Catalytic asymmetric synthesis of chromenes and tetrahydroquinolines via sequential allylic alkylation and intramolecular Heck coupling

Highly enantioselective synthesis of chiral chromenes and tetrahydroquinolines is achieved by combining asymmetric copper-catalyzed allylic substitution with Grignard reagents and an efficient intramolecular Heck reaction. Moreover, the exocyclic double bond formed in the cyclisation was subjected to RCM, hydroboration and hydrogenation illuminating the synthetic versatility of these heterocycles.     

Phenolic profile of hazelnut (Corylus avellana L.) leaves cultivars grown in Portugal

In this study, phenolic compounds of hazelnut leaves of 10 different cultivars with the same cultural, geographical, geological and climatic conditions were analyzed by HPLC/DAD and HPLC/DAD/MS/MS - ESI. Eight phenolic compounds (3-caffeoylquinic acid, 5-caffeoylquinic acid, caffeoyltartaric acid, p-coumaroyltartaric acid, myricetin 3-rhamnoside, quercetin 3-glycoside, quercetin 3-rhamnoside and kaempferol 3-rhamnoside) were identified and quantified. All of the analyzed samples showed a similar phenolic profile, in which myricetin 3-rhamnoside and quercetin 3-rhamnoside were the major compounds and caffeoyltartaric and p-coumaroyltartaric acids were present in vestigial amounts.     

Perovskites in high dimensions

We study the (D+1) band Hubbard model on generalizedD-dimensional perovskite structures. We show that in the limit of high dimensions the possible scaling behaviour is uniquely determined via the bandstructure and that the model without direct oxygen-oxygen hopping necessarily scales to the cluster limit. A 1/dimension expansion then leads to at-J like Hamiltonian and the Zhang-Rice analysis becomes rigorous. The large dimension fixed point, in general, still remains the cluster model even when a hopping term between n.n. oxygensites is included. Only for a unique ratio of the oxygen onsite energies to the oxygen-oxygen hopping amplitude is a new fixed point possible, corresponding to a heavy-Fermion Hamiltonian.     

A new integrable system on the sphere and conformally equivariant quantization

Taking full advantage of two independent projectively equivalent metrics on the ellipsoid leading to Liouville integrability of the geodesic flow via the well-known Jacobi–Moser system, we disclose a novel integrable system on the sphere Sⁿ$S^n$, namely the dual Moser system. The latter falls, along with the Jacobi–Moser and Neumann–Uhlenbeck systems, into the category of (locally) Stäckel systems. Moreover, it is proved that quantum integrability of both Neumann–Uhlenbeck and dual Moser systems is ensured by means of the conformally equivariant quantization procedure.     

High pressure chemistry of molecular systems: Recent experimental results and developments

Abstract

It is widely recognized that relevant new chemistry is being discovered by applying high pressures. The study of the equation of state, pressure-induced phase transitions, reactivity, etc., of molecular systems are topics of increasing interest in high pressure science. This paper compiles recent studies performed by the author on molecular systems at high pressures. This includes, on the theoretical side, a reference to a universal model of EOS for both liquids and solids at high pressure. Several experiments performed by the author are also discussed; among others, a high pressure polymerization of carbon monoxide, the design of an anvil cell system developed in our laboratory, introducing an alternative Raman pressure scale when sapphires are mounted as anvils (SAC configuration) and, finally, several actual SAC experiments are presented, including examples of phase transitions and reactivity at high pressure on double and triple bonded molecular systems.     

Tuning the adhesion of layer-by-layer films to the physicochemical properties of inner limiting membranes using nanoparticles

Retinal trauma is a serious concern for patients undergoing inner limiting membrane (ILM) peeling to correct for various vitreoretinal interface conditions. This mechanical trauma can be prevented by modifying the surface of surgical instruments to increase adhesion to the ILM. To this effect, we have studied the effects of roughness and surface charge on the adhesive properties of ILMs by utilizing layer-by-layer (LbL) films with embedded gold nanoparticles (LbL-AuNP films). LbL films were assembled on atomic force microscopy (AFM) tipless cantilevers. Topographical analysis of these films, with and without nanoparticles, showed that LbL films with nanoparticles had a higher rms roughness compared to films alone or unmodified cantilevers. Nanoparticle-modified LbL films significantly increased the adhesion forces at the cantilever-ILM interface, compared to LbL films without particles. Surprisingly, adsorption of gold nanoparticles onto the AFM cantilevers caused increases in adhesion forces greater than those measured with LbL-AuNP films. These results have important implications for the design of surface modifications for vitreoretinal surgical instruments.     

Two pressure-induced transitions in TiOCl: Mott insulator to anisotropic metal

Using Car-Parrinello molecular dynamics we investigate the behavior of the low-dimensional multiorbital Mott insulator TiOCl under pressure. We show that the system undergoes two consecutive phase transitions, first at Pc from a Mott-insulator to a metallic phase in the ab plane with a strong Ti-Ti dimerization along b. At a pressure Pc' > Pc the dimerization disappears and the system behaves as a uniform metal. This second transition has not yet been reported experimentally. We show that the insulator-to-metal transition at Pc is driven by the widening of the bandwidth rather than structural changes or reduction of crystal field splittings and it shows a redistribution of the electronic occupation within the t2g bands. Our computed pressure-dependent lattice parameters are consistent with experimental observations and the existing controversy on the change of crystal symmetry at high pressures is discussed.