Dendrimer oxide surface

Very recently, poly(amidoamine) dendrimers were surface-functionalized with four, eight (85), 16, and 32 nitroxyl radical units [155], In all these dendrimers electrochemical oxidation in acetonitrile of the appended radical units occurs at the same potential in a single reversible process, the number of exchanged electrons being equal to the number of units present. Thus, all the nitroxyl radical fragments in the dendrimer behave independently and are accessible from the electrode surface. 

Paramagnetic centers can be directly attached to the site of interest via covalent bonds. Such methodology is particularly well developed for proteins, where the amino acid residue of interest can be converted to a cysteine residue by site-directed mutagenesis, and a thiol-reactive spin label can be attached under mild conditions. If a peptide or protein is synthesized, the nonnative spin-labeled amino acid TOAC can be incorporated directly into the chain.In other synthetic systems, nitroxides can be conveniently attached via ether, ester, or amide bonds, an approach that is also viable for labeling ceramic and metal oxide surfaces. The complexity of supramolecular systems that can be investigated by this approach is exemplified by a study on the interaction between spin-labeled starburst dendrimers and DNA. ... 

Dendrimer-protected colloids are capable of adsorbing carbon monoxide while suspended in solution, but upon removal from solution and support on a high surface area metal oxide, CO adsorption was nil presumably due to the collapse of the dendrimer [25]. It is proposed that a similar phenomena occurs on PVP-protected Pt colloids because removal of solvent molecules from the void space in between polymer chains most likely causes them to collapse on each other. Titration of the exposed surface area of colloid solution PVP-protected platinum nanoparticles demonstrated 50% of the total metal surface area was available for reaction, and this exposed area was present as... 

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. 

As prepared and purified G4-OH(Pt5o) DENs solutions (ca. 20 /xM) can also be used to prepare high surface area sol-gel Pt/silica catalysts. This process can be used to carefully control metal loadings without condensing the solution provided the loadings remain low (less than 0.2 % Pt). The low concentrations do not allow the dendrimer to serve as a porosity template. Eurther, low loadings combined with delayed introduction of the DENs solution to a preformed sol likely lead to the occlusion of metal nanoparticles within the oxide matrix. ... 

A working model for dendrimer thermolysis during calcination involves the PA-MAM dendrimer backbone initially reacting with oxygen (which may or may not be activated by a nanoparticle) in a relatively facile process to generate carboxylates and other surface species. Removal of carbonaceous species closely associated with the nanoparticle is required for complete activation of the catalyst. For Pt DENs, the surface carboxylates may be strongly adsorbed to the nanoparticle surface and extended O2 treatments are required for deep oxidation of the hydrocarbon to reach reasonably volatile species. Once formed, however, it appears that they can be removed more readily with a hydrogen treatment than with further oxidation. 

Using the dendrimer route, it is possible to prepare supported catalysts not available via traditional routes. Dendrimer derived Pt-Au catalysts having compositions within the bulk miscibility gap can be prepared on several oxide supports. For all the supports studied, the bimetallic catalysts exhibited synergism with respect to mono- and cometallic catalysts for the CO oxidation and hydrocarbon NOx SCR reactions. The bimetallic Pt-Au catalysts also showed evidence of exchanging surface and subsurface atoms in response to strongly binding ligands such as CO. 

Dendrimers containing Pt " or Pt-metal nanoparticles are easily attached to Au and other surfaces by immersion in a dilute aqueous solution of the composite for 20 h, followed by careful rinsing and drying [59,129]. Therefore it is possible to use X-ray photoelectron spectroscopy (XPS) to determine the elemental composition and the oxidation states of Pt within dendrimers. For example, Pt(4f7/2) and Pt(4f5/2) peaks are present at 72.8 eV and 75.7 eV, respectively, prior to reduction, but after reduction they shift to 71.3 eV and 74.4 eV, respectively, which is consistent with the change in oxidation state from -i-2 to 0 (Fig. 13 a]. 

