Two-dimensional core-shell donor-acceptor assemblies at metal-organic interfaces promoted by surface-mediated charge transfer.

Organic charge transfer (CT) complexes obtained by combining molecular electron donors and acceptors have attracted much interest due to their potential applications in organic opto-electronic devices. In order to work, these systems must have an electronic matching - the highest occupied molecular orbital (HOMO) of the donor must couple with the lowest unoccupied molecular orbital (LUMO) of the acceptor - and a structural matching, so as to allow direct intermolecular CT. Here it is shown that, when molecules are adsorbed on a metal surface, novel molecular organizations driven by surface-mediated CT can appear that have no counterpart in condensed phase non-covalent assemblies of donor and acceptor molecules. By means of scanning tunneling microscopy and spectroscopy it is demonstrated that the electronic and self-assembly properties of an electron acceptor molecule can change dramatically in the presence of an additional molecular species with marked electron donor character, leading to the formation of unprecedented core-shell assemblies. DFT and classical force-field simulations reveal that this is a consequence of charge transfer from the donor to the acceptor molecules mediated by the metallic substrate.

Dysprosium-carboxylate nanomeshes with tunable cavity size and assembly motif through ionic interactions.

We report the design of dysprosium directed metallo-supramolecular architectures on a pristine Cu(111) surface. By an appropriate selection of the ditopic molecular linkers equipped with terminal carboxylic groups (TPA, PDA and TDA species), we create reticular and mononuclear metal-organic nanomeshes of tunable internodal distance, which are stabilized by eight-fold DyO interactions. A thermal annealing treatment for the reticular Dy:TDA architecture gives rise to an unprecedented quasi-hexagonal nanostructure based on dinuclear Dy clusters, exhibiting a unique six-fold DyO bonding motif. All metallo-supramolecular architectures are stable at room temperature. Our results open new avenues for the engineering of supramolecular architectures on surfaces incorporating f-block elements forming thermally robust nanoarchitectures through ionic bonds.

[60]Fullerene-porphyrin [n]pseudorotaxanes: self-assembly, photophysics and third-order NLO response.

By means of different spectroscopic techniques, we investigate a novel series of porphyrin derivatives (H2TPP), connected to dibenzo-24-crown-8 (DB24C8) moieties, which undergo self-assembly with different methano[60]fullerene units bearing dibenzylammonium (DBA) cations. The formation of both [2] and [3]pseudorotaxanes was proved by means of NMR, UV-Vis-NIR absorption and emission spectroscopies. With the support of molecular modelling studies, spectroscopic investigations showed the presence of a secondary interaction between the porphyrin and the C60 chromophores leading to the formation of different types of "face-to-face" assemblies. Remarkably, investigations of the non-linear optical response of these supramolecular systems showed that individual porphyrin and fullerene derivatives exhibit significantly lower second hyperpolarizability values when compared to their pseudorotaxanes functionalised counterparts. This proves that this class of supramolecular materials possesses relevant NLO response, which strongly depends on the structural arrangement of the chromophores in solution.

Successful private-public funding of paediatric medicines research: lessons from the EU programme to fund research into off-patent medicines.

UNLABELLED: The European Paediatric Regulation mandated the European Commission to fund research on off-patent medicines with demonstrated therapeutic interest for children. Responding to this mandate, five FP7 project calls were launched and 20 projects were granted. This paper aims to detail the funded projects and their preliminary results. Publicly available sources have been consulted and a descriptive analysis has been performed. Twenty Research Consortia including 246 partners in 29 European and non-European countries were created (involving 129 universities or public-funded research organisations, 51 private companies with 40 SMEs, 7 patient associations). The funded projects investigate 24 medicines, covering 10 therapeutic areas in all paediatric age groups. In response to the Paediatric Regulation and to apply for a Paediatric Use Marketing Authorisation, 15 Paediatric Investigation Plans have been granted by the EMA-Paediatric Committee, including 71 studies of whom 29 paediatric clinical trials, leading to a total of 7,300 children to be recruited in more than 380 investigational centres. CONCLUSION: Notwithstanding the EU contribution for each study is lower than similar publicly funded projects, and also considering the complexity of paediatric research, these projects are performing high-quality research and are progressing towards the increase of new paediatric medicines on the market. Private-public partnerships have been effectively implemented, providing a good example for future collaborative actions. Since these projects cover a limited number of off-patent drugs and many unmet therapeutic needs in paediatrics remain, it is crucial foreseeing new similar initiatives in forthcoming European funding programmes.

The role of daily hassles in binge eating.

OBJECTIVE: The present study investigated the relationship between daily hassles and the frequency and caloric intake of eating episodes among normal-weight women who engage in binging (n = 17) and those who do not (n = 17). METHOD: For 2 weeks, participants self-monitored their food intake during the day and completed The Hassles Scale each evening before retiring. RESULTS: Results indicated that women who engage in binge eating rated daily hassles as significantly more stressful than women who do not binge. Also, women who engage in binge eating consumed significantly more calories on those days characterized by higher as opposed to lower levels of stress. DISCUSSION: Theoretical and clinical implications of these findings are discussed.

Validity of questionnaires for assessing dysfunctional cognitions in bulimia nervosa.

OBJECTIVE: This research investigated the validity of the Bulimic Cognitive Distortions Scale and the Mizes Anorectic Cognitions Questionnaire. The ability of these questionnaires to discriminate among individuals with bulimia, restrained eaters, and normals was also investigated. METHOD: Scores on these retrospective self-report questionnaires were compared to cognitions assessed via in vivo thought-sampling. Cognitions of 15 women with bulimia nervosa, 15 restrained eaters, and 15 non-eating disordered women were assessed. RESULTS: Results indicated that both the BCDS and the MAC successfully discriminated among individuals with bulimia, restrained eaters, and normals, and adequately measured in vivo attitudes and beliefs associated with food and eating, weight and body-image, and low self-efficacy. DISCUSSION: These findings support the continued use of both the BCDS and the MAC.

An overview of anorexia and bulimia nervosa, and the impact of eating disorders on the oral cavity.

The two most common eating disorders, anorexia nervosa and bulimia nervosa, can severely impact oral health. This article will discuss and describe the nature of these disorders and attempt to explain why mostly women suffer from them. In addition, the signs and symptoms of these disorders will be described as they present on medical and oral examination, and recommendations for rehabilitating these patients will be presented.