Cobalt oxide as a selective co-catalyst for water oxidation in the presence of an organic dye.

In photobiocatalytical processes involving the simultaneous oxidation of water and reduction of specific organic molecules (e.g., cofactors), the lack of physical separation of the redox half-reactions adversely affects the product stability. This is largely because organic molecules are generally less stable within harsh oxidative environments. In general, surface co-catalysts are able to improve the selectivity of photocatalysts towards water oxidation. However, harsh oxidative environments reduce the chemical stability of the organic molecules. Herein, we show that the use of Co3O4 as a surface co-catalyst on silver orthophosphate improve water photo-oxidation in the presence of organic dye molecules, such as methylene blue, that typically exhibits susceptibility toward photodegradation. The presence of Co3O4 on the photocatalyst surface prevents the adsorption of the organic dye, thus reducing its degradation rate. These findings provide a promising scenario for the visible light-driven reduction of organic molecules using water as an electron donor.

The effect of top-layer chemistry on the formation of supported lipid bilayers on polyelectrolyte multilayers: primary versus quaternary amines.

The influence of the surface chemistry of polyelectrolyte multilayers (PEMs) on the formation of lipid bilayers is studied here for PEMs with either polyallylamine hydrochloride (PAH) or polydiallyldimethylammonium chloride (PDADMAC) as a polycation as a top layer, and polystyrene sulfonate (PSS) as a polyanion. Small unilamellar vesicles (SUVs) composed of phosphatidyl choline and phosphatidyl serine at a 50 : 50 molar ratio are deposited on top of the PEM films. The assembly of the SUVs into bilayers is studied via a quartz crystal microbalance with dissipation (QCM-D) and fluorescence recovery after photobleaching (FRAP). SUV deposition on PDADMAC/PSS results in vesicle adsorption while on PAH/PSS under the same conditions a bilayer is formed mainly due to weak interactions between the quaternary amines of PDADMAC. FRAP measurements confirm that SUVs are not fused on top of PDADMAC/PSS. The effect of phosphate ions, in solution, on the formation of lipid bilayers is also analysed. X-ray photoelectron spectroscopy shows the complexation of phosphate salts to the primary amines of PAH and no interaction with the quaternary amines of PDADMAC. ζ-potential measurements show a potential close to 0 for the PAH/PSS multilayers in PBS while PDADMAC/PSS displays a potential of 25 mV. A model is presented for the formation of lipid bilayers on PAH/PSS PEMs taking into account the role of phosphate ions in decreasing the electrostatic interactions between SUVs and PEMs and the formation of hydrogen bonds between the phospholipids and the primary amines of PAH.

Near infrared photolysis of a Ru polypyridyl complex by upconverting nanoparticles.

NaYF4:Yb(3+)/Er(3+)nanocrystals upconvert near infrared light (980 nm) into higher energy visible photons capable of effecting the photodissociation of the monodentate pyridyl ligand in cis-[Ru(bpy)2(py)2]Cl2: opening an opportunity for advancing the use of photoactivatable metal complexes in medicine and biology.