Stereoisomeric Tris-BINOL-Menthol Bulky Monophosphites: Synthesis,Characterisation and Application in Rhodium-Catalysed Hydroformylation

Four stereoisomeric monoether derivatives, based on axially chiral (R)- or (S)-BINOL bearing a chiral (+)- or (−)-neomenthyloxy group were synthesised and fully characterised by NMR spectroscopy and X-ray crystallography. The respective tris-monophosphites were thereof prepared and fully characterised. The coordination ability of the new bulky phosphites with Rh(CO)₂(acac), was attested by ³¹P NMR, which presented a doublet in the range of δ = 120 ppm, with a ¹J(¹⁰³Rh-³¹P) coupling constant of 290 Hz. The new tris-binaphthyl phosphite ligands were further characterised by DFT computational methods, which allowed us to calculate an electronic (CEP) parameter of 2083.2 cm⁻¹ and an extremely large cone angle of 345°, decreasing to 265° upon coordination with a metal atom. Furthermore, the monophosphites were applied as ligands in rhodium-catalysed hydroformylation of styrene, leading to complete conversions in 4 h, 100% chemoselectivity for aldehydes and up to 98% iso-regioselectivity. The Rh(I)/phosphite catalytic system was also highly active and selective in the hydroformylation of disubstituted olefins, including (E)-prop-1-en-1-ylbenzene and prop-1-en-2-ylbenzene.     

Interpenetrating networks of conjugated ionic polyacetylenes

An interpenetrating polymer network (IPN) based on poly(N-butyl 2-ethynylpyridinum bromide) (PB2EPB) and polycarbonate-urethane (PCU) has been prepared and characterized. The simultaneous full IPNs of PCU and PB2EPB have two glass transition temperatures corresponding to those of the linear chain blends measured by DSC. This suggests immiscibility of the two networks in the IPNs. The IPNs display a multiphase morphology which is confirmed by SEM observation. The full IPNs exhibit excellent solvent resistance, good thermal stability and good mechanical properties. High UV absorption of these materials extending to the visible range and beyond indicates that the polyacetylene network is extensively conjugated. The electrical conductivity of the IPNs increases linearly with increasing polyacetylene content reaching 10^-4 S/cm. © 1996 John Wiley & Sons, Inc.     

Tuning Cellular Biological Functions Through the Controlled Release of NO from a Porous Ti‐MOF

Materials for the controlled release of nitric oxide (NO) are of interest for therapeutic applications. However, to date, many suffer from toxicity and stability issues, as well as poor performance. Herein, we propose a new NO adsorption/release mechanism through the formation of nitrites on the skeleton of a titanium‐based metal–organic framework (MOF) that we named MIP‐177, featuring a suitable set of properties for such an application: (i) high NO storage capacity (3 μmol mg^?1_solid), (ii) excellent biocompatibility at therapeutic relevant concentrations (no cytotoxicity at 90 μg mL^?1 for wound healing) due to its high stability in biological media (<9 % degradation in 72 hours) and (iii) slow NO release in biological media (≈2 hours for 90 % release). The prospective application of MIP‐177 is demonstrated through NO‐driven control of mitochondrial respiration in cells and stimulation of cell migration, paving the way for the design of new NO delivery systems for wound healing therapy.     

Probing the Brønsted Acidity of the External Surface of Faujasite-Type Zeolites

We outline two methodologies to selectively characterize the Brønsted acidity of the external surface of FAU-type zeolites by IR and NMR spectroscopy of adsorbed basic probe molecules. The challenge and goal are to develop reliable and quantitative IR and NMR methodologies to investigate the accessibility of acidic sites in the large pore FAU-type zeolite Y and its mesoporous derivatives often referred to as ultra-stable Y (USY). The accessibility of their Brønsted acid sites to probe molecules (n-alkylamines, n-alkylpyridines, n-alkylphosphine- and phenylphosphine-oxides) of different molecular sizes is quantitatively monitored either by IR or ³¹P NMR spectroscopy. It is now possible, for the first time to quantitatively discriminate between the Brønsted acidity located in the microporosity and on the external surface of large pore zeolites. For instance, the number of external acid sites on a Y (LZY-64) zeolite represents 2 % of its total acid sites while that of a USY (CBV760) represents 4 % while the latter has a much lower framework Si/Al ratio.     

Insights into the Complexity of Weak Intermolecular Interactions Interfering in Host–Guest Systems

The recognition properties of heteroditopic hemicryptophane hosts towards anions, cations, and neutral pairs, combining both cation–π and anion–π interaction sites, were investigated to probe the complexity of interfering weak intermolecular interactions. It is suggested from NMR experiments, and supported by CASSCF/CASPT2 calculations, that the binding constants of anions can be modulated by a factor of up to 100 by varying the fluorination sites on the electron‐poor aromatic rings. Interestingly, this subtle chemical modification can also reverse the sign of cooperativity in ion‐pair recognition. Wavefunction calculations highlight how short‐ and long‐range interactions interfere in this recognition process, suggesting that a disruption of anion–π interactions can occur in the presence of a co‐bound cation. Such molecules can be viewed as prototypes for examining complex processes controlled by the competition of weak interactions.     

Localized Ligand Induced Electroless Plating (LIEP) Process for the Fabrication of Copper Patterns Onto Flexible Polymer Substrates

The “ligand induced electroless plating (LIEP) process” is a simple process to obtain localized metal plating onto flexible polymers such as poly(ethylene terephtalate) and polyvinylidene fluoride sheets. This generic and cost‐effective process, efficient on any common polymer surface, is based on the covalent grafting by the GraftFast process of a thin chelating polymer film, such as poly(acrylic acid), which can complex copper ions. The entrapped copper ions are then chemically reduced in situ and the resulting Cu⁰ species act as a seed layer for the electroless copper growth which, thus, starts inside the host polymer. The present work focuses on the application of the LIEP process to the patterning of localized metallic tracks via two simple lithographic methods. The first is based on a standard photolithography process using a positive photoresist masking to prevent the covalent grafting of PAA in designated areas of the polymer substrate. In the second, the patterning is performed by direct printing of the mask with a commercial laser printer. In both cases, the mask was lifted off before the copper electroless plating step, which provides ecological benefits, since only the amount of copper necessary for the metallic patterning is used.