Surface functionalization nanoparticles

Surface-functionalized nanoparticles are very good candidates as templates for crystallization on the outside surface of the particles owing to their monodisperse size and large surface area. The use of such nanoparticles for biomimetic HAP... 

Fig. 9 (a) Surface-functionalized nanoparticles as templates for biomineralization, (b) TEM micrographs of carboxylated nanoparticles with hydroxyapatite nanocrystals [101]... 

The microemulsion polymerization and copolymerization of amphiphilic monomers and macromonomers can produce the fine polymer latex in the absence of emulsifier [98-100], The surface active block or graft copolymer stabilizes the latex particles. The chemically bound emulsifier (surface active copolymer) onto the particles surface is known to be much more efficient emulsifier than the emulsifier physically adsorbed onto the particle surface and, therefore, very stable and fine polymer latexes are formed. The similar behavior is expected with the transferred emulsifier radicals. For example, the surface-functionalized nanoparticles in the 12 - 20 nm diameter range can be prepared by a one-step or two-step microemulsion copolymerisation process of styrene (and/or divinylbenzene (DVB)) with the polymerisable macromonomer (Fig. 7) [93, 101]. 

Schellenberger, E. A. Reynolds, F Weissleder, R. Josephson, L. Surface-functionalized nanoparticle library yields probes for apoptotic cells. ChemBioChem 2004,5,275-279. 

Choi, S. W., W. S. Kim, and J. H. BCim. 2005. Surface-functionalized nanoparticles for controlled drug delivery. Methods Mol Biol 303 121-31. 

The rapid development of nanotechnology has revolutionized scientific developments in recent decades [1]. The synthesis, characterization, and application of functionalized nanoparticles are currently a very active field of research [2], Due to the size limitation of metal nanoparticles, they show very unique properties, which are called nano-size effect or quantum-size effect , which is different from those of both bulk metals and metal atoms. Such specific properties are usually dominated by the atoms located on the surface. In nanoparticles systems, the number of atoms located on the surface of the particles increases tremendously with decreasing of the particle diameter [3]. 

Shi, X., Wang, S., Sun, H., and Baker Jr., J.R. (2007) Improved biocompatibility of surface functionalized dendrimer-entrapped gold nanoparticles. Soft Matter 3, 71-74. 

It is difficult to predict the effect of surface functionalization on the optical properties of nanoparticles in general. Surface ligands have only minor influence on the spectroscopic properties of nanoparticles, the properties of which are primarily dominated by the crystal field of the host lattice (e.g., rare-earth doped nanocrystals) or by plasmon resonance (e.g., gold nanoparticles). In the case of QDs, the fluorescence quantum yield and decay behavior respond to surface functionalization and bioconjugation, whereas the spectral position and shape of the absorption and emission are barely affected. 

Despite the promising possibilities offered by the different types of nanoparticles, their routine use is still strongly limited by the very small number of commercially available systems and the limited amount of data on their reproducibility (in preparation, spectroscopic properties, and apphcation) and comparability (e.g., fluorescence quantum yields, stability) as well as on their potential for quantification. To date, no attempt has yet been published comparing differently functionalized nanoparticles from various sources (industrial and academic) in a Round Robin test, to evaluate achievable fluorescence quantum yields, and batch-to-batch variations for different materials and surface chemistries (including typical ligands and bioconjugates). Such data would be very helpful for practitioners and would present the first step to derive and establish quality criteria for these materials. 

Based on well established silica chemistry, the surface of silica nanomaterials can be modified to introduce a variety of functionalizations [3, 11, 118]. The toxicity of surface-modified nanomaterials is largely determined by their surface functional groups. As an example, Kreuter reported that an apolipoprotein coating on silica nanoparticles aided their endocytosis in brain capillaries through the LDL-receptor [122-124]. Overall, silica nanomaterials are low-toxicity materials, although their toxicity can be altered by surface modifications. 

Zhang, H.L, et ah, Vapour sensing using surface functionalized gold nanoparticles. Nanotechnology, 2002.13(3) p. 439. 

Li et al. reported first on the decoration of hydrothermal carbon spheres obtained from glucose with noble metal nanoparticles [19]. They used the reactivity of as-prepared carbon microspheres to load silver and palladium nanoparticles onto then-surfaces, both via surface binding and room-temperature surface reduction. Furthermore, it was also demonstrated that these carbon spheres can encapsulate nanoparticles in their cores with retention of the surface functional groups. Nanoparticles of gold and silver could be encapsulated deep in the carbon by in situ hydrothermal reduction of noble-metal ions with glucose (the Tollens reaction), or by using silver nanoparticles as nuclei for subsequent formation of carbon spheres. Some TEM images of such hybrid materials are shown in Fig. 7.4. 

Specific, surface confined reactions not only directly involve catalysis but also the built-up of sdf-assembled multilayers (see Fig. 9.1 (3)) with co-functionalities for more complex (bio-) catalytic systems such as proteins or the directed deposition of active metals. Furthermore, SAM on flat substrates can be used for the study and development of e.g. catalytic systems, but are not useful for large scale applications because they have very limited specific surface. Here, nanoparticle systems covered with 3D-SAMs are the ideal solution of combining the advantages of high surface area, defined surface composition and accessibility of proximal active catalytic centers. 

Figure 13. Selective Surface Functionalization and Selective deposition of Pd Nanoparticles in the micropores of SBA-15.

---