Core-shell surface activity

A wide variety of capsules loaded with water-immiscible or water-iasoluble materials have been prepared by complex coacervation. Capsule size typically ranges from 20—1000 p.m, but capsules outside this range can be prepared. Core contents usually are 80—95 wt %. Complex coacervation processes are adversely affected by active agents that have finite water solubiUty, are surface-active, or are unstable at pH values of 4.0—5.0. The shell of dry complex coacervate capsules is sensitive to variations ia atmospheric moisture content and becomes plasticized at elevated humidities. 

In 1989, we developed colloidal dispersions of Pt-core/ Pd-shell bimetallic nanoparticles by simultaneous reduction of Pd and Pt ions in the presence of poly(A-vinyl-2-pyrrolidone) (PVP) [15]. These bimetallic nanoparticles display much higher catalytic activity than the corresponding monometallic nanoparticles, especially at particular molecular ratios of both elements. In the series of the Pt/Pd bimetallic nanoparticles, the particle size was almost constant despite composition and all the bimetallic nanoparticles had a core/shell structure. In other words, all the Pd atoms were located on the surface of the nanoparticles. The high catalytic activity is achieved at the position of 80% Pd and 20% Pt. At this position, the Pd/Pt bimetallic nanoparticles have a complete core/shell structure. Thus, one atomic layer of the bimetallic nanoparticles is composed of only Pd atoms and the core is completely composed of Pt atoms. In this particular particle, all Pd atoms, located on the surface, can provide catalytic sites which are directly affected by Pt core in an electronic way. The catalytic activity can be normalized by the amount of substance, i.e., to the amount of metals (Pd + Pt). If it is normalized by the number of surface Pd atoms, then the catalytic activity is constant around 50-90% of Pd, as shown in Figure 13. 

In the literature a difference is made between matrix encapsulation and true encapsulation. In matrix encapsulation the resulting particles are more correctly described as aggregates of actives in a matrix material. A significant portion of the active is lying on the surface of the particles. True encapsulation is used for processes leading to core-shell-type products. However, this distinction of true and matrix is prone to argumentation. 

Micelles are colloidal dispersions that form spontaneously, under certain concentrations, from amphiphilic or surface-active agents (surfactants), molecules of which consist of two distinct regions with opposite afL nities toward a given solvent such as water (Torchilin, 2007). Micelles form when the concentration of these amphiphiles is above the critical micelle concentration (CMC). They consist of an inner core of assembled hydrophobic segments and an outer hydrophilic shell serving as a stabilizing interface between the hydrophobic core and the external aqueous environment. Micelles solubilize molecules of poorly soluble nonpolar pharmaceuticals within the micelle core, while polar molecules could be adsorbed on the micelle surface, and substances with intermediate polarity distributed along surfactant molecules in intermediate positions. 

The presence of a hydrophobic-hydrophilic interface can dramatically change the reaction conditions. The hydrophobic core will selectively absorb hydrophobic species from the solution (Fig. 12), and this will result in a redistribution of monomer concentrations between the core and bulk solution. Because the probability of attachment for each comonomer is determined by its concentration in a relatively small reaction volume near an active chain end, the active center inside the hydrophobic core will mainly attach more hydrophobic species on the other hand, when the active center is located on the globule surface, it will mainly attach polar (soluble) monomers. In this way, the two-layer globule will grow, retaining its core-shell structure with a predominantly hydrophobic core and a hydrophilic outer envelope (see Fig. 12). 

Figure 3.3.14 Experimental ORR activity of dealloyed Pt-Cu and Pt-Ni core-shell nanoparticle ORR catalysts compared to a pure-Pt nanoparticle catalyst. All three catalyst particles are supported on a high surface area carbon material indicated by the suffix 1C. The shift of the j-E curve of the core-shell catalysts indicates the onset of oxygen reduction catalysis at a more anodic electrode potential (equivalent to a lower overpotential) and hence represents improved ORR reactivity compared to pure Pt.

To inspect and compare the activation overvoltage of the three catalysts in more detail, so-called Tafel plots are used, which plot the cell voltage as a function of the logarithm of the current density. Figure 3.3.16B shows the Tafel plots derived from Figure 3.3.15A. At a cell voltage of 0.9 V, where the overall reaction rate is limited by the chemical surface catalysis, the dealloyed core-shell catalysts perform three... 

Fig. 8 Composite particles consisting of thermosensitive core-shell particles in which metallic nanoparticles are embedded. Left The composite particles are suspended in water, which swells the thermosensitive network attached to the surface of the core particles. In this state, the reagents can diffuse freely to the nanoparticles, which act as catalysts. Right At higher temperatures (T > 32°C) the network shrinks and the catalytic activity of the nanoparticles is strongly diminished...

In addition to the benefits of MEF from metal nanostructures deposited onto solid supports that are very useful in surface bioassays, MEF can also be observed from individual nanostructures in bioassays carried out in solution. In this regard, fluorophores and metal nanostructures can be assembled in core-shell architecture and can be used as fluorescent nanoparticles as indicators in biological plications such as imaging of cellular activity or single-molecule sensing. 

Two different nanomaterials, namely colloidal core / shell Quantum Dots (QDs) and Quantum Rods (QRs) were synthesized as described in [51]. In the case of CdSe / ZnS QDs, the synthesis yielded samples emitting at Inux = 580 nm widi a spectral width of the fluorescence emission of 40 nm. CdSe quantum rods showed an emission peak centered at l x = 567 nm with similar linewidth. The NCs were subsequently dispersed in PMMA and deposited onto the substrate by spin-coating. In order to study tiie influence of the average fluorophore-metallic surface distance on the MEF efi t, several thicknesses of the active layer were investigated, finding an o(Aimum value of 35 nm, as measured from the surface of the metallic nanostructures. 

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