Annual Scientific Report 2016

A concave compound self assembles thanks to reversible and controllable hydrogen bonding to form a dynamic capsule able to selectively extract fullerene derivatives of given size and shape. The process for the separation of fullerene derivatives is based on a sequential selective encapsulation in an appropriate solvent system of the fullerenes contained in a mixture. The capsule is formed by reversible self‐assembly of two concave fragments. The encapsulation of the fullerene derivative having the best fitting geometry for the cavity of the capsule is fast and selective.

A process for the direct cupration of fluoroform has been developed. This exceedingly simple process employs only cheap reagents and is advantageously run at room temperature to produce CuCF₃ reagents that are useful in trifluoromethylation reactions. Chemical compounds bearing a trifluoromethyl group are widely used in the production of various pharmaceuticals and agrochemicals as well as specialty materials, polymers, composites, building blocks, and intermediates for various needs. Fluoroform, CF₃H, is an ideal source of CF₃ because it is inexpensive, readily available in large industrial quantities, non‐toxic, and not an ozone depleter.

Chemical reduction of carbon dioxide to methanol and its derivatives (such as DME) is considered one of the key technologies to reduce both global warming and fossil fuels dependency. Unlike the currently used process for methanol synthesis, ICIQ’s process provides excellent conversions and selectivity to methanol in one pass through the reactor, thereby providing the highest time yield observed for the chemical reduction of CO₂.

SCIPIO is a software that allows to handle, store and manipulate output files from computational chemistry experiments. SCIPIO is a general data extractor and manager that is here presented as a Computational Chemistry Results Repository, which is a sort of tailored electronic notebook allowing for substructure searches and for the generation of “ready to publish” reports

A nanoparticle containing two different populations of chromophores and funcionalized with a dye-labelled peptide sensitive to the action of a hydrolytic enzyme has been developed. In that way, the optical response of the system can directly be correlated, in a quantitative manner, to the activity of a specific enzyme found in the medium where the nanoparticle is placed, thereby allowing for enzyme quantification.  This technology was applied to cystic fibrosis, through the analysis of the trypsin amount of faeces samples. It was shown that this system could allow for the determination of patient’s phenotype, thus avoiding genetic testing.

Benzene is a volatile and toxic organic compound with strong regulations with respect to exposure. The developed sensor is highly sensitive and selective to benzene, and is based on a specific molecular receptor linked to a carbon nanotube through gold nanoparticles. Benzene recognition by the receptor provokes a bending of the nanotube, which affects the resistivity of the system.

A new catalyst based on nanoparticles of cobalt oxide and carbon black has been developed for the generation of hydrogen from water in Polymer Electrolyte Membrane cells. Under high applied potentials (i.e. 2-3 V), the catalyst allows reaching a productivity of hydrogen similar or superior to that obtained using conventional platinum based expensive catalysts.

A potentiometric sensor based on a calix[4]pyrrole receptor specific for creatinine recognition has been developed. The sensor is highly sensitive to creatinine, a biomarker relevant to muscle operation and kidney function. Creatinine quantification in urine samples correlates well with state of the art enzymatic methods (Jaffé).

New unsaturated analogs of (-)-Englerin A, a natural product highly active for the treatment of renal cancer, have been developed and found to be more active against certain types of cancers than the natural product itself.

A new method for the synthesis of pyrrolidine compounds and other heterocycles have been developed. The method involves the use of catalytic amounts of iodine and an oxidant under light irradiation, the substrate of the reaction being a butylamine derivative, which undergoes intramolecular cyclization under the conditions of the reaction.

A new polymer-bound catalyst based on a fluorinated proline derivative for nitroaldol reactions has been developed. The catalyst is prepared by co-polymerzation and is highly active, robust and recyclable, while offering a high chiral induction in nitroaldol reactions.

ioChem-BD is a piece of software allowing for the handling, storage and management of the output files of computational chemistry experiments.
ioChem-BD allows for substructure searches and the generation of reports and ready-to-publish materials to make the life of the computational chemist easier.

A sample holder equipped with a circuit of optic fibers and a lens system has been developed, so that it allows the measurement of the spectroscopic properties of solids and other materials when those are placed under controlled environments, such as within a magnetometer or a cryostat.

A tert-leucine derivative has been successfully anchored onto a polymeric support and shown to be a highly active and selective catalyst for the preparation of the Wieland-Miescher and Hajos-Parrish ketones from readily available starting materials. This catalyst allows for continuous flow preparation of these key building blocks, for the large scale preparation of several natural products and pharmaceutical ingredients.

Carbon dioxide is hydrogenated to methanol under high pressure conditions in almost quantitative yields in the presence of stoichiometric amounts of hydrogen. The process is a catalytic heterogeneous process, operating under flow conditions and using a commercial, conventional, methanol synthesis catalyst. Productivity of up to 15 g of methanol per gram of catalyst and per hour can be reached.

Olefins and secondary alkyl bromides are carboxylated under mild conditions using a nickel (II) catalyst with a phenanthroline derived ligand. The process goes through a “chain-walking” event, meaning that, regardless the position of the bromine atom or the double bond on the aliphatic chain, CO₂ will incorporate in terminal position. This process allows for the preparation of a terminal carboxylic acid from a simple hydrocarbon, using non-selective radical bromination, followed by this regioconvergent process.

Hydrogenated polyacene compounds are readily prepared in a limited number of synthetic steps using a gold-catalyzed intramolecular cyclization reaction as key synthetic step. The reaction proceeds in mild conditions and exhibits a wide substrate scope. The corresponding unsaturated polyacene compound can be obtained by simple oxidation of the compound. Polyacene compounds are widely used as semi-conductors and as organic electronics.

A copper (II) based metal organic framework (MOF) is readily prepared from a triazol substituted histidine derivative. The MOF is stable and exhibits good gas absorption properties as well as chirality. The MOF has been proven suitable for CO₂ separation, catalysis applications (CO₂ hydrogenation, asymmetric catalysis) and chiral resolution. In particular, the MOF offers the possibility to carry out CO₂ separation in a continuous manner.