Palladium nanoparticles in catalytic carbon nanoreactors: the effect of confinement on Suzuki-Miyaura reactions

We explore the construction and performance of a range of catalytic nanoreactors based on palladium nanoparticles encapsulated in hollow graphitised nanofibres. The optimum catalytic material, with small palladium nanoparticles located almost exclusively at the graphitic step-edges within nanoreactors, exhibits attractive catalytic properties in Suzuki-Miyaura cross-coupling reactions. Confinement of nanoparticles at the step-edges facilitates retention of catalytic centres and recycling of catalytic nanoreactors without any significant loss of activity or selectivity over multiple catalytic cycles. Furthermore, careful comparison of the catalytic properties of palladium nanoparticles either on or in nanoreactors reveals that nanoscale confinement of catalysts fundamentally affects the pathways of the Suzuki-Miyaura reaction, with the yield and selectivity for the cross-coupled product critically dependent on the steric properties of the aryl iodide reactant, whereas no effects of confinement are observed for aryl boronic acid reactants possessing substituents in different positions. These results indicate that the oxidative addition step of the Suzuki-Miyaura reaction occurs at the step-edge of nanofibres, where the mechanisms and kinetics of chemical reactions are known to be sensitive to nanoscale confinement, and thus the extent of confinement in carbon nanoreactors can be discretely controlled by careful selection of the aryl iodide reactant

Validation Of Persuasive Messages For The Promotion Of Physical Activity Among People With Coronary Heart Disease [validação De Mensagens Persuasivas Para Promoção De Atividade Física Entre Coronariopatas]

Objective: to validate the content of persuasive messages for promoting walking among patients with coronary heart disease (CHD). The messages were constructed to strengthen or change patients' attitudes to walking. Method: the selection of persuasive arguments was based on behavioral beliefs (determinants of attitude) related to walking. The messages were constructed based in the Elaboration Likelihood Model and were submitted to content validation. Results: the data was analyzed with the content validity index and by the importance which the patients attributed to the messages' persuasive arguments. Positive behavioral beliefs (i.e. positive and negative reinforcement) and self-efficacy were the appeals which the patients considered important. The messages with validation evidence will be tested in an intervention study for the promotion of the practice of physical activity among patients with CHD.20610151023Smith, S.C., Benjamin, E.J., Bonow, R.O., Braun, L.T., Creager, M.A., Franklin, B.A., AHA/ACCF Secondary Prevention and Risk Reduction Therapy for Patients With Coronary and Other Atherosclerotic Vascular Disease: 2011 Update. A Guideline from the American Heart Association and American College of Cardiology Foundation (2011) Circulation., 124, pp. 2458-2473Hammill, B.G., Curtis, L.H., Schulman, K.A., Whellan, D.J., Relationship between cardiac rehabilitation and long-term risks of death and myocardial infarction among elderly medicare beneficiaries (2010) Circulation., 121, pp. 63-70Lisspers, J., Sundin, O., Ohman, A., Hofman-Bang, C., Ryden, L., Nygren, A., Long-term effects of lifestyle behavior change in coronary artery disease: Effects on recurrent coronary events after percutaneous coronary intervention (2005) Health Psychol., 24 (1), pp. 41-48Dorn, J., Correlates of compliance in a randomized exercise trial in myocardial infarction patients (2001) Med Sci Sports Exerc., 33, pp. 1081-1089Latimer, A.E., Brawler, L.R., Bassett, R., A systematic review of three approaches for constructing physical activity messages: What messages work and what improvements are needed? (2010) Int J Behav Nutr Phys Act., 7, p. 36Blanchard, C., Understanding exercise behaviour during home-based cardiac rehabilitation: A theory of planned behaviour perspective (2008) Can J Physiol Pharmacol., 86, pp. 8-15Vallance, J.K., Murray, T.C., Johnson, S.T., Elavsky, S., Understanding physical activity intentions and behavior in postmenopausal women: An application of the theory of planned behavior (2011) Int J Behav Med., 18 (2), pp. 139-149Mendez, R.D.R., (2008) Fatores individuais determinantes da realização de atividade física pelos pacientes com síndrome coronária aguda após a alta hospitalar, p. 164. , [dissertação de mestrado]. Campinas (SP): Universidade Estadual de CampinasJones, L.W., Sinclair, R.C., Rhodes, R.E., Courneya, K.S., Promoting exercise behaviour: An integration of persuasion theories and the Theory of Planned Behavior (2004) Br J Health Psychol., 9 (4), pp. 505-521Winkielman, P., Cacioppo, J.T., Mind at ease puts a smile on the face: Psychophysiological evidence that processing facilitation elicits positive affect (2004) J Per Soc Psychol., 81, pp. 989-1000Brinõl, P., Ibáñez, L.C., Grande, A.B., (2008) Qué es Persuasión, p. 270. , 2. ed. Madrid: Ed. Bibliotheca NuevaPetty, R.E., Cacioppo, J.T., The effects of involvement on response to argument quantity and quality: Central and peripheral routes to persuasion (1984) J Pers Soc Psychol., 46, pp. 69-81Petty, R.E., Barden, J., Wheeler, S.C., The elaboration likelihood model of persuasion: Developing health promotions to produce sustained behavior change (2009) Emerging theories in health promotion practice and research, , In: Di Clemente RJ, Crosby RA, Kegler M., San Francisco: Jossey-BassBrawley, L.R., Latimer, A.E., Physical activity guides for Canadians: Messaging strategies, realistic expectations for change, and evaluation (2007) J Public Health., 98 (SUPPL. 2), pp. s170-s184Gallani, M.C.B.J., (2000) O exercício físico e o paciente infartado: Determinantes comportamentais [tese de doutorado], , São Paulo (SP): Escola de Enfermagem da Universidade São PauloCialdini, R.B., (2001) Influence: Science and practice, , Needham Heights, MA: Allyn e BaconBaum, M.W., (2006) Compreender o behaviorismo, , Porto Alegre: ArtmedAlexandre, N.M.C., Coluci, M.Z.O., Validade de conteúdo nos processos de construção e adaptação de instrumentos de medida (2011) Cienc Saude Coletiva., 16 (7), pp. 3061-3068Isen, A.M., Daubman, K.A., The influence of affect on categorization (1984) J Pers Soc Psychol., 47 (6), pp. 1206-1217Mowen, J.C., Minor, M.S., (2003) Comportamento do Consumidor, p. 403. , São Paulo. Perason Prentice HallJones, L.W., Sinclair, R.C., Courneya, K.S., The effects of source credibility and message framing on exercise intentions, behaviors, and attitudes: An integration of the Elaboration Likelihood Model and prospect theory (2003) J Appl Soc Psychol., 33 (1), pp. 179-19