Brust-Schiffrin method

Figure3.9 Brust-Schiffrin method for the synthesis of monolayer protected gold clusters. Reproduced from reference [62] by permission of The Royal Society of Chemistry.

Other modifications to the reaction conditions of the Brust-Schiffrin method, such as a reduction temperature of — 78 °C and the use of a hyperexcess of hexanethiol, results in an Au38(thiolate)24, based on observations, LDI-TOF mass spectrometry, TGA analysis and elemental analysis [69]. The influence of preparation temperature on the size and monodispersity of dodecylthiol monolayer protected gold clusters has also been reported. Both and SAXS measurements show that higher temperatures increase polydispersity. This modification of poly-dispersity may be related to the existence of a dynamic exchange of thiols at the particle surface with thiols in the solvent [70]. 

The modification to the Brust-Schiffrin method through the addition of lauryla-mine (LAM) or octadecylamine (ODA) instead of thiols to colloidal gold particles... 

As mentioned above, the grafting to technique enables in a one-pot reaction the synthesis of Au NPs stabilized by sulfur-containing polymers, which bear functional groups such as dithioester, trithioester, thiol, thioether and disulfide at the end of a polymer chain or in the middle. This method leads to nanoparticles similar to those obtained by the Brust-Schiffrin method in which alkanethiol-protected Au NPs of small size are obtained. This grafting to technique leads to very stable nanomaterials that also present a high surface graft density of polymer brush on the Au NP surface. 

For example, Wuelfing et al. reported on the synthesis of Au NPs using the thiolated polymer, a-methoxy-co-mercapto-poly(ethylene glycol) (PEG-SH), as stabilizer in a modification of the Brust-Schiffrin method using a 1/12 polymer thiol/ AuC14 ratio. Transmission electron microscopy showed that the product had modestly polydisperse Au cores of average diameter 2.8 1 nm. This nanomaterial led to characteristics uniquely different from alkanethiolate MPCs, notably aqueous solubility, thermal and chemical stability, ligand footprint size, and ionic conductivity [66]. 

The fourth method for the preparation of polymer stabilized Au NPs is the postmodification of pre-formed Au NPs . This method is used to avoid broad distribution of sizes of Au NPs stabilized with polymers through any of the methods described previously. As we have mentioned before, in a first step very monodisperse Au NPs are obtained by common methods, such as the citrate reduction or the Brust-Schiffrin method. In a second step, the exchange of weakly bound citrate ions with polymer or modification ofend-functionalized thiols with polymers is performed. 

The third class of AuNPs-dendrimer nanomaterials is Nanoparticle Cored Dendrimers (NCDs). The first report on this topic describes a new strategy in which Frechet-type dendrons with a single thiol group at the focal point were used as a surface stabilizer of Au NPs. These dendronized Au NPs were synthesized using a modification of the two-phase Brust-Schiffrin method, giving rise to highly stable and very monodisperse Au NPs of small size (about 2.4—3.1 nm) [129] (Figure 3.13). 

Scheme 1 The one- and two-phase Brust-Schiffrin method for the synthesis of thiol-capped gold nanoparticles, and the first step of the reaction prior to the reduction step with NaBIL [63]...

The Brust—Schiffrin Method Two-Phase Synthesis and Stabilization by Thiols... 

Fig. 4.5 Brust-Schiffrin method for two-phase synthesis of AuNPs by reduction of gold salts in presence of external thiol hgands (Reprinted with permission from Saha et al. 2012, Copyright 2012 American Chemical Society)...

In the twentieth century, various methods for the preparation of gold colloids (AuNPs) were reported and reviewed [41] among them, the Brust-Schiffrin method for AuNPs synthesis [42], published in 1994, has had considerable impact on the field since it allowed, for the first time, the facile synthesis of thermally stable and air-stable AuNPs of reduced dispersity and controlled size. 

Disclosing the binding motif of multiblock RAFT polymers on AuNPs from citrate reduction raises the questimi of whether the polymer binding can vary for different types of AuNPs. It is known that AuNPs from the two-phase Brust-Schiffrin synthesis can assemble into spherical particle networks when treated with low molecular weight crosslinking agent [106, 107]. When tetraocty-lammonium bromide-capped AuNPs from this two-phase method are functionalized in toluene dispersion with multiblock RAFT polymers of styrene, the formation of spherical AuNP assemblies can be observed by TEM (Fig. 9) [108]. It can be concluded from these TEM images that the particle density inside... 

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