Ligand tethering by ion-exchange for the immobilization of homogeneous catalysts

A Rh phosphine complex, derived from the Wilkinson’s catalyst, has been immobilized by ion-exchange on the ammonium form of a Al-MCM-41 sample. Ammonium ions have been exchanged by cholamine ions, which act as an amine ligand, and then the Wilkinson’s catalyst has been immobilized by substitution of a phosphine ligand by the anchored amine. This is a novel immobilization procedure, as a ligand, instead of the whole complex, is tethered to the support by ion exchange. The obtained hybrid catalyst has been characterized by Elemental Analysis, DRIFTS and XPS. The quantitative exchange of ammonium by cholamine and coordination of Rh to amines has been observed. Most of the anchored Rh is considered to be coordinated to the ligand tethered to the support and a small proportion seems to be interacting with the protonated ligand or with the support surface. The catalyst has been tested in the hydrogenation of cyclohexene and in the hydroformylation of 1-octene. In the first case the catalyst is active and reusable, while a strong Rh leaching takes place in the second one.

Growing Neural Gas approach for obtaining homogeneous maps by restricting the insertion of new nodes

The Growing Neural Gas model is used widely in artificial neural networks. However, its application is limited in some contexts by the proliferation of nodes in dense areas of the input space. In this study, we introduce some modifications to address this problem by imposing three restrictions on the insertion of new nodes. Each restriction aims to maintain the homogeneous values of selected criteria. One criterion is related to the square error of classification and an alternative approach is proposed for avoiding additional computational costs. Three parameters are added that allow the regulation of the restriction criteria. The resulting algorithm allows models to be obtained that suit specific needs by specifying meaningful parameters.

Preparation of homogeneous CNT coatings in insulating capillary tubes by an innovative electrochemically-assisted method

Preparation of homogeneous CNT coatings in insulating silica capillary tubes is carried out by an innovative electrochemically-assisted method in which the driving force for the deposition is the change in pH inside the confined space between the inner electrode and the capillary walls. This method represents a great advancement in the development of CNT coatings following a simple, cost-effective methodology.

Multidecadal variability of the continental precipitation annual amplitude driven by AMO and ENSO

As the water vapor content in the atmosphere scales with temperature, a warmer world is expected to feature an intensification of the hydrological cycle. Work to date has mainly focused on mean precipitation changes, whose connection to climatic modes is elusive at a global scale. Here we show that continental precipitation annual amplitude, which represents the annual range between minimum and maximum (monthly) rainfall, covaries with a linear combination of the Atlantic Multidecadal Oscillation and low-frequency variations in the El Niño–Southern Oscillation on a decadal to multidecadal scale with a correlation coefficient of 0.92 (P<0.01). The teleconnection is a result of changes in moisture transport in key regions. Reported trends in the annual amplitude of global precipitation in recent decades need to be assessed in light of this substantial low-frequency variability, which could mask or enhance an anthropogenic signal in hydrological cycle changes.

Synthesis of Robust Hierarchical Silica Monoliths by Surface-Mediated Solution/Precipitation Reactions over Different Scales: Designing Capillary Microreactors for Environmental Applications

A synthetic procedure to prepare novel materials (surface-mediated fillings) based on robust hierarchical monoliths is reported. The methodology includes the deposition of a (micro- or mesoporous) silica thin film on the support followed by growth of a porous monolithic SiO2 structure. It has been demonstrated that this synthesis is viable for supports of different chemical nature with different inner diameters without shrinkage of the silica filling. The formation mechanism of the surface-mediated fillings is based on a solution/precipitation process and the anchoring of the silica filling to the deposited thin film. The interaction between the two SiO2 structures (monolith and thin film) depends on the porosity of the thin film and yields composite materials with different mechanical stability. By this procedure, capillary microreactors have been prepared and have been proved to be highly active and selective in the total and preferential oxidation of carbon monoxide (TOxCO and PrOxCO).

An approximate Hahn–Banach theorem for positively homogeneous functions

This note provides an approximate version of the Hahn–Banach theorem for non-necessarily convex extended-real valued positively homogeneous functions of degree one. Given p : X → R∪{+∞} such a function defined on the real vector space X, and a linear function defined on a subspace V of X and dominated by p (i.e. (x) ≤ p(x) for all x ∈ V), we say that can approximately be p-extended to X, if is the pointwise limit of a net of linear functions on V, every one of which can be extended to a linear function defined on X and dominated by p. The main result of this note proves that can approximately be p-extended to X if and only if is dominated by p∗∗, the pointwise supremum over the family of all the linear functions on X which are dominated by p.