This tutorial review describes the physical–chemical aspects one must consider when building photocatalytic liposomes for solar fuel production.

van der Waals functionals have recently been applied to obtain a potential energy surface to describe the dissociation of H2 on Ru(0001), where an improvement was found for computed reaction probabilities compared to experiment, which could not be achieved with the use of other exchange-correlation functionals. It is, however, not yet clear to what extent van der Waals functionals give a better description of other molecule-metal surface systems. In this study, the optPBE-vdW-DF functional is compared to the SRP48 functional, which was originally fitted to describe the dissociation of H2 on Cu(111), in terms of the resulting potential energy surfaces and results of quasi-classical dynamics calculations and their agreement with experiment for different H2-metal surface systems. It is found that overall the optPBE-vdW-DF functional yields potential energy surfaces that are very similar to potential energy surfaces computed with the SRP48 functional. In dynamics calculations the optPBE-vdW-DF functional gives a slightly better description of molecular beam experiments. Also a different dependence of reaction on the rotational quantum number J is found, which is in better agreement with experimental data for H2 dissociation on Cu(111). The vibrational efficacy is found to be relatively insensitive to which of the two functionals is chosen.

Covalent functionalisation with alkyl tails is a common method for supporting molecular catalysts and photosensitisers onto lipid bilayers, but the influence of the alkyl chain length on the photocatalytic performances of the resulting liposomes is not well understood. In this work, we first prepared a series of rhenium-based CO 2 -reduction catalysts [Re(4, 9, 12, 15, 17, and 19). We then prepared a series of PEGylated DPPC liposomes containing RuC n and ReC n , hereafter noted C n , to perform photocatalytic CO 2 reduction in the presence of sodium ascorbate. The photocatalytic performance of the C n liposomes was found to depend on the alkyl tail length, as the turnover number for CO (TON) was inversely correlated to the alkyl chain length, with a more than fivefold higher CO production (TON = 14.5) for the C 9 liposomes, compared to C 19 (TON = 2.8). Based on immobilisation efficiency quantification, diffusion kinetics, and time-resolved spectroscopy, we identified the main reason for this trend: two types of membranebound RuC n species can be found in the membrane, either deeply buried in the bilayer and diffusing slowly, or less buried with much faster diffusion kinetics. Our data suggest that the higher photocatalytic performance of the C 9 system is due to the higher fraction of the more mobile and less buried molecular species, which leads to enhanced electron transfer kinetics between RuC 9 and ReC 9 .

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This paper compares the characteristics of adult children who provide comfort and sympathy and serve as confidants to parents with those whom parents perceive as disappointing. Interview information from 117 couples having children who had left home was analyzed using aggregate and intrafamilial strategies. The latter analyses compared the characteristics of the selected child with those of her or his sibs instead of comparing the aggregate of selected children with the aggregate of their siblings. Differences in the findings from the 2 techniques are discussed. The findings confirmed the importance of daughters who live nearby as understanding children. More important than proximity among the factors influencing parental judgments on disappointing and understanding children were intergenerational shared interests and values.

This paper compares the characteristics of adult children who provide comfort and sympathy and serve as confidants to parents with those whom parents perceive as disappointing. Interview information from 117 couples having children who had left home was analyzed using aggregate and intrafamilial strategies. The latter analyses compared the characteristics of the selected child with those of her or his sibs instead of comparing the aggregate of selected children with the aggregate of their siblings. Differences in the findings from the 2 techniques are discussed. The findings confirmed the importance of daughters who live nearby as understanding children. More important than proximity among the factors influencing parental judgments on disappointing and understanding children were intergenerational shared interests and values.