Origin of the Bright Photoluminescence of Thiolate-protected Gold Nanoclusters: Confined Structural Water Molecules as Real Emitters

The availability of a range of excited states has enriched zero-, one- and two- dimensional quantum nanomaterials with interesting luminescence properties, in particular for noble metal nanoclusters (NCs) as typical examples. But, the elucidation and origin of optoelectronic properties remains elusive. In this report, using widely used Au(I)-alkanethiolate complex (Au(I)-SRs, R = -(CH2)12H) with AIE characteristics as a model system, by judiciously manipulating the delicate surface ligand interactions at the nanoscale interface, together with a careful spectral investigations and an isotope diagnostic experiment of heavy water (D2O), we evidenced that the structural water molecules (SWs) confined in the nanoscale interface or space are real emitter centers for photoluminescence (PL) of metal NCs and the aggregate of Au(I)-SRs complexes, instead of well-organized metal core dominated by quantum confinement mechanics. Interestingly, the aggregation of Au(I)-SRs generated dual fluorescence-phosphorescence emission and the photoluminescence intensity was independent on the degree of aggregation but showed strong dependency on the content and state of structural water molecules (SWs) confined in the aggregates. SWs are different from traditional hydrogen bonded water molecules, wherein, due to interfacial adsorption or spatial confinement, the p orbitals of two O atoms in SWs can form a weak electron interaction through spatial overlapping, which concomitantly constructs a group of interfacial states with π bond characteristics, consequently providing some alternative channels (or pathways) to the radiation and/or non-radiation relaxation of electrons. Our results provide completely new insights to understand the fascinating properties (including photoluminescence, catalysis and chirality, etc.) of other low-dimension quantum dots and even for aggregation-induced emission luminophores (AIEgens). This also answers the century old debate on whether and how water molecules emit bright color.

Impact of Saturation of Fatty Acids of Phosphatidylcholine and Oil Phase on Properties of β-Lactoglobulin at the Oil/Water Interface

Oil in water emulsions are commonly stabilized by emulsifying constituents like proteins and/or low molecular weight emulsifiers. The emulsifying constituents can compete or coexist at the interface. Interfacial properties thus depend on molecular structure of the emulsifying constituents and the oil phase and the resulting molecular interactions. The present study systematically analyzed the impact of fatty acid saturation of triacylglycerides and phosphatidylcholine on the interfacial properties of a β-lactoglobulin-stabilized interface. The long-term adsorption behaviour and the viscoelasticity of β-lactoglobulin-films were analyzed with or without addition of phosphatidylcholine via drop tensiometry and dilatational rheology. Results from the present study showed that increasing similarity in fatty acid saturation and thus interaction of phosphatidylcholine and oil phase increased the interfacial tension for the phosphatidylcholine alone or in combination with β-lactoglobulin. The characteristics and stability of interfacial films with β-lactoglobulin-phosphatidylcholine are further affected by interfacial adsorption during changes in interfacial area and crystallization events of low molecular weight emulsifiers. This knowledge gives guidance for improving physical stability of protein-based emulsions in foods and related areas. Graphic abstract