New Photolabile Functional Polymers for Patterning onto Gold Obtained by Click Chemistry

Abstract

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.

Click Chemistry, A Powerful Tool for Pharmaceutical Sciences

“…There are often unreacted pendent functional groups leftover. Because of its high reaction yield and mild reaction conditions, people have tried to introduce azides or acetylenes as novel pendent functionalities to the polymer backbone so that it can be used for further click modifications (76,77). One concern, however, is that this strategy will make sense only when the click functionalities are introduced by copolymerization, not polymer analogous reaction.…”

Modification of Polymer Surfaces by Click Chemistry

“…[26] Haddleton and coworkers [27] ''clicked'' azido functionalized, well-defined polymers onto organic resins and, very recently, Lee et al [28] modified nanobrushes by click chemistry. We could already demonstrate that alkyne containing random and block copolymers can be effectively modified in solution by such a 1,3-dipolar cycloaddition reaction to allow the introduction of photolabile and anchoring groups for their covalent attachment on various substrates [29] as well as pendant bulky adamantanyl units. [30] Furthermore, our approach resorting predominately to partly protected hydroxystyrene diblock copolymers synthesized by controlled radical polymerization (CRP) techniques has demonstrated that functionalized nanostructured surfaces can be successfully prepared.…”

“…The synthesis of an azido-functionalized fluorescent dye (5) has been recently shown in our laboratories. [29] 4-Nitrobenzyl Azide, 4…”

The Influence of Pendant Carboxylic Acid Loading on Surfaces of Statistical Poly[(4‐hydroxystyrene)‐co‐styrene]s

“…Recently the application of nitroxidemediated free radical polymerization of AS has been used to prepare poly(hydroxystyrene/styrene) copolymers that were post functionalized by a similar approach. [16] Here we present the preparation of statistic copolymers of styrene and tBS for the preparation of polymers with variable loadings of functional groups through click chemistry.…”