Julia Witt

Nanoparticle-Imprinted Polymers for Size-Selective Recognition of Nanoparticles**

Citrate-stabilized gold nanoparticles 15 nm and 33 nm in diameter were transferred concomitantly with a monolayer of positively charged polyaniline by Langmuir-Blodgett transfer at pH 5 onto a conducting indium-doped tin oxide (ITO) support. Films consisting of one to three layers of polyaniline with thicknesses of 1-3 nm were prepared and characterized by scanning electron microscopy (SEM), atomic force microscopy (AFM), and X-ray photoelectron spectroscopy. After electro-oxidation of the Au nanoparticles in 0.1 M KCl, cavities were left behind in the film that could be analyzed by SEM. These cavities were able to recapture analyte nanoparticles from a solution of pH 10 and showed size-exclusion properties. The amount of nanoparticles taken up by the cavities was conveniently analyzed by measuring the charge associated with the electro-oxidation of these particles in 0.1 M KCl after the film had been rinsed with water. The size-exclusion properties improved with the number of Langmuir-Blodgett layers transferred.

Microelectrospotting as a new method for electrosynthesis of surface-imprinted polymer microarrays for protein recognition

Here we introduce microelectrospotting as a new approach for preparation of protein-selective molecularly imprinted polymer microarrays on bare gold SPR imaging chips. During electrospotting both the gold chip and the spotting tip are electrically connected to a potentiostat as working and counter electrodes, respectively. The spotting pin encloses the monomer-template protein cocktail that upon contacting the gold surface is in-situ electropolymerized resulting in surface confined polymer spots of ca. 500 µm diameter. By repeating this procedure at preprogrammed locations for various composition monomer-template mixtures microarrays of nanometer-thin surface-imprinted films are generated in a controlled manner. We show that the removal and rebinding kinetics of the template and various potential interferents to such microarrays can be monitored in real-time and multiplexed manner by SPR imaging. The proof of principle for microelectrospotting of electrically insulating surface-imprinted films is made by using scopoletin as monomer and ferritin as protein template. It is shown that microelectrospotting in combination with SPR imaging can offer a versatile platform for label-free and enhanced throughput optimization of the molecularly imprinted polymers for protein recognition and for their analytical application.

Local control of protein binding and cell adhesion by patterned organic thin films.

Control of the cell adhesion and growth on chemically patterned surfaces is important in an increasing number of applications in biotechnology and medicine, for example implants, in-vitro cellular assays, and biochips. This review covers patterning techniques for organic thin films suitable for site-directed guidance of cell adhesion to surfaces. Available surface patterning techniques are critically evaluated, with special emphasis on surface chemistry that can be switched in time and space during cultivation of cells. Examples from the authors’ laboratory include the use of cell-repellent self-assembled monolayers (SAM) terminated by oligoethylene glycol (OEG) units and the lifting of the cell repellent properties by use of electrogenerated Br2/HOBr which can be performed with positionable microelectrodes. Structural changes of the SAM were analyzed by polarization-modulated infrared reflection absorption spectroscopy (PM IRRAS). Use of a soft array system of individually addressable microelectrodes enables formation of flexible and complex patterns in a short time and has the potential for further acceleration of probe-induced local manipulation of cell adhesion.

Fourier-transform spatial modulation spectroscopy of single gold nanorods

Abstract Sensing the scattered fields of single metallic nanostructures is a crucial step towards the applications of isolated plasmonic antennas, such as for the sensing of single molecules or nanoparticles. In the past, both near- and far-field spectroscopy methods have been applied to monitor single plasmonic resonances. So far, however, these spectral-domain techniques do not yet provide the femtosecond time resolution that is needed to probe the dynamics of plasmonic fields in the time domain. Here, we introduce a time-domain technique that combines broadband Fourier-transform spectroscopy and spatial modulation spectroscopy (FT-SMS) to quantitatively measure the extinction spectra of the isolated gold nanorods with a nominal footprint of 41×10 nm2. Using a phase-stable pulse pair for excitation, the technique is capable of rejecting off-resonant stray fields and providing absolute measurements of the extinction cross section. Our results indicate that the method is well suited for measuring the optical response of strongly coupled hybrid systems with high signal-to-noise ratio. It may form the basis for new approaches towards time-domain spectroscopy of single nanoantennas with few-cycle time resolution.