Physical or electrochemical adsorption uses non-covalent forces to affix the nucleic acid to the solid support and represents a relatively simple mechanism for attachment that is easy to automate. Adsorption was favoured and described in some chapters as suitable immobilization technique when multisite attachment of DNA is needed to exploit the intrinsic DNA oxidation signal in hybridization reactions. Dendrimers such as polyamidoamine with a high density of terminal amino groups have been reported to increase the surface coverage of physically adsorbed DNA to the surface. Furthermore, electrochemical adsorption is described as a useful immobihzation strategy for electrochemical genosensor fabrication. 

In a subsequent paper, the authors developed another type of silica-supported dendritic chiral catalyst that was anticipated to suppress the background racemic reaction caused by the surface silanol groups, and to diminish the multiple interactions between chiral groups at the periphery of the dendrimer 91). The silica-supported chiral dendrimers were synthesized in four steps (1) grafting of an epoxide linker on a silica support, (2) immobilization of the nth generation PAMAM dendrimer, (3) introduction of a long alkyl spacer, and (4) introduction of chiral auxiliaries at the periphery of the dendrimer with (IR, 2R)-( + )-l-phenyl-propene oxide. Two families of dendritic chiral catalysts with different spacer lengths were prepared (nG-104 and nG-105). 

Ferrocenyl-based polymers are established as useful materials for the modification of electrodes, as electrochemical biosensors, and as nonlinear optical systems. The redox behavior of ferrocene can be tuned by substituent effects and novel properties can result for example, permethylation of the cyclopentadienyl rings lowers the oxidation potential, and the chaige transfer salt of decamethylfer-rocene with tetracyanocthylene, [FeCpJ]" (TCNE], is a ferromagnet below = 4.8 K, and electrode surfaces modified with a pentamethylferrocene derivative have been used as sensors for cytochrome c These diverse properties have provided an added impetus to studies on ferrocene dendrimers. 

The ferrocenyl dendrimers were electrodeposited in their oxidized forms onto the electrode surfaces (platinum, glassy-caibon, and gold) either by controlled potential electrolysis or by repeated cycling between the appropriate anodic and cathodic potential limits therefore the amount of electroactive material electrode-posited can be controlled with the electrolysis time or the number of scans. The electrochemical behavior of films of the polyfeirocenyl dendrimers was studied by cyclic voltammetry in fresh CH2CI2 and CHjCN solutions containing only supporting electrolyte. 

The persistence of the dendrimer decomposition products is the likely cause of the catalyst deactivation over time. The presence of dendrimer and dendrimer byproducts indicates that even the more active catalysts are not particularly clean. It is difficult to distinguish between species adsorbed on the NPs from those primarily on the support however, it is likely that the location of the dendrimer decomposition varies widely along the surface of the catalyst. The dendrimer fragments present on the support could migrate over time and poison the metal active sites, resulting in the lower catalytic activity over time. It is also possible that the residual dendrimer undergoes some slower oxidation processes that result in a stronger, unobservable poison. 

Dendrimers are large molecules, and their solubility is often an issue. Thus, it is not surprising that dendrimers can be good candidates to precipitate upon and thus modify the surface of an electrode. Dendrimers with ferrocenyl peripheral units were shown to display well-defined redox waves with the ferrocenyl units oxidizing independently.176-178 These molecules oxidatively precipitated onto the electrode surface and were characterized electrochemically and by atomic force microscopy.44 It was later shown that cyclodextrin complexation increased the solubility of these molecules.179 Similar results were obtained with dendrimers containing pendant ruthenium tris (bipyridine) and bis(terpyridine) groups.180... 

Silicon-based dendrimers 8 and 9 (Fc = ferrocenyl) also showed oxidative precipitation onto electrodes to give idealized electrochemistry as films.181 Specifically, the peak current was linear with scan rate and the potential difference between the anodic and cathodic waves was small (AE = 10 mV at a scan rate of 100 mV/s).182 This latter observation indicated that the rate of electron transfer was rapid. For molecule 9, the surface coverage was measured as = 2 x 10 10 mol/cm2. These molecules were also explored as mediators in amperometric biosensors.183 In contrast, molecule 10 showed two redox peaks, indicative of interaction between the two ferrocenyl units at each peripheral site. 181 When oxidation of one of the two interacting redox units results in some electron sharing between the two units (Robin-Day class II mixed valence species), the second oxidation is naturally... 

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