Stefan Zürcher

Surface Functionalization of Single Superparamagnetic Iron Oxide Nanoparticles for Targeted Magnetic Resonance Imaging

Magnetic resonance imaging (MRI), a non-invasive, non-radiative technique, is thought to lead to cellular or even molecular resolution if optimized targeted MR contrast agents are introduced. This would allow diagnosing progressive diseases in early stages. Here, it is shown that the high binding affinity of poly(ethylene glycol)-gallol (PEG-gallol) allows freeze drying and re-dispersion of 9 +/- 2-nm iron oxide cores individually stabilized with approximately 9-nm-thick stealth coatings, yielding particle stability for at least 20 months. Particle size, stability, and magnetic properties of PEGylated particles are compared to Feridex, a commercially available untargeted negative MR contrast agent. Biotin-PEG(3400)-gallol/methoxy-PEG(550)-gallol stabilized nanoparticles are further functionalized with biotinylated human anti-VCAM-1 antibodies using the biotin-neutravidin linkage. Binding kinetics and excellent specificity of these nanoparticles are demonstrated using quartz crystal microbalance with dissipation monitoring (QCM-D). These MR contrast agents can be functionalized with any biotinylated ligand at controlled ligand surface density, rendering them a versatile research tool.

Stability of the hydrophilic behavior of oxygen plasma activated SU-8

The effect of O2 plasma treatment on surface energy, topography and surface chemistry of the negative photoresist epoxy novolak SU-8 was investigated by contact angle goniometry, atomic force microscopy (AFM) and x-ray photoelectron spectroscopy (XPS). Directly after plasma treatment, the surfaces were completely wetted by water with a contact angle between water and the SU-8 surface below 5°. The surface free energy can be increased significantly depending on the plasma dose. The surfaces remained hydrophilic for several months showing a moderate hydrophobic recovery. The surface topography of the plasma treated SU-8 showed a formation of nanoscale aggregates. The rms-roughness of the topography was correlated with the plasma dose. An increased plasma dose induced aggregates of up to 200 nm in size. XPS measurements revealed changes in surface chemistry due to the oxygen plasma process and an increased antimony concentration on the surface.

Beyond the lotus effect: roughness influences on wetting over a wide surface-energy range.

To enhance our understanding of liquids in contact with rough surfaces, a systematic study has been carried out in which water contact angle measurements were performed on a wide variety of rough surfaces with precisely controlled surface chemistry. Surface morphologies consisted of sandblasted glass slides as well as replicas of acid-etched, sandblasted titanium, lotus leaves, and photolithographically manufactured golf-tee shaped micropillars (GTMs). The GTMs display an extraordinarily stable, Cassie-type hydrophobicity, even in the presence of hydrophilic surface chemistry. Due to pinning effects, contact angles on hydrophilic rough surfaces are shifted to more hydrophobic values, unless roughness or surface energy are such that capillary forces become significant, leading to complete wetting. The observed hydrophobicity is thus not consistent with the well-known Wenzel equation. We have shown that the pinning strength of a surface is independent of the surface chemistry, provided that neither capillary forces nor air enclosure are involved. In addition, pinning strength can be described by the axis intercept of the cosine-cosine plot of contact angles for rough versus flat surfaces with the same surface chemistries.

Poly(ethylene glycol) Adlayers Immobilized to Metal Oxide Substrates Through Catechol Derivatives: Influence of Assembly Conditions on Formation and Stability

We have investigated five different poly(ethylene glycol) (PEG, 5 kDa) catechol derivatives in terms of their spontaneous surface assembly from aqueous solution, adlayer stability, and resistance to nonspecific blood serum adsorption as a function of the type of catechol-based anchor, assembly conditions (temperature, pH), and type of substrate (SiO(2), TiO(2), Nb(2)O(5)). Variable-angle spectroscopic ellipsometry (VASE) was used for layer thickness evaluation, X-ray photoelectron spectroscopy (XPS) for layer composition, and ultraviolet-visible optical spectroscopy (UV-vis) for cloud point determination. Polymer surface coverage was influenced by the type of catechol anchor, type of the substrate, as well as pH and temperature (T) of the assembly solution. Furthermore, it was found to be highest for T close to the cloud point (T(CP)) and pH of the assembly solution close to pK(a1) (dissociation constant of the first catechol hydroxy group) of the polymer and to the isoelectric point (IEP) of the substrate. T(CP) turned out to depend on not only the ionic strength of the assembly solution, but also the type of catechol derivative and pH. PEG-coating dry thickness above 10 A correlated with low serum adsorption. We therefore conclude that optimum coating protocols for catechol-based polymer assembly at metal oxide interfaces have to take into account specific physicochemical properties of the polymer, anchor, and substrate.

