Bengt Kasemo

Viscoelastic Acoustic Response of Layered Polymer Films at Fluid-Solid Interfaces: Continuum Mechanics Approach

We have derived the general solution of a wave equation describing the dynamics of two-layer viscoelastic polymer materials of arbitrary thickness deposited on solid (quartz) surfaces in a fluid environment. Within the Voight model of viscoelastic element, we calculate the acoustic response of the system to an applied shear stress, i.e. we find the shift of the quartz generator resonance frequency and of the dissipation factor, and show that it strongly depends on the viscous loading of the adsorbed layers and on the shear storage and loss moduli of the overlayers. These results can readily be applied to quartz crystal acoustical measurements of the viscoelasticity of polymers which conserve their shape under the shear deformations and do not flow, and layered structures such as protein films adsorbed from solution onto the surface of self-assembled monolayers.

Quartz crystal microbalance setup for frequency and Q‐factor measurements in gaseous and liquid environments

An experimental setup has been constructed for simultaneous measurements of the frequency, the absolute Q factor, and the amplitude of oscillation of a quartz crystal microbalance (QCM). The technical solution allows operation in vacuum, air, or liquid. The crystal is driven at its resonant frequency by an oscillator that can be intermittently disconnected causing the crystal oscillation amplitude to decay exponentially. From the recorded decay curve the absolute Q factor (calculated from the decay time constant), the frequency of the freely oscillating crystal, and the amplitude of oscillation are obtained. All measurements are fully automated. One electrode of the QCM in our setup was connected to true ground which makes possible simultaneous electrochemistry. The performance is illustrated by experiments in fluids of varying viscosity (gas and liquid) and by proteinadsorptionin situ. We found, in addition to the above results, that the amplitude of oscillation is not always directly proportional to the Q factor, as the commonly used theory states. This puts limitations on the customary use of the amplitude of oscillation as a measure of the Q factor.

Biological surface science

Abstract Biological surface science (BioSS), as defined here is the broad interdisciplinary area where properties and processes at interfaces between synthetic materials and biological environments are investigated and biofunctional surfaces are fabricated. Six examples are used to introduce and discuss the subject: Medical implants in the human body, biosensors and biochips for diagnostics, tissue engineering, bioelectronics, artificial photosynthesis, and biomimetic materials. They are areas of varying maturity, together constituting a strong driving force for the current rapid development of BioSS. The second driving force is the purely scientific challenges and opportunities to explore the mutual interaction between biological components and surfaces. Model systems range from the unique water structures at solid surfaces and water shells around proteins and biomembranes, via amino and nucleic acids, proteins, DNA, phospholipid membranes, to cells and living tissue at surfaces. At one end of the spectrum the scientific challenge is to map out the structures, bonding, dynamics and kinetics of biomolecules at surfaces in a similar way as has been done for simple molecules during the past three decades in surface science. At the other end of the complexity spectrum one addresses how biofunctional surfaces participate in and can be designed to constructively participate in the total communication system of cells and tissue. Biofunctional surfaces call for advanced design and preparation in order to match the sophisticated (bio) recognition ability of biological systems. Specifically this requires combined topographic, chemical and visco-elastic patterns on surfaces to match proteins at the nm scale and cells at the micrometer scale. Essentially all methods of surface science are useful. High-resolution (e.g. scanning probe) microscopies, spatially resolved and high sensitivity, non-invasive optical spectroscopies, self-organizing monolayers, and nano- and microfabrication are important for BioSS. However, there is also a need to adopt or develop new methods for studies of biointerfaces in the native, liquid state. For the future it is likely that BioSS will have an even broader definition than above and include native interfaces, and that combinations of molecular (cell) biology and BioSS will contribute to the understanding of the “living state”.

Surface Specific Kinetics of Lipid Vesicle Adsorption Measured with a Quartz Crystal Microbalance

We have measured the kinetics of adsorption of small (12.5-nm radius) unilamellar vesicles onto SiO2, oxidized gold, and a self-assembled monolayer of methyl-terminated thiols, using a quartz crystal microbalance (QCM). Simultaneous measurements of the shift in resonant frequency and the change in energy dissipation as a function of time provide a simple way of characterizing the adsorption process. The measured parameters correspond, respectively, to adsorbed mass and to the mechanical properties of the adsorbed layer as it is formed. The adsorption kinetics are surface specific; different surfaces cause monolayer, bilayer, and intact vesicle adsorption. The formation of a lipid bilayer on SiO2 is a two-phase process in which adsorption of a layer of intact vesicles precedes the formation of the bilayer. This is, to our knowledge, the first direct evidence of intact vesicles as a precursor to bilayer formation on a planar substrate. On an oxidized gold surface, the vesicles adsorb intact. The intact adsorption of such small vesicles has not previously been demonstrated. Based on these results, we discuss the capacity of QCM measurements to provide information about the kinetics of formation and the properties of adsorbed layers.

