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1.
J Chem Phys ; 159(7)2023 Aug 21.
Article in English | MEDLINE | ID: mdl-37602805

ABSTRACT

The transition to renewable energy sources comes along with the search for new energy storage solutions. Molecular solar thermal systems directly harvest and store solar energy in a chemical manner. By a suitable molecular design, a higher overall efficiency can be achieved. In this study, we investigate the surface chemistry of oxa-norbornadiene/quadricyclane derivatives on a Pt(111) surface. Specifically, we focus on the energy storage and release properties of molecules that are substituted with ester moieties of different sizes. For our model catalytic approach, synchrotron radiation-based x-ray photoelectron spectroscopy measurements were conducted in ultra-high vacuum (UHV) and correlated with the catalytic behavior in the liquid phase monitored by photochemical infrared reflection absorption spectroscopy. The differences in their spectral appearance enabled us to unambiguously differentiate the energy-lean and energy-rich isomers and decomposition products. Next to qualitative information on the adsorption motifs, temperature-programmed experiments allowed for the observation of thermally induced reactions and the deduction of the related reaction pathways. We analyzed the selectivity of the cycloreversion reaction from the energy-rich quadricyclane derivative to its energy-lean norbornadiene isomer and competing processes, such as desorption and decomposition. For the 2,3-bis(methylester)-substitution, the cycloreversion reaction was found to occur between 310 and 340 K, while the thermal stability limit of the compounds was determined to be 380 K. The larger 2,3-bis(benzylester) derivatives have a lower apparent adsorption energy and a decomposition onset already at 135 K. In the liquid phase (in acetonitrile), we determined the rate constants for the cycloreversion reaction on Pt(111) to k = 5.3 × 10-4 s-1 for the 2,3-bis(methylester)-substitution and k = 6.3 × 10-4 s-1 for the 2,3-bis(benzylester) derivative. The selectivities were of >99% and 98% for the two molecules, respectively. The difference in the catalytic behavior of Pt(111) for both derivatives is less pronounced in the liquid phase than in UHV, which we attribute to the passivation of the Pt(111) surface by carbonaceous species under ambient conditions.

2.
J Health Psychol ; 21(9): 2098-107, 2016 09.
Article in English | MEDLINE | ID: mdl-25759374

ABSTRACT

The objective was to explore the general public's views on the role of health professionals in the management of weight with diet and the implementation of behaviour change. Semi-structured interviews were conducted. An inductive grounded theory approach utilised a coding framework; recurring concepts/themes explored in future interviews and thematic saturation achieved. Two themes summarised views on the role of health professionals in supporting dieting and weight management: responsibility to initiate talk and what patients expect. Individuals perceive health professionals as having a role in their weight management. Individuals have disparate views about responsibility for initiation of weight management talk.


Subject(s)
Diet, Reducing/psychology , Overweight/psychology , Physician's Role , Physician-Patient Relations , Public Opinion , Social Support , Adolescent , Adult , Aged , Body Weight Maintenance , Feeding Behavior , Female , Humans , Male , Middle Aged , Overweight/therapy , United Kingdom , Young Adult
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