Self-Assembly of Poly(ethylene glycol)-Poly(alkyl phosphonate) Terpolymers on Titanium Oxide Surfaces: Synthesis, Interface Characterization, Investigation of Nonfouling Properties, and Long-Term Stability

This contribution deals with the self-assembling of a terpolymer on titanium oxide (TiO(2)) surface. The polymer structure was obtained by polymerization of different methacrylates, i.e., alkyl-phosphonated, butyl and PEG methacrylate, in the presence of a chain transfer agent. The resulting PEG-poly(alkyl phosphonate) material, characterized mainly by SEC and NMR, self-organized at the interface of TiO(2). AR-XPS demonstrated the binding of phosphonate groups to TiO(2) substrate and the formation of a PEG-brush layer at the outermost part of the system. The stability of this terpolymer adlayer, after exposure to solutions of pH 2, 7.4, and 9 up to 3 weeks, was evaluated quantitatively by XPS and ellipsometry. We demonstrated an overall stability improvements of this coating against desorption in contact with aqueous solutions in comparison with reference self-assembly systems. Finally, the PEG-terpolymer adlayer proved to impart to TiO(2) substrate antifouling properties when exposed to full blood serum.

Protein-Resistant Surfaces through Mild Dopamine Surface Functionalization

The synthesis and evaluation of new dopamine-based catechol anchors coupled to poly(ethylene glycol) (PEG) for surface modification of TiO(2) are reported. Dopamine is modified by dimethylamine-methylene (7) or trimethylammonium-methylene (8) groups, and the preparation of mPEG-Glu didopamine polymer 11 is presented. All these PEG polymers allow stable adlayers on TiO(2) to be generated through mild dip-and-rinse procedures, as evaluated both by variable angle spectroscopic ellipsometry and X-ray photoelectron spectroscopy. The resulting surfaces substantially reduced protein adsorption upon exposure to full human serum.

Fabricating chemical gradients on oxide surfaces by means of fluorinated, catechol-based, self-assembled monolayers.

Catechols bind strongly to several metal oxides and can thus be used as a binding group for generating self-assembled monolayers. Furthermore, their derivatives can be used to produce well-defined, centimeter-scale surface-chemical gradients on technologically relevant surfaces, such as titanium dioxide (TiO(2)). A simple dip-and-rinse gradient-preparation technique was utilized to produce surface-hydrophobicity gradients from perfluoro-alkyl catechols and nitrodopamine (ND). Chemical composition, quality, and properties of the functionalized surfaces were determined by means of X-ray photoelectron spectroscopy (XPS), variable-angle spectroscopic ellipsometry (VASE), and static water contact angle (sCA) measurements. Contact angles were found to be in the range of 30°-95°, correlating well with the determined surface chemical composition and adlayer thickness.

Cassie-state wetting investigated by means of a hole-to-pillar density gradient.

The superhydrophobicity of rough surfaces owes its existence to heterogeneous wetting. To investigate this phenomenon, density gradients of randomly placed holes and pillars have been fabricated by means of photolithography. On such surfaces, drops can be observed in the Cassie state over the full range of f(1) (fraction of the drops footprint area in contact with the solid). The gradient was produced with four different surface chemistries: native PDMS (polydimethylsiloxane), perfluorosilanized PDMS, epoxy, and CH(3)-terminated thiols on gold. It was found that f(1) is the key parameter influencing the static water contact angle. Advancing and receding contact angles at any given position on the gradient are sensitive to the type of surface feature--hole or pillar--that is prevalent. In addition, roll-off angles have been measured and found to be influenced not only by the drop weight but also by suction events, edge pinning, and f(1).

Poly(ethylene glycol) and Hydroxy Functionalized Alkane Phosphate Mixed Self-Assembled Monolayers to Control Nonspecific Adsorption of Proteins on Titanium Oxide Surfaces

The spontaneous formation of alkane phosphate self-assembled monolayers (SAMs) on titanium oxide was chosen as a tool to tailor the surface physicochemical properties in terms of nonspecific adsorption of proteins. For this aim, poly(ethylene glycol)-modified (PEG) alkane phosphate was codeposited with OH-terminated alkane phosphates. X-ray photoelectron spectroscopy and ellipsometry of the resulting mixed SAMs indicate that the PEG density can be controlled by varying the mole fraction of PEG-terminated phosphates in the solutions used during the deposition process, leading to surfaces with different degrees of protein resistance.

New Single‐Source Precursors for the MOCVD of High‐κ Dielectric Zirconium Silicates to Replace SiO2 in Semiconducting Devices

Two new single-source zirconium silicate precursors Zr(acac) 2 (OSiMe 3 ) 2 A, and Zr(acac) 2 (OSi t BuMe 2 ) 2 B, have been synthesized. The stability and vapor pressure of the two compounds were investigated. They have been used to deposit films of Zr 1-x Si x O 2 by metal-organic (MO)CVD in the temperature range 400-700 °C. Zirconium silicate films with very low carbon contamination and silicon content, x, in the range 0.05-0.25 have been obtained. The two precursors differ, by a factor of two, in activation energy for the MOCVD of films (63 kJ mol -1 for A, and 145 kJ mol -1 for B), and differential scanning calorimetry (DSC) shows they have quite different decomposition temperatures. The film composition was determined by X-ray photoelectron spectroscopy (XPS) and the crystallinity of the layers was studied by X-ray diffraction (XRD). Preliminary electrical characterizations of the zirconium silicate films were conducted on MOS capacitors with Al as gate electrodes. The experiments exhibit the generation of negative charges in the layers during the measurements, shown by a large hysteresis in the CV curves and a shift of the IV curves from the first to the following measurements. Low leakage current densities in the lower voltage regime are observed.