Pluronics‐Stabilized Gold Nanoparticles: Investigation of the Structure of the Polymer–Particle Hybrid

Hybrid gold–polymer nanoparticles are obtained by self‐assembly of amphiphilic copolymers (Pluronics) in solutions containing preformed gold nanoparticles (diameter ca. 12 nm). Dynamic light scattering, TEM, cryo‐TEM, and small‐angle neutron scattering experiments with contrast variation are used to characterize the structure of the gold–polymer particles. Five Pluronics (F127, F68, F88, F108, P84) with different molecular weights and hydrophilic/hydrophobic balances are investigated. Gold nanoparticles are individually embedded within globules of polymer, even under conditions for which Pluronics micelles do not form in solution. The hybrid particles are several tens of nanometers in size (larger than micelles of the corresponding Pluronics), and the size can be tuned by changing the temperature.     

Solvation of Co(III)-cysteinato complexes in water: a DFT-based molecular dynamics study

Structural, dynamical, and vibrational properties of complexes made of metal cobalt(III) coordinated to different amounts of cysteine molecules were investigated with DFT-based Car-Parrinello molecular dynamics (CPMD) simulations in liquid water solution. The systems are composed of Co(III):3Cys and Co(III):2Cys immersed in liquid water which are modeled by about 110 explicit water molecules, thus one of the biggest molecular systems studied with ab initio molecular simulations so far. In such a way, we were able to investigate structural and dynamical properties of a model of a typical metal binding site used by several proteins. Cobalt, mainly a toxicological agent, can replace the natural binding metal and thus modify the biochemical activity. The structure of the surrounding solvent around the metal-ligands complexes is reported in detail, as well as the metal-ligands coordination bonds, using radial distribution functions and electronic analyses with Mayer bond orders. Structures of the Cocysteine complexes are found in very good agreement with EXAFS experimental data, stressing the importance of considering the surrounding solvent in the modeling. A vibrational analysis is also conducted and compared to experiment, which strengthens the reliability of the solvent interactions with the Cocysteine complexes from our molecular dynamics simulations, as well as the dynamics of the systems. From this preliminary analysis, we could suggest a vibrational fingerprint able to distinguish Co(III):2Cys from Co(III):3Cys. Our simulations also show the importance of considering a quantum explicit solvent, as solute-to-solvent proton transfer events have been observed.     

Synthesis of 2-Azanorbornanes via Strain-Release Formal Cycloadditions Initiated by Energy Transfer

Rigid bicycles are becoming more popular in the pharmaceutical industry because they allow for expansion to new and unique chemical spaces. This work describes a new strategy to construct 2-azanorbornanes, which can act as rigid piperidine/pyrrolidine scaffolds with well-defined exit vectors. To achieve the synthesis of 2-azanorbornanes, new strain-release reagent, azahousane, is introduced along with its photosensitized strain-release formal cycloaddition with alkenes. Furthermore, new reactivity between a housane and an imine is disclosed. Both strategies lead to various substituted 2-azanorbornanes with good selectivities.     

Photodetachment of Deprotonated R-Mandelic Acid: The Role of Proton Delocalization on the Radical Stability

The photodetachment and stability of R-Mandelate, the deprotonated form of the R-Mandelic acid, was investigated by observing the neutral species issued from either simple photodetachment or dissociative photodetachment in a cold anions set-up. R-Mandalate has the possibility to form an intramolecular ionic hydrogen-bond between adjacent hydroxyl and carboxylate groups. The potential energy surface along the proton transfer (PT) coordinate between both groups (O⁻…H⁺…⁻OCO) features a single local minima, with the proton localized on the O⁻ group (OH…⁻OCO). However, the structure with the proton localized on the ⁻OCO group (O⁻…HOCO) is also observed because it falls within the extremity of the vibrational wavefunction of the OH…⁻OCO isomer along the PT coordinate. The stability of the corresponding radicals, produced upon photodetachment, is strongly dependent on the position of the proton in the anion: the radicals produced from the OH…⁻OCO isomer decarboxylate without barrier, while the radicals produced from the O⁻…HOCO isomer are stable.     

Nickel(II) chain with alternating end-on/end-to-end single azido bridges: a combined structural, magnetic, and theoretical study

The reaction of a tridentate Schiff base LH (L-: 1,1,1-trifluoro-7-(dimethylamino)-4-methyl-5-aza-3-hepten-2-onato) with a Ni(II) salt in the presence of azide salt has led to a new alternating end-on (EO)/end-to-end (EE) azido-bridged Ni(II) chain of formula {[Ni2(micro1,1-N3)(micro1,3-N3)(L)2(MeOH)2]}n. Its originality lies in the presence of single EE and EO coordination modes for the azide. It crystallizes in the C2/c space group, a=21.570(7) A, b=10.79(1) A, c=16.154(5) A, beta=120.81(2) degrees, Z=4. The chain can be viewed as {Ni2(N3)(L)2(MeOH)2}+ dimeric units linked to each other in a zigzag pattern by the other azide. Magnetic susceptibility and magnetization measurements have been performed and revealed that the chain can magnetically be depicted as isolated {Ni2(N3)} units exhibiting antiferromagnetic interaction (JAF approximately -37 cm(-1)). Ab initio calculations confirmed the efficient magnetic coupling through the EE bridge and vanishingly small EO {Ni2(micro1,1-N3)} interactions.     

Hyperbranched polyamidoamine as stabilizer for catalytically active nanoparticles in water

Poly(amidoamine) hyperbranched polymers (HYPAM) were successfully used to synthesize platinum nanoparticles of ca. 1.8 nm and to stabilize these particles in water. Furthermore these hyperbranched-stabilized platinum nanoparticles proved to be effective and robust for hydrogenation reaction in water.     

Timetabling of sorting slots in a logistic warehouse

We study a problem that occurs at the end of a logistic stream in a warehouse and which concerns the timetabling of the sorting slots that are used to accommodate the prepared orders before they are dispatched. We consider a set of orders to be prepared in a certain number of preparation shops over a given time horizon. Each order is associated with the truck that will transport it to the customer. A sorting slot is an accumulation area where processed orders wait to be loaded onto a truck. For a given truck a known number of sorting slots is needed from the time the first order for this truck begins to be prepared, right up until the truck’s scheduled departure time. Since several orders destined for different trucks are processed simultaneously, and since the number of sorting slots is limited, the timetabling of these resources is necessary to ensure that all orders can be processed over the considered time horizon. In this paper we describe the general industrial context of the problem and we formalize it. We state that some particular cases of the problem are polynomially solvable while the general problem is NP-complete. We then propose optimization methods for solving the problem.