Structural Properties of Gas-Phase Molybdenum Oxide Clusters [Mo4O13]2-, [HMo4O13]-, and [CH3Mo4O13]- Studied by Collision-Induced Dissociation.

Molybdenum oxide-based catalysts are widely used for the ammoxidation of toluene, methanation of CO, or hydrodeoxygenation. As a first step towards a gas-phase model system, we investigate here structural properties of mass-selected [Mo4O13]2-, [HMo4O13]-, and [CH3Mo4O13]- by a combination of collision-induced dissociation (CID) experiments and quantum chemical calculations. According to calculations, the common structural motif is an eight-membered ring composed of four MoO2 units and four O atoms. The 13th O atom is located above the center of the ring and connects two to four Mo centers. For [Mo4O13]2- and [HMo4O13]-, dissociation requires opening or rearrangement of the ring structure, which is quite facile for the doubly charged [Mo4O13]2-, but energetically more demanding for [HMo4O13]-. In the latter case, the hydrogen atom is found to stay preferentially with the negatively charged fragments [HMo2O7]- or [HMoO4]-. The doubly charged species [Mo4O13]2- loses one MoO3 unit at low energies while Coulomb explosion into the complementary fragments [Mo2O6]- and [Mo2O7]- dominates at elevated collision energies. [CH3Mo4O13]- affords rearrangements of the methyl group with low barriers, preferentially eliminating formaldehyde, while the ring structure remains intact. [CH3Mo4O13]- also reacts efficiently with water, leading to methanol or formaldehyde elimination.

Gas-phase reactions of cationic vanadium-phosphorus oxide clusters with C2H(x) (x=4, 6): a DFT-based analysis of reactivity patterns.

The reactivities of the adamantane-like heteronuclear vanadium-phosphorus oxygen cluster ions [V(x)P(4-x)O(10)](.+) (x=0, 2-4) towards hydrocarbons strongly depend on the V/P ratio of the clusters. Possible mechanisms for the gas-phase reactions of these heteronuclear cations with ethene and ethane have been elucidated by means of DFT-based calculations; homolytic C-H bond activation constitutes the initial step, and for all systems the P-O(.) unit of the clusters serves as the reactive site. More complex oxidation processes, such as oxygen-atom transfer to, or oxidative dehydrogenation of the hydrocarbons require the presence of a vanadium atom to provide the electronic prerequisites which are necessary to bring about the 2e(-) reduction of the cationic clusters.

The research agenda for general practice/family medicine and primary health care in Europe. Part 3. Results: person centred care, comprehensive and holistic approach.

The recently published 'Research Agenda for General Practice/Family Medicine and Primary Health Care in Europe' summarizes the evidence relating to the core competencies and characteristics of the Wonca Europe definition of GP/FM, and its implications for general practitioners/family doctors, researchers and policy makers. The European Journal of General Practice publishes a series of articles based on this document. In a first article, background, objectives, and methodology were discussed. In a second article, the results for the two core competencies 'primary care management' and 'community orientation' were presented. This article reflects on the three core competencies, which deal with person related aspects of GP/FM, i.e. 'person centred care', 'comprehensive approach' and 'holistic approach'. Though there is an important body of opinion papers and (non-systematic) reviews, all person related aspects remain poorly defined and researched. Validated instruments to measure these competencies are lacking. Concerning patient-centredness, most research examined patient and doctor preferences and experiences. Studies on comprehensiveness mostly focus on prevention/care of specific diseases. For all domains, there has been limited research conducted on its implications or outcomes.