Correlation of the EPR properties of perchlorotriphenylmethyl radical and their efficiency as DNP polarizers

Water soluble perchlorinated trityl (PTM) radicals were found to be effective 95 GHz DNP (dynamic nuclear polarization) polarizers in ex situ (dissolution) 13C DNP (Gabellieri et al., Angew Chem., Int. Ed. 2010, 49, 3360). The degree of the nuclear polarization obtained was reported to be dependent on the position of the chlorine substituents on the trityl skeleton. In addition, on the basis of the DNP frequency sweeps it was suggested that the 13C NMR signal enhancement is mediated by the Cl nuclei. To understand the DNP mechanism of the PTM radicals we have explored the 95 GHz EPR characteristics of these radicals that are relevant to their performance as DNP polarizers. The EPR spectra of the radicals revealed axially symmetric g-tensors. A comparison of the spectra with the 13C DNP frequency sweeps showed that although the solid effect mechanism is operational the DNP frequency sweeps reveal some extra width suggesting that contributions from EPR forbidden transitions involving 35,37Cl nuclear flips are likely. This was substantiated experimentally by ELDOR (electron-electron double resonance) detected NMR measurements, which map the EPR forbidden transitions, and ELDOR experiments that follow the depolarization of the electron spin upon irradiation of the forbidden EPR transitions. DFT (density functional theory) calculations helped to assign the observed transitions and provided the relevant spin Hamiltonian parameters. These results show that the 35,37Cl hyperfine and nuclear quadrupolar interactions cause a considerable nuclear state mixing at 95 GHz thus facilitating the polarization of the Cl nuclei upon microwave irradiation. Overlap of Cl nuclear frequencies and the 13C Larmor frequency further facilitates the polarization of the 13C nuclei by spin diffusion. Calculation of the 13C DNP frequency sweep based on the Cl nuclear polarization showed that it does lead to an increase in the width of the spectra, improving the agreement with the experimental sweeps, thus supporting the existence of a new heteronuclear assisted DNP mechanism.

Bonding of gold nanoclusters to oxygen vacancies on rutile TiO2(110)

Through an interplay between scanning tunneling microscopy (STM) and density functional theory (DFT) calculations, we show that bridging oxygen vacancies are the active nucleation sites for Au clusters on the rutile TiO2(110) surface. We find that a direct correlation exists between a decrease in density of vacancies and the amount of Au deposited. From the DFT calculations we find that the oxygen vacancy is indeed the strongest Au binding site. We show both experimentally and theoretically that a single oxygen vacancy can bind 3 Au atoms on average. In view of the presented results, a new growth model for the TiO2(110) system involving vacancy-cluster complex diffusion is presented.

Essential factors for control of the equilibrium in the reversible rearrangement of M3N@Ih-C80 fulleropyrrolidines: Exohedral functional groups versus endohedral metal clusters

The effects of exohedral moieties and endohedral metal clusters on the isomerization of M3N@Ih-C80 products from the Prato reaction through [1,5]-sigmatropic rearrangement were systematically investigated by using three types of fulleropyrrolidine derivatives and four different endohedral metal clusters. As a result, all types of derivatives provided the same ratios of the isomers for a given trimetallic nitride template (TNT) as the thermodynamic products, thus indicating that the size of the endohedral metal clusters inside C80 was the single essential factor in determining the equilibrium between the [6,6]-isomer (kinetic product) and the [5,6]-isomer. In all the derivatives, the [6,6]- and [5,6]-Prato adducts with larger metal clusters, such as Y3N and Gd3N, were equally stable, which is in good agreement with DFT calculations. The reaction rate of the rearrangement was dependent on both the substituent of exohedral functional groups and the endohedral metal-cluster size. Further DFT calculations and 13C NMR spectroscopic studies were employed to rationalize the equilibrium in the rearrangement between the [6,6]- and [5,6]-fulleropyrrolidines

Parametrització de contorns oberts

Un dels principals problemes quan es realitza un anàlisi de contorns és la gran quantitat de dades implicades en la descripció de la figura. Per resoldre aquesta problemàtica, s’aplica la parametrització que consisteix en obtenir d’un contorn unes dades representatives amb els mínims coeficients possibles, a partir dels quals es podrà reconstruir de nou sense pèrdues molt evidents d’informació. En figures de contorns tancats, la parametrització més estudiada és l’aplicació de la transformada discreta de Fourier (DFT). Aquesta s’aplica a la seqüència de valors que descriu el comportament de les coordenades x i y al llarg de tots els punts que formen el traç. A diferència, en els contorns oberts no es pot aplicar directament la DFT ja que per fer-ho es necessita que el valor de x i de y siguin iguals tan en el primer punt del contorn com en l’últim. Això és degut al fet que la DFT representa sense error senyals periòdics. Si els senyals no acaben en el mateix punt, representa que hi ha una discontinuïtat i apareixen oscil·lacions a la reconstrucció. L’objectiu d’aquest treball és parametritzar contorns oberts amb la mateixa eficiència que s’obté en la parametrització de contorns tancats. Per dur-ho a terme, s’ha dissenyat un programa que permet aplicar la DFT en contorns oberts mitjançant la modificació de les seqüencies de x i y. A més a més, també utilitzant el programari Matlab s’han desenvolupat altres aplicacions que han permès veure diferents aspectes sobre la parametrització i com es comporten els Descriptors El·líptics de Fourier (EFD). Els resultats obtinguts han demostrat que l’aplicació dissenyada permet la parametrització de contorns oberts amb compressions òptimes, fet que facilitarà l’anàlisi quantitatiu de formes en camps com l’ecologia, medicina, geografia, entre d’altres.