No abstract

A simple, fast, and versatile approach to the fabrication of outstanding surface enhanced Raman spectroscopy (SERS) substrates by exploiting the optical properties of the Ag nanoparticles and functional as well as organizational characteristics of the polymer brushes is reported. First, poly(2‐(dimethylamino)ethyl methacrylate) brushes are synthesized directly on glassy carbon by self‐initiated photografting and photopolymerization and thoroughly characterized in terms of their thickness, wettability, morphology, and chemical structure by means of ellipsometry, contact angle, AFM, and XPS, respectively. Second, Ag nanoparticles are homogeneously immobilized into the brush layer, resulting in a sensor platform for the detection of organic molecules by SERS. The surface enhancement factor (SEF) as determined by the detection of Rhodamine 6G is calculated as 6 × 106.

A straightforward method is presented for the preparation of homogeneous as well as structured polymer brushes on SiC substrates. The self-initiated photografting and photopolymerization (SIPGP) of styrene and N,N-dimethylaminoethyl methacrylate (MAEMA) allows the preparation of polymer brush layers directly and selectively onto C;OH terminated (0001) 6H-SiC surfaces in a single step reaction. In contrast, the analogous reaction on Si;OH terminated (0001) 6H-SiC does not occur. The reactivity contrast between Si;OH and C;OH terminated crystal faces for SIPGP was studied using the density functional theory method which showed a higher SiO;H bond dissociation energy for hydrogen abstraction on the Si-polar relative to the C-polar crystal face. Furthermore, structured polymer brushes on the submicrometer scale could be prepared by the carbon templating (CT) technique on Si;OH terminated (0001) 6H-SiC surfaces. First, an ultrathin template layer was formed by electron beam induced carbon deposition (EBCD) on SiC by means of a focused electron beam. Amplification of the template by SIPGP resulted in polymer brush structures with controlled three-dimensional shapes. The effect of the applied electron dose as well as the initial lateral structure size on the brush layer morphology was investigated.

Micro- and nanostructured polymer brushes on diamond can be directly prepared by carbon templating and amplification of the latent structures by photografting of a broad variety of vinyl monomers such as styrenes, acrylates and methacrylates. Even template structures with lateral dimensions as small as 5 nm can be selectively amplified and defined polymer brush gradients of a variety of functional polymers are realizable by this technique. Furthermore, conjugation with a model protein (GFP) results in protein density gradients of high loading and improved chemical stability. The effective functionalization of chemically and biologically inert diamond surfaces with stable functional polymer brushes, the possibility of structuring by the carbon templating technique and the direct biofunctionalization are crucial steps for the development of diamond based biosensors

We report on the preparation of microstructured poly(2-oxazoline) bottle-brush brushes (BBBs) on nanocrystalline diamond (NCD). Structuring of NCD was performed by photolithography and plasma treatment to result in a patterned NCD surface with oxidized and hydrogenated areas. Self-initiated photografting and photopolymerization (SIPGP) of 2-isopropenyl-2-oxazoline (IPOx) resulted in selective grafting of poly(2-isopropenyl-2-oxazoline) (PIPOx) polymer brushes only at the oxidized NCD areas. Structured PIPOx brushes were converted by methyl triflate into the polyelectrolyte brush macroinitiator for the living cationic ring-opening polymerization (LCROP) of 2-oxazolines. The LCROP was performed with 2-ethyl-2-oxazoline (EtOx) as well as 2-(carbazolyl)ethyl-2-oxazoline (CarbOx) as monomers, resulting in structured bottle-brush brushes (BBB) with different pendant side chains and functionalities. FT-IR spectroscopy, fluorescence microscopy, and AFM measurements indicated a high side chain grafting density as well as quantitative and selective reactions. Poly(2-oxazoline) BBBs containing hole conducting carbazole moieties on NCD as electrode material may open the way to advanced amperometric biosensing systems.