatin with Free and Restrained Nucleophiles: Microsolvation Effects and Base Selectivity in Cisplatin–DNA Interactions

The reactivity of cisplatin towards different nucleophiles has been studied by using density functional theory (DFT). Water was considered first to analyze the factors that govern the transformation of cisplatin into more electrophilic aquated species by using an activation‐strain model. It was found that the selectivity and reactivity of cisplatin is a delicate trade‐off between strain and interaction energies and that the second chloride is a worse leaving group than the first. When similar studies were carried out with imidazole, guanine (G), and adenine (A), it was found that in general the second nucleophilic substitution reactions have lower activation barriers than the first ones. Finally, simulations of the structural restrictions imposed by the DNA scaffold in intra‐ and interstrand processes showed that the geometries of the reaction products are nonoptimal with respect to the unrestrained A and G nucleophiles, although the energetic cost is not considerable under physiological conditions, which thus permits nucleophilic substitution reactions that lead to highly distorted DNA.     

Optimizing fragment and scaffold docking by use of molecular interaction fingerprints

Protein-ligand interaction fingerprints have been used to postprocess docking poses of three ligand data sets: a set of 40 low-molecular-weight compounds from the Protein Data Bank, a collection of 40 scaffolds from pharmaceutically relevant protein ligands, and a database of 19 scaffolds extracted from true cdk2 inhibitors seeded in 2230 scaffold decoys. Four popular docking tools (FlexX, Glide, Gold, and Surflex) were used to generate poses for ligands of the three data sets. In all cases, scoring by the similarity of interaction fingerprints to a given reference was statistically superior to conventional scoring functions in posing low-molecular-weight fragments, predicting protein-bound scaffold coordinates according to the known binding mode of related ligands, and screening a scaffold library to enrich a hit list in true cdk2-targeted scaffolds.     

Synthesis of symmetrical amino and aminomethyl derivatives of Tröger's base via Pd-catalyzed C-C and C-N bond formation

In this paper, we report the synthesis of amino and aminomethyl derivatives of Tröger's base (±)-1 and (±)-2. The key steps in the synthesis of (±)-1 and (±)-2 are Pd-catalyzed amination and cyanation, respectively, of the easily accessible dihalo derivatives (±)-3. These compounds are important intermediates in the synthesis of new ligands and building blocks for H-bonded supramolecular architectures.