Metal nanoparticles functionalization

Another recent article by Kneipp et al. demonstrates the use of multiplexing within live cells [69]. Two different SERS particles, aggregates of metal nanoparticles functionalized with two different reporter molecules could be imaged within cells using SERS. The data obtained was analyzed using cluster methods and principal components analysis to detect the two SERS reporters within the live cells. 

The optical properties of metal nanoparticles have traditionally relied on Mie tlieory, a purely classical electromagnetic scattering tlieory for particles witli known dielectrics [172]. For particles whose size is comparable to or larger tlian tire wavelengtli of the incident radiation, tliis calculation is ratlier cumbersome. However, if tire scatterers are smaller tlian -10% of tire wavelengtli, as in nearly all nanocrystals, tire lowest-order tenn of Mie tlieory is sufficient to describe tire absorjDtion and scattering of radiation. In tliis limit, tire absorjDtion is detennined solely by tire frequency-dependent dielectric function of tire metal particles and the dielectric of tire background matrix in which tliey are... 

ROsch N (1999) A Critical Assessment of Density Functional Theory with Regard to Applications in Organometallic Chemistry. 4 109-163 Roucoux A (2005) Stabilized Noble Metal Nanoparticles An Unavoidable Family of Catalysts for Arene Derivative Hydrogenation. 16 261-279... 

The preparation and study of metal nanoparticles constitutes an important area of current research. Such materials display fascinating chemical and physical properties due to their size [62, 63]. In order to prevent aggregation, metal nanoparticles are often synthesized in the presence of ligands, functionalized polymers and surfactants. In this regard, much effort has focused on the properties of nanoparticles dispersed into LCs. In contrast, the number of nanoparticles reported that display liquid crystal behavior themselves is low. Most of them are based on alkanethiolate stabilized gold nanoparticles. 

Thiols and gold surfaces are ideal partners to write any kind of structure in nanometre dimensions. Artificial patterns of appropriately functionalized molecules can be used to bind metal nanoparticles specifically. Figure 25 gives an impression of the individual steps leading to a distinct cluster arrangement. 

Figure 25. Formation of an artificial structure of metal nanoparticles by dip pen nanolithography using an AFM (a), tip to transport functionalized thiol molecules onto a gold surface (b) and to trap the nanoparticles (c).

The synthesis of bimetallic nanoparticles is mainly divided into two methods, i.e., chemical and physical method, or bottom-up and top-down method. The chemical method involves (1) simultaneous or co-reduction, (2) successive or two-stepped reduction of two kinds of metal ions, and (3) self-organization of bimetallic nanoparticle by physically mixing two kinds of already-prepared monometallic nanoparticles with or without after-treatments. Bimetallic nanoparticle alloys are prepared usually by the simultaneous reduction while bimetallic nanoparticles with core/shell structures are prepared usually by the successive reduction. In the preparation of bimetallic nanoparticles, one of the most interesting aspects is a core/shell structure. The surface element plays an important role in the functions of metal nanoparticles like catal5dic and optical properties, but these properties can be tuned by addition of the second element which may be located on the surface or in the center of the particles adjacent to the surface element. So, we would like to use following marks to inscribe the bimetallic nanoparticles composed of metal 1, Mi and metal 2, M2. 

In the early work on the thermolysis of metal complexes for the synthesis of metal nanoparticles, the precursor carbonyl complex of transition metals, e.g., Co2(CO)8, in organic solvent functions as a metal source of nanoparticles and thermally decomposes in the presence of various polymers to afford polymer-protected metal nanoparticles under relatively mild conditions [1-3]. Particle sizes depend on the kind of polymers, ranging from 5 to >100 nm. The particle size distribution sometimes became wide. Other cobalt, iron [4], nickel [5], rhodium, iridium, rutheniuim, osmium, palladium, and platinum nanoparticles stabilized by polymers have been prepared by similar thermolysis procedures. Besides carbonyl complexes, palladium acetate, palladium acetylacetonate, and platinum acetylac-etonate were also used as a precursor complex in organic solvents like methyl-wo-butylketone [6-9]. These results proposed facile preparative method of metal nanoparticles. However, it may be considered that the size-regulated preparation of metal nanoparticles by thermolysis procedure should be conducted under the limited condition. 

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]. 

