The strongly polarized light scattering of gold nanorods at their longitudinal plasmon frequency allows for the tracking of single gold nanorod lateral positions and orientations via optical dark-field microscopy. We monitor both lateral and rotational diffusion of polymer-coated gold nanorods attached to artificial biomembranes on solid supports. The attachment is mediated by the biotin-streptavidin receptor-ligand system, but weak interaction is also observed in the absence of streptavidin. In the latter case, we observe a two-dimensional lateral diffusion of the nanorods with a diffusion coefficient of 0.5 mu m(2) s(-1). This lateral motion is strongly reduced with the addition of streptavidin. However, the particles are still able to rotate, and we study their rotational motion using polarization contrast microscopy. The rotational diffusion time in the range of 100 ms depends on the biotin concentration in the membrane, hence the number of anchor points, and oil the temperature. Cooling the membrane beyond its gel-fluid transition point leads to a reduction of the rotational motion. The experimental results can be understood in terms of dragging forces introduced by. the surface viscosity of the membrane. A quantitative analysis shows that entire patches of the membrane move with the particles.

The specific interaction of annexin A1 with phospholipid bilayers is scrutinized by means of scanning force and fluorescence microscopy, quartz crystal microbalance, ellipsometry, and modeled by dynamic Monte Carlo simulations. It was found that POPC/POPS bilayers exhibit phase separation in POPC- and POPS-enriched domains as a function of Ca2+ concentration. Annexin A1 interacts with POPC/POPS bilayers by forming irreversibly bound protein domains with monolayer thickness on POPS-enriched nanodomains, while the attachment of proteins to the POPC-enriched regions is fully reversible. A thorough kinetic analysis of the process reveals that both, the binding constant of annexin A1 at the POPC-rich areas as well as the irreversible adsorption rate to the POPS-rich domains increases with calcium ion concentration. Based on the thermodynamic and kinetic data, a possible mechanism of the annexin A1 membrane interaction can be proposed.

Lipid bilayers consisting of lipids with terminally perfluoroalkylated chains have remarkable properties. They exhibit increased