All electron calculations of open-shell polyatomic molecules. III. Perturbation treatment of the spin polarization in vinyl and methyl radicals

A first order perturbation treatment starting with SCF-MO 'S in canonical or equivalent quasi-localized form is presented for the hyperfine coupling constants of vinyl and methyl radicals. The spin-polarisation contribution to hyperfine splittings is found to be large, negative for the proton of the radical center in both radicals and positive for the β protons of vinyl.     

Spectrométrie de Masse d'Hétérocycles Azotés. X–Contribution à l'Etude du Comportement de ll'Ion Aniline et des Ions Aminopyridines avant Fragmentation par Perte de HCN

The study of the mass analysed ion kinetic energy spectra of deuterated derivatives of aniline, aminopyridines and 2-chloro-5-aminopyridine shows that prior to HCN loss, hydrogen scrambling does not occur for aminopyridines and is limited but noticeable for aniline. In the case of this last compound the extent of scrambling varies markedly for small variations in the energy of the ions studied, these variations being within the energy window corresponding to metastable ions. Furthermore, an examination of the mass analysed ion kinetic energy spectra of monodeuterated derivatives of aminopyridines leads to the rejection of the generally accepted mechanism for HCN loss from the molecular ions of these compounds.     

Thin-film antimony trisulphide photoelectrodes

The properties of n-type thin polycrystalline films of antimony trisulphide obtained by tarnishing reactions have been studied by photoelectrochemical and spectroellipsometric techniques. The photoelectrochemical behaviour is analysed using a recombination model.     

Strained aromatic oligoamide macrocycles as new molecular clips

Can one join both ends of a helix? A helical aromatic oligoamide was macrocyclized into a saddle-shaped bifunctional clip molecule that self-assembles into discrete circular dodecamers in the solid state and shows great potential for binding aromatic acid guests in solution. The cyclization step requires that the helix is only partly denatured in the reaction medium.     

Reactions CO/H2 en phase liquide. Synthese de precurseurs de l'ethanol par homologation du methanol.: I. Influences de la temperature et de la pression

The CO/H₂ homologation of methanol to acetaldehyde and subsequently to its dimethyl acetal in the presence of cobalt acetate promoted by iodine was examined under various conditions. Temperature and pressure were found as critical parameters. High pressures (140 MPa) and low temperatures (160–170°C) give optimal yields and selectivity to acetaldehyde. According to pressure, temperature, contact time, gas ratio and ligand/catalyst ratio, the reaction is oriented towards acetaldehyde, its dimethyl acetal or methyl acetate.     

Combining the lattice-sum and reaction-field approaches for evaluating long-range electrostatic interactions in molecular simulations

A new scheme, the lattice-sum-emulated reaction-field (LSERF) method, is presented that combines the lattice-sum (LS) and reaction-field (RF) approaches for evaluating electrostatic interactions in molecular simulations. More precisely, the LSERF scheme emulates a RF calculation (based on an atomic cutoff) via the LS machinery. This is achieved by changing the form of the electrostatic interactions in a standard LS calculation (Coulombic) to the form corresponding to RF electrostatics (Coulombic plus quadratic reaction-field correction term, truncated at the cutoff distance). It is shown (both analytically and numerically) that in the limit of infinite reciprocal-space accuracy, (i) the LSERF scheme with a finite reaction-field cutoff and a given reaction-field permittivity is identical to the RF scheme with the same parameters (and an atomic cutoff), and (ii) the LSERF scheme is identical to the LS scheme in the limit of an infinite reaction-field cutoff, irrespective of the reaction-field permittivity. This new scheme offers two key advantages: (i) from a conceptual point of view, it shows that there is a continuity between the RF and LS schemes and unifies them into a common framework; (ii) from a practical point of view, it allows us to perform RF calculations with arbitrarily large reaction-field cutoff distances for the same computational costs as a corresponding LS calculation. The optimal choice for the cutoff will be the one that achieves the best compromise between artifacts arising from the dielectric heterogeneity of the system (short cutoff) and its artificial periodicity (long cutoff). The implementation of the LSERF method is extremely easy, requiring only very limited modifications of any standard LS code. For practical applications to biomolecular systems, the use of the LSERF scheme with large reaction-field cutoff distances is expected to represent a significant improvement over the current RF simulations involving comparatively much shorter cutoffs.     

