Modification of the Mechanical Properties of Core-Shell Liquid Gallium Nanoparticles by Thermal Oxidation at Low Temperature

Gallium nanoparticles (Ga NPs) are attracting increasing attention because of their appealing physical-chemical properties. In particular, their mechanical properties play a key role in the implementation of these core-shell structures on certain applications, such as soft and stretchable electronics. Thus, efforts are being addressed to modulate them mainly by chemical means. In contrast, this study investigates how the mechanical properties of the outer gallium thin oxide shell change when its thickness is increased through a thermal oxidation strategy. Specifically, as-deposited Ga NPs, as well as those subjected to thermal oxidation at 300 °C for three different times, are studied by performing single-particle indentations by atomic force microscopy over a wide range of NP radius. This analysis helps to confirm that the Reissner's thin-shell model for small deformations within the elastic regime is obeyed. From these data, the dependence of the shell stiffness and the Young's modulus of the gallium oxide on the thermal treatment is obtained. It is found that the shell stiffness increases with the annealing time, even by a factor of 50 under prolonged thermal oxidation, while the gallium oxide Young's modulus, close to 30 GPa, does not change significantly.     

An experimental and computational study on the dissociation behavior of hydroxypyridine N‐oxides in atmospheric pressure ionization mass spectrometry

A tandem mass spectrometric study of protonated isomeric hydroxypyridine N‐oxides was carried out with a hybrid quadrupole/time‐of‐flight mass spectrometer coupled with different atmospheric pressure ionization sources. The behavior observed in the collision‐induced dissociation (CID) mass spectra of the parent cations, was similar irrespective of the source employed. However, there were intrinsic differences in the intensities of the two fragments observed for each isomer. The major fragment because of elimination of a hydroxyl radical, dominated the CID spectra (in contrast with weaker water loss) at different energy thresholds. Therefore, it was possible to differentiate both isomers at collision energies above 13 eV by comparing the ratio of intensities of the major fragment relative to the precursor cation. In addition, quantum chemical calculations at the B3LYP/6‐31 + + G(d,p) level of theory were performed for the protonated isomers of hydroxypyridine N‐oxide and their radical cation products in order to gain insight into the major routes of dissociation. The results suggest that dissociation from the lowest triplet excited state of the protonated species would provide a reasonable rationalization for the difference in behavior of both isomers. Copyright © 2010 John Wiley & Sons, Ltd.     

Rapid and high-yielding cysteine labelling of peptides with N-succinimidyl 4-[18F]fluorobenzoate

Fast cysteine labelling of peptides promoted by an adjacent arginine has been observed with a standard labelling agent specific for amines, N-succinimidyl 4-[(18)F]fluorobenzoate.     

Prediction of pKa values of nido-carboranes by density functional theory methods

A great parallel exists between metal complexes of cyclopentadienyl and arene ligands on one side and metal complexes of the nido derivatives of the icosahedral o-carborane clusters. With few exceptions, the metal complexation in the cluster can be viewed as the substitution of one or more bridging hydrogen atoms by the metal. Therefore, a necessary requirement for the complexation is the deprotonation of the nido cluster to generate a coordination site for that metal. The reaction to remove these protons, which most probably is one of the most commonly done processes in boron and metallaborane chemistry, is barely known, and no quantitative data are available on the magnitude of their pKa values. With the purpose of determining the acidity of nido-carboranes, a procedure to calculate the pKa values of nido boron clusters is presented in this paper for the first time. To this objective, some nido clusters have been selected and their geometry and NMR-spectroscopic properties have been studied, giving a good correlation between the theoretical and experimental data in both geometry distances and 11B NMR spectroscopy. Of notice is the result that proves that the singular carbon atom in the thermodynamic isomer of [C2B10H13]- is definitely part of the cluster and that its connection with the C2B3 face would be better defined by adding additional interactions with the two boron atoms nearest to the second cluster carbon. The pKa values of the nido species have been calculated by correlating experimental pK(a) values and calculated reaction Gibbs energies DeltaG(s). Some pKa values of importance are -4.6 and +13.5 for 7,8-[C2B9H13] (1) and 7,8-[C2B9H12]- (2), respectively.     

Enantioselective synthesis and absolute configuration assignment of gabosine O. Synthesis of (+)- and (-)-gabosine N and (+)- and (-)-epigabosines N and O

[reaction: see text] A rational approach to the synthesis of gabosines and other related carba-sugars starting from a masked p-benzoquinone has been designed. The enantioselective acetylation of the hydroxyketal 2 provides a practical entry to either enantiomer of the target products. The strategy has been applied to the synthesis of (+)- and (-)-gabosines N and O and (+)- and (-)-epigabosines N and O. The absolute configuration of natural gabosine O has been established.