Dendrimer activated surface

Srikant, P., Singh, A.K., McElhanon, J.R., and Dentinger, P.M. (2004) Dendrimer-activated surfaces for high density and high activity protein chip applications. Langmuir 20(15), 6075-6079. 

The density of immobilized proteins was successfully improved when a dendrimer-activated surface was used.24 Poly(propyleneimine) dendrimers were bound to the Si and glass surface that was modified with l,l -carbonyldiimidazole under anhydrous conditions. Due to the high concentration of charged amine groups of dendrimers, this method provides a fine platform for high density protein immobilization. 

Hong et al. (2004) also found that modification of PAMAM dendrimers with a short PEG linker arm could act to reduce nonspecificity caused by the amines on the dendrimer-modified surface. An azido-PEGj-aininc spacer was activated with nitrophenyl carbamate to yield an activated intermediate that could be used to modify the amines on the dendrimer (Figure 7.24). Reaction at high molar ratio resulted in about 61 PEG-azido spacers on the dendrimer. Reduction of the azido group to an amine using triphenylphosphine in THF provided the dendrimer-PEG-amine derivative for surface modification. The added presence of the PEG spacer arm reduced... 

On account of their controllable size, geometry, and functionality, dendrimers command interest for surface modification and for enlargement of (active) surfaces. 

Catalyst Activation Gas phase activation of supported DENs was examined using in-situ FTIR spectroscopy and FTIR spectroscopy of adsorbed CO. For in-situ dendrimer decomposition studies, the spectra were collected under a gas flow composed of 20% 02/He or 20% H2/He. The supported DEN sample was pressed into a self-supporting wafer, loaded into a controlled atmosphere IR cell, and collected as the sample background. The temperature was raised stepwise and spectra were collected at each temperature until little or no change was observed. After oxidation, the sample was reduced in 20% H2/He flow with various time/temperature combinations. The sample was then flushed with He for lhr at the reduction temperature. After cooling under He flow, a background spectrum was collected at room temperature. A 5% CO/He mixture was flowed over the sample for 15 minutes, followed by pure He. IR spectra of CO adsorbed on the catalyst surface were collected after the gas phase CO had been purged from the cell. 

Supported, intact DENs do not bind CO and are not active catalysts. Presumably, in the absence of solvent, the dendrimer collapses onto the nanoparticles preventing even small substrates from accessing the metal surface (11,12). This means that the organic dendrimer must be removed in order to prepare active catalysts. 

Organometallic dendrimers have been constructed to act as potential electro-or photo-active materials, the synthesis of which will be discussed in the following section. Apart from the examples discussed above, surface modification of dendrimers with a variety of functional groups has afforded novel redox active materials [110-116]. 

Regen and Watanabe [158] fabricated multi-layers close to a thickness of 800 A by using fourth or sixth generation PAM AM dendrimers with 16 or 12 cycles, respectively. The construction techniques involved activation with K2PtCl4 on a silicon wafer containing amino groups on the surface, which was followed by deposition of the dendrimer layer. However, elimination of Pt2+ layer resulted in absence of layer growth, as examined by X-ray photoelectron spectroscopy. 

In another experiment, alkyl chains have been introduced as spacers between the surface NH2 groups of the dendrimer and the N-BOC-(S)-phenylalanine groups. In this case, too, the optical activity per end group remained constant for both, the dendrimer of the 1st (with four end groups) and of the 5th generation... 

The rate of a catalytic reaction depends on the rate of diffusion of both substrates and products to and from the catalytic sites. Therefore it is of outmost importance that the catalytically active sites are freely accessible for reactions. Only dendrimers of low generation number can possibly be expected to be suitable carriers for catalytically active sites, especially when these are located in the interior. In high-generation dendrimers with crowded surfaces catalytic activity of an internal site would be prevented. On the other hand, a crowded surface will not only hinder access to an interior ligand site but will also cause steric hindrance between groups attached to it and thus prevent high reactivity of sites at the periphery. 

The latter effect has been demonstrated by Meijer et al., who attached chiral aminoalcohols to the peripheral NH2-groups of polypropylene imine) dendrimers of different generations [100]. In the enantioselective addition of diethyl-zinc to benzaldehyde (mediated by these aminoalcohol appendages) both the yields and the enantioselectivities decreased with increasing size of the dendrimer (Fig. 28). The catalyst obtained from the 5th-generation dendrimer carrying 64 aminoalcohol groups at its periphery showed almost no preference for one enantiomer over the other. This behavior coincides with the absence of measurable optical rotation as mentioned in Sect. 3 above. The loss of activity and selectivity was ascribed to multiple interactions on the surface which were... 

Figure 7.9 Amine-containing dendrimers can be activated with SPDP to create thiol-reactive derivatives. Alternatively, the pyridyl dithiol group may be reduced to create free thiols on the dendrimer surface for subsequent conjugation.

Use of sulfo-NHS-LC-SPDP or other heterobifunctional crosslinkers to modify PAMAM dendrimers may be done along with the use of a secondary conjugation reaction to couple a detectable label or another protein to the dendrimer surface. Patri et al. (2004) used the SPDP activation method along with amine-reactive fluorescent labels (FITC or 6-carboxytetramethylrhodamine succinimidyl ester) to create an antibody conjugate, which also was detectable by fluorescent imaging. Thomas et al. (2004) used a similar procedure and the same crosslinker to thiolate dendrimers for conjugation with sulfo-SMCC-activated antibodies. In this case, the dendrimers were labeled with FITC at a level of 5 fluorescent molecules per G-5 PAMAM molecule. 

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