Periodic Mesoporous Organosilica Nanoparticles for CO2 Adsorption at Standard Temperature and Pressure

(1) Background: Due to human activities, greenhouse gas (GHG) concentrations in the atmosphere are constantly rising, causing the greenhouse effect. Among GHGs, carbon dioxide (CO₂) is responsible for about two-thirds of the total energy imbalance which is the origin of the increase in the Earth’s temperature. (2) Methods: In this field, we describe the development of periodic mesoporous organosilica nanoparticles (PMO NPs) used to capture and store CO₂ present in the atmosphere. Several types of PMO NP (bis(triethoxysilyl)ethane (BTEE) as matrix, co-condensed with trialkoxysilylated aminopyridine (py) and trialkoxysilylated bipyridine (Etbipy and iPrbipy)) were synthesized by means of the sol-gel procedure, then characterized with different techniques (DLS, TEM, FTIR, BET). A systematic evaluation of CO₂ adsorption was carried out at 298 K and 273 K, at low pressure. (3) Results: The best values of CO₂ adsorption were obtained with 6% bipyridine: 1.045 mmol·g⁻¹ at 298 K and 2.26 mmol·g⁻¹ at 273 K. (4) Conclusions: The synthetized BTEE/aminopyridine or bipyridine PMO NPs showed significant results and could be promising for carbon capture and storage (CCS) application.     

Easy and effective method to produce functionalized particles for cellular uptake

In this contribution, a versatile approach for the synthesis of functionalized particles for drug delivery is presented, using two nonaggressive standardized procedures. The first procedure considered is the functionalization of an azido‐terminated α‐norbornenyl poly(ethylene oxide) (PEO) macromonomer with an alkyne‐containing active molecule via the copper catalyzed azide alkyne cycloaddition, click type reaction. The functionalized macromonomer is then polymerized by Ring‐Opening Metathesis Polymerization (ROMP) in dispersion to form functionalized particles. The second procedure consists in synthesizing particles by ROMP in dispersed media of norbornene with azido‐terminated α‐norbornenyl PEO macromonomer. The ROMP was initiated by the first generation Grubbs catalyst. Such functionalized core‐shell particles have stealthy properties due to their PEO shell and can be viewed as universal nanocarriers on which any alkyne‐modified active molecule can be grafted by click chemistry. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Pyridylmagnesiates: generation by bromine–metal exchange and enantioselective addition to aldehydes

Butyl and dibutylmagnesiates incorporating chiral ligands have been prepared and their reactivity studied. The reagents were efficient to promote the clean bromine–magnesium exchange of azinyl bromides at room temperature and subsequent reaction with aldehydes affording pyridylcarbinols. (R,R)-TADDOL-based dibutylmagnesiate was the best reagent leading to acceptable to good enantioselectivities, depending on the substrate and on the aldehyde substitution. This is the first example of enantioselective addition of in situ generated pyridylmagnesiate to carbonyl electrophiles.     

Aerodynamic optimization of the flat-plate leading edge for experimental studies of laminar and transitional boundary layers

This work is concerned with the design of a leading edge for a flat-plate model used to study laminar and transitional boundary layers. For this study, the flow over the complete boundary-layer model, including leading edge, flat section, and trailing-edge flap, is modeled. The effect of important geometrical features of the leading edge on the resulting pressure distribution, starting from the well-known symmetric modified super ellipse, is investigated. A minimal pressure gradient on the measurement side of the plate is achieved using an asymmetrical configuration of modified super ellipses, with a thickness ratio of 7/24. An aerodynamic shape optimization is performed to obtain a novel leading edge shape that greatly reduces the length of the non-zero pressure gradient region and the adverse pressure gradient region compared to geometries defined by ellipses. Wind tunnel testing is used to validate the numerical solutions.