Nitroxide-mediated radical polymerization (NMRP) was used for the synthesis of the random copolymer poly[styrene-r-(4-propargyloxystyrene)] with a narrow molecular weight distribution (PDI ∼ 1.2). The material was postfunctionalized by polymer analogous reactions and via Cu(I)-catalyzed 1,3-dipolar cycloadditions (“click chemistry approach”) to provide a family of photopatternable functional polymers for nanotechnology applications. For this, a series of azides were designed in order to incorporate subunits with specific properties into the materials. Photopatterning was made possible by the introduction of units with a photoremovable amino protecting group (PRG) (nitroveratryloxycarbonyl, NVOC) which may lead to the release of amino functions after selective UV/laser irradiation. Covalent attachment of the functional polymers onto gold was promoted by sulfide-containing anchoring units again introduced as pending groups onto the polymer backbone via the 1,3-dipolar cycloaddition reaction. The modified materials were obtained in almost quantitative yields under mild conditions according to IR and NMR studies. Thermal characterization was accomplished by DSC and TGA. Click chemistry is once more proven to be a useful tool for material science, in this particular case for the preparation of functional polymers for photopatterning with modulated properties.

We present the synthesis and characterization of a series of photolabile phenacyl derivative polymers and their subsequent thin film preparation. These systems are composed of up to three methacrylate units: a photolabile component including a p-methoxyphenacyl moiety which after selective irradiation (UV/laser) can provide free carboxylic groups in specific areas for further modification; an anchoring unit, trimethoxysiloxane or glycidyl methacrylate derivative, which allows the covalent attachment of the polymer to the substrate; and a spacer, methyl methacrylate or styrene, which in the appropriate proportion ensures the formation of films with good quality. Structural and thermal properties of these materials have been analyzed by means of NMR, FTIR, elemental analysis, UV, gel permeation chromatography, differental scanning calorimetry, and thermogravimetric analysis. The polymers have been subsequently processed by spin coating to render ultrathin films (<50 nm). Topographic and structural characterization studies of the films have been carried out with atomic force microscopy, contact angle measurements, and X-ray photoelectron spectroscopy. The extent of the substrate attachment of the polymers depending on the nature of the anchoring groups have been studied by ellipsometry and FTIR.

The surface properties of films made of p-methoxyphenacyl derivative terpolymers, associated with photocleavage by UV irradiation, and their optical patterning are investigated. The deprotection reaction has been monitored by UV and FTIR spectroscopy, contact angle measurements, and X-ray photoelectron spectroscopy, revealing the photoremoval of the protecting p-methoxyphenacyl group in high yields under mild conditions. Parallel and serial patterning of the films has been performed by selective irradiation through optical masks and by laser irradiation via fiber tips of a scanning near-field optical microscope, respectively. By irradiation of photolabile protected functional groups, free carboxylic groups become exposed to the surface with which fluorescent dyes and proteins can be associated specifically.

Abstract-We present the synthesis and characterization of a family of photolabile co-and terpolymers (acrylate/methacrylate type) suitable for nanotechnology applications. They have been obtained by free radical polymerization of the corresponding monomers: a photosensitive component (nitroveratryl methacrylamide type), which allows the release of amino functionalities after the irradiation with UV light, a dithiol derivative that enables the covalent attachment of these materials onto gold substrates, and methyl methacrylate or styrene acting as a spacer between both functional units, promoting the formation of films with good quality. The polymers have been characterized using techniques as NMR, FTIR, GPC, TGA, DSC and UV spectroscopy. The deprotection of the amino function in the terpolymers by UV irradiation has been proven.

The successful selective metal deposition using a photolabile polymer consisting of a diazosulfonate side chain group has been reported. In addition to 20 mol% diazosulfonate monomer the terpolymer contains 5 mol% of a silane compound, which is necessary for the covalent anchoring of the film onto the substrate. Furthermore, films were prepared using photolabile polymers containing protected amines onto glass and silicon substrates. These films are suitable for imagewise structuring by UV‐light and laser irradiation, and nanoelements like DNA strands could be attached individually in further steps. These polymeric amines with similar structure like the diazosulfonate terpolymers were synthesized by free radical polymerization of three monomer units which are methyl methacrylate (MMA) (spacer), 3‐(trimethoxysilyl)propylmethacrylate (anchoring group) and N‐(N‐nitroveratryloxycarbonyl‐aminopropyl)‐methacrylamide (photolabile compound). The anchoring groups were varied to enable covalent attachment of the polymers, for example, onto gold substrates. Azosulfonates, sulfonate esters, and both protected amines and carboxylic acid groups were used as thermally labile or photolabile functionalities. Selective deprotection using heat or light could be varied. Finally block copolymers based on orthogonally protected hydroxystyrenes could be prepared by controlled radical polymerization. A highly ordered nanostructure could be realized in thin films of these polymers exhibiting strong changes using heat or light treatment. Copyright © 2006 John Wiley & Sons, Ltd.