For transition and precious metals, thiols have been successfully employed as the stabilizing reagent (capping reagent) of metal nanoparticles [6]. In such cases, various functionalities can be added to the particles and the obtained nanoparticles may be very unique. It is well known that thiols provide good self-assembled monolayers (SAM) on various metal surfaces. When this SAM technique is applied to the nanoparticle preparation, nanoparticles can be covered constantly by functionalized moieties, which are connected to the terminal of thiol compounds. 

In 1994, thiols were firstly used as stabilizers of gold nanoparticles [6a]. Thiols form monolayer on gold surface [18] and highly stable nanoparticles could be obtained. Purification of nanoparticles can be carried out, which makes chemical method of metal nanoparticles a real process for nanomaterial preparation. Various thiol derivatives have been used to functionalize metal nanoparticles [6b, 19]. Cationic and anionic thiol compounds were used to obtain hydrosols of metal nanoparticles. Quaternary ammonium-thiol compounds make the nanoparticle surface highly positively charged [20]. In such cases, cationic nanoparticles were densely adsorbed onto oppositely charged surfaces. DNA or other biomolecule-attached gold nanoparticles have been proposed for biosensors [21]. 

Wet preparation of metal nanoparticles and their covalent immobilization onto silicon surface has been surveyed in this manuscript. Thiol-metal interaction can be widely used in order to functionalize the surface of metal nanoparticles by SAM formation. Various thiol molecules have been used for this purpose. The obtained functionalized particles can be purified to avoid the effect of unbounded molecules. On the other hand, hydrogen-terminated silicon surface is a good substrate to be covered by Si-C covalently bonded monolayer and can be functionalized readily by this link formation. Nanomaterials, such as biomolecules or nanoparticles, can be immobilized onto silicon surface by applying this monolayer formation system. 

As we have seen in the previous chapter, the apparent topography and corrugation of thin oxide films as imaged by STM may vary drastically as a function of the sample bias. This will of course play an important role in the determination of cluster sizes with STM, which will be discussed in the following section. The determination of the size of the metallic nanoparticles on oxide films is a crucial issue in the investigation of model catalysts since the reactivity of the particles may be closely related to their size. Therefore, the investigation of reactions on model catalysts calls for a precise determination of the particle size. If the sizes of the metal particles on an oxidic support are measured by STM, two different effects, which distort the size measurement, have to be taken into account. 

As described in this chapter, the sonochemical reduction technique appears to be a promising method for the preparation of various types of metal nanoparticles in an aqueous solution. By choosing more efficient organic additives, easily-reducible metal precursors, supports and templates with an appropriate role, more advanced functional nanoparticles could be synthesized successfully using the sonochemical reduction technique. In future, it is also possible to develop effective synthetic methods by combining the sonochemical method with other chemical methods. 

In this review, the potential uses of sonochemistry for the preparation of monometallic and bimetallic metal nanoparticles and metal-loaded semiconductor nanoparticles have been highlighted. While specific examples available in the literature were discussed, the sonochemical technique seems to offer a platform technique that could be used for synthesizing a variety of functional materials. Most of the studies to date deal with laboratory scale exploration , it would be ideal if the concepts are tested under large scale experimental conditions involving specific applications. The authors sincerely hope that the information provided in this review would prompt such experimental investigation in a new dimension. 

Functionalization and Defunctionalization Reactions Using Metal Nanoparticles in Ionic Liquids... 

This method of silanation, which uses organic solvent without the addition of water, is suitable for highly reactive silane derivatives, such as chlorosilanes, aminosilanes, and methoxysilanes. This procedure will not work for ethoxysilanes, as these compounds are not reactive enough without prior hydrolysis to create the silanol. This method is convenient to use for silica particle modification and for the functionalization of metallic nanoparticles having the requisite—OH groups present (see Chapter 14, Section 5). 

Dendrimer interior functional groups and cavities can retain guest molecules selectively, depending on the nature of the guest and the dendritic endoreceptors, the cavity size, the structure, and the chemical composition of the peripheric groups. Two main methods are known for the synthesis of metal nanoparticles inside dendrimers. The first method consists of the direct reduction of dendrimer-encapsulated metal ions (Scheme 9.4) the second method corresponds to the displacement of less-noble metal clusters with more noble elements [54]. 

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