Chiral metal-organic frameworks (MOFs) with porous and tunable nature show promise as heterogeneous asymmetric catalysts. Through incorporating the stereoselective organocatalyst L- or D-pyrrolidin-2-ylimidazole (PYI) and a triphenylamine photoredox group into a single framework, we have developed two enantiomeric MOFs, Zn-PYI1 and Zn-PYI2, to prompt the asymmetric α-alkylation of aliphatic aldehydes in a heterogeneous manner. The strong reductive excited state of the triphenylamaine moiety within these MOFs initiated a photoinduced electron transfer, rendering an active intermediate for the α-alkylation. The chiral PYI moieties acted as cooperative organocatalytic active sites to drive the asymmetric catalysis with significant stereoselectivity. Control experiments using the lanthanide-based metal-organic frameworks Ho-TCA and MOF-150, assembled from 4,4',4"-nitrilotribenzoic acid, as catalysts suggested that both the photosensitizer triphenylamine moiety and the chiral organocatalyst D-/L-PYI moiety were necessary for the light-driven α-alkylation reactions. Further investigations demonstrated that the integration of both photocatalyst and asymmetric organocatalyst into a single MOF makes the enantioselection superior to that of simply mixing the corresponding MOFs with the chiral adduct. The easy availability, excellent stereoselectivity, great separability, and individual components fixed with their well-defined porous and repeating structures make the MOF a versatile platform for a new type of tandem catalyst and cooperative catalyst.
A simple electrostatic self-assembly technique was used to fabricate a photo-switched azobenzene monolayer, on which superhydrophobicity and a large reversible CA change could be realized.
Photosynthetic microalgae can capture solar energy and convert it to bioenergy and biochemical products. In nature or industrial processes, microalgae live together with bacterial communities and may maintain symbiotic relationships. In general interactions, microalgae exude dissolved organic carbon that becomes available to bacteria. In return, the bacteria remineralize sulphur, nitrogen and phosphorous to support the further growth of microalgae. In specific interactions, heterotrophic bacteria supply B vitamins as organic cofactors or produce siderophores to bind iron, which could be utilized by microalgae, while the algae supply fixed carbon to the bacteria in return. In this review, we focus on mutualistic relationship between microalgae and bacteria, summarizing recent studies on the mechanisms involved in microalgae-bacteria symbiosis. Symbiotic bacteria on promoting microalgal growth are described and the relevance of microalgae-bacteria interactions for biofuel production processes is discussed. Symbiotic microalgae-bacteria consortia could be utilized to improve microalgal biomass production and to enrich the biomass with valuable chemical and energy compounds. The suitable control of such biological interactions between microalgae and bacteria will help to improve the microalgae-based biomass and biofuel production in the future.
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