Simultaneous frequency and dissipation factor QCM measurements of biomolecular adsorption and cell adhesion

We have measured the energy dissipation of the quartz crystal microbalance (QCM), operating in the liquid phase, when mono- or multi-layers of biomolecules and biofilms form on the QCM electrode (with a time resolution of ca. 1 s). Examples are taken from protein adsorption, lipid vesicle adsorption and cell adhesion studies. Our results show that even very thin (a few nm) biofilms dissipate a significant amount of energy owing to the QCM oscillation. Various mechanisms for this energy dissipation are discussed. Three main contributions to the measured increase in energy dissipation are considered. (i) A viscoelastic porous structure (the biofilm) that is strained during oscillation, (ii) trapped liquid that moves between or in and out of the pores due to the deformation of the film and (iii) the load from the bulk liquid which increases the strain of the film. These mechanisms are, in reality, not entirely separable, rather, they constitute an effective viscoelastic load. The biofilms can therefore not be considered rigidly coupled to the QCM oscillation. It is further shown theoretically that viscoelastic layers with thicknesses comparable to the biofilms studied in this work can induce energy dissipation of the same magnitude as the measured ones.

The interface zone of inorganic implantsIn vivo: Titanium implants in bone

The interface zone between titanium implants and bone is considered at the macroscopic, microscopic, and molecular levels. A high rate of successful dental implants of pure titanium is associated with a very close apposition of the bone to the titanium surface, called osseointegration. At the macroscopic level, osseointegration allows efficient stress transfer from the implant to the bone without abrasion or progressive movement that can take place if a fibrous layer intervenes. At the microscopic level, surface roughness and porosity provide interlocking of the implant and bone tissue which grows into direct contact with titanium. Sections studied in the electron microscope show that calcified tissue can be identified within 50 Å of the implant surface. The interface zone includes a tightly adherent titanium oxide layer on the surface of the implant which may be similar to a ceramic material in relation to tissue response. The five year success rate of 90% in 2895 implants in clinical trials since 1965 is associated with the favorable behavior of bone tissue at the interface zone with pure titanium.

Interparticle coupling effects in nanofabricated substrates for surface-enhanced Raman scattering

Surface-enhanced Raman scattering (SERS) substrates, consisting of arrays of electromagnetically coupled Ag nanoparticles on Si, were manufactured by electron-beam lithography. Substrate Raman efficiency, evaluated from the relative SERS intensities of the adsorbates rhodamine 6G and thiophenol, was found to increase rapidly with decreasing interparticle separation, signaling the importance of strong interparticle coupling effects in SERS. The observed SERS efficiency variation can be qualitatively explained in terms of electrostatic models of coupled metal structures.

Bone response to surface-modified titanium implants: studies on the early tissue response to machined and electropolished implants with different oxide thicknesses

The bone formation around titanium implants with varied surface properties is investigated. Machined and electropolished samples with and without thick, anodically formed surface oxides were prepared, surface characterized and inserted in the cortical bone of rabbits (1, 3 and 6 weeks). Scanning electron microscopy, scanning Auger electron spectroscopy and atomic force microscopy revealed marked differences in oxide thickness, surface topography and roughness, but no significant differences in surface chemical composition, between the different groups of implants. Light microscopic morphology and morphometry showed that all implants were in contact with bone and had a large proportion of bone within the threads at 6 weeks. The smooth, electropolished implants, irrespective of anodic oxidation, were surrounded by less bone than the machined implants after 1 week. After 6 weeks the bone volume as well as the bone-implant contact were lower for the merely electropolished implants than for the other three groups. Our study shows that a high degree of bone contact and bone formation are achieved with titanium implants which are modified with respect to oxide thickness and surface topography. However, the result with the smooth (electropolished) implants indicates that a reduction of surface roughness, in the initial phase, decreases the rate of bone formation in rabbit cortical bone.

Localized Surface Plasmon Resonances in Aluminum Nanodisks

The plasmonic properties of arrays of supported Al nanodisks, fabricated by hole-mask colloidal lithography (HCL), are analyzed for the disk diameter range 61-492 nm at a constant disk height of 20 nm. Strong and well-defined (UV-vis-NIR) localized surface plasmon resonances are found and experimentally characterized with respect to spectral peak positions, peak widths, total cross sections, and radiative and nonradiative decay channels. Theoretically, the plasmon excitations are described by electrostatic spheroid theory. Very good qualitative and quantitative agreement between model and experiment is found for all these observables by assuming a nanoparticle embedded in a few nanometer thick homogeneous (native) aluminum oxide shell. Other addressed aspects are: (i) the role of the strong interband transition in Al metal, located at 1.5 eV, for the plasmonic excitations of Al nanoparticles, (ii) the role of the native oxide layer, and (iii) the possibility of using the plasmon excitation as an ultrasensitive, remote, real-time probe for studies of oxidation/corrosion kinetics in metal nanoparticle systems.

Nanoscale features influence epithelial cell morphology and cytokine production

Available, easy and fast fabrication methods of nanostructured surfaces, and the knowledge that cells in vivo interacts with nanometer-sized structures/objects, led us to study the impact of nanotopography on cell morphology and cytokine production. Uroepithelial cells were seeded on three different substrate types: two with defined nanometer topographies and a flat control, all three having identical surface chemistry. The nanostructured substrates contained hemispherical pillars or step edges, the latter in the form of parallel grooves and ridges. Qualitative and quantitative analysis of cell morphology and cytokine production were studied. Both quantities were significantly different between cells cultured on hemispherically structured surfaces compared to flat control surfaces. Cells cultured on hemispherically structured surfaces showed a decrease in IL-6 and IL-8 production and were less spread, less round and more stellate (larger dispersion). Only cell morphology differed between cells cultured on grooved surfaces and flat control surfaces. These findings suggest that epithelial cell morphology and cytokine production are dependent on the underlying nanotopography.