Daniel Kessler

Double Thermoresponsive Block Copolymers Featuring a Biotin End Group

A poly(oligo(ethylene glycol) monomethyl ether methacrylate)-block-poly(N-isopropyl methacrylamide) (POEGMA-b-PNIPMAM) block copolymer with a biotin end group on the PNIPMAM block as a biotarget was synthesized as a model system for temperature-controlled polymer immobilization. The synthesis was based on RAFT polymerization followed by postpolymerization modification of an activated ester precursor block and an exchange of the dithioester end group within one step. NMR, differential scanning calorimetry (DSC), dynamic light scattering (DLS), and turbidimetry measurements were performed to investigate the stimulus-responsive properties. The double thermoresponsive POEGMA-b-PNIPMAM with biotin end group showed a temperature-dependent multistage assembly behavior as it was completely soluble in water at temperatures below the LCST of both blocks, formed micellar structures above the LCST of PNIPMAM but below the LCST of POEGMA, or precipitated from solution above the LCST of both blocks. At room temperature, the polymer could be immobilized onto a streptavidin surface via its biotin end group, as shown in surface plasmon resonance (SPR) experiments. At 50 °C, at which the block copolymer formed micelles trapping the biotin target within the PNIPMAM core, no immobilization was observed, showing that the biological binding ability of the model could be controlled via external stimuli.

Reactive surface coatings based on polysilsesquioxanes: universal method toward light-responsive surfaces.

Reactive surface coatings were used as an ideal precursor coating for the fabrication of three different photoswitchable surface coatings in parallel. Different light-responsive moieties, such as azobenzene, salicylideneaniline, and spiropyran, were immobilized on glass, polycarbonate, and steel surfaces. Independent from the underlying substrate, wettability could be switched reversibly by UV irradiation. The maximum switching range was obtained after functionalization of the reactive coating with spiropyran, resulting in a contact angle difference between the two isomeric states of almost 30°.

Reactive surface coatings based on polysilsesquioxanes: controlled functionalization for specific protein immobilization.

The key designing in reliable biosensors is the preparation of thin films in which biomolecular functions may be immobilized and addressed in a controlled and reproducible manner. This requires the controlled preparation of specific binding sites on planar surfaces. Poly(methylsilsesquioxane)-poly(pentafluorophenyl acrylates) (PMSSQ-PFPA) are promising materials to produce stable and adherent thin reactive coatings on various substrates. Those reactive surface coatings could be applied onto various materials, for example, gold, polycarbonate (PC), poly(tetrafluoroethylene) (PTFE), and glass. By dipping those substrates in a solution of a desired amine, specific binding sites for protein adsorption could be immobilized on the surface. The versatile strategy allowed the attachment of various linkers, for example, biotin, l-thyroxine, and folic acid. The adsorption processes of streptavidin, pre-albumin, and folate-binding protein were monitored using surface plasmon resonance (SPR), Fourier transform infrared (FTIR) spectroscopy, fluorescence spectroscopy, and atomic force microscopy (AFM). The presented protein immobilization strategy, consisting of four steps (a) spin-coating of PMSSQ-PFPA hybrid polymer from tetrahydrofuran (THF) solution, (b) annealing at 130 degrees C for 2 h to induce thermal cross-linking of the PMSSQ part, (c) surface analogues reaction with different amino-functionalized specific binding sites for proteins, and (d) controlled assembly of proteins on the surface, may find various applications in future biosensor design.

Reactive Surface Coatings Based on Polysilsesquioxanes: Defined Adjustment of Surface Wettability

We have investigated a generally applicable protocol for a substrate-independent reactive polymer coating that offers interesting possibilities for further molecular tailoring via simple wet chemical derivatization reactions. Poly(methylsilsesquioxane)-poly(pentafluorophenyl acrylate) hybrid polymers have been synthesized by RAFT polymerization, and stable reactive surface coatings have been prepared by spin-coating on the following substrates: Si, glass, gold, PMMA, PDMS, and steel. These coatings have been used for a defined adjustment of surface wettability by surface-analogous reaction with various amines (e.g., glutamic acid to obtain hydrophilic surfaces (Theta(a) = 18 degrees) or perfluorinated amines to obtain hydrophobic surfaces (Theta(a) = 138 degrees)). Besides the successful covalent attachment of small molecules and polymers, amino-functionalized nanoparticles could also be deposited on the surface, resulting in nanostructured coatings, thereby expanding the accessible contact angle of hydrophobic surfaces further to Theta(a) = 152 degrees. The surface-analogous conversion of the reactive coating with isopropyl amine produced in situ temperature-responsive coatings. Using the presented simple, generally applicable protocol for substrate-independent reactive polymer coatings, the contact angle of water could be switched reversibly by almost 60 degrees.

Surface Coatings Based on Polysilsesquioxanes: Solution-Processible Smooth Hole-Injection Layers for Optoelectronic Applications

Optoelectronic devices usually consist of a transparent conductive oxide (TCO) as one electrode. Interfacial engineering between the TCO electrode and the overlying organic layers is an important method for tuning device performance. We introduce poly(methylsilsesquioxane)-poly(N,N-di-4-methylphenylamino styrene) (PMSSQ-PTPA) as a potential hole-injection layer forming material. Spin-coating and thermally induced crosslinking resulted in an effective planarization of the anode interface. HOMO level (-5.6 eV) and hole mobility (1 × 10(-6)  cm(2)  · Vs(-1) ) of the film on ITO substrates were measured by cyclovoltammetry and time-of-flight measurement demonstrating the hole injection capability of the layer. Adhesion and stability for further multilayer built-up could be demonstrated. Contact angle measurements and tape tests after several solvent treatments proved the outstanding film stability.

Modular approach towards multi-functional surfaces with adjustable and dual-responsive wettability using a hybrid polymer toolbox

Poly(methylsilsesquioxane)-based hybrid polymers carrying orthogonally reactive moieties demonstrate an effective modular approach to creating multi-reactive surface coatings. By a sequential surface-analogous reaction different functions could be immobilized in a defined ratio, resulting in dual- or triple-functionalized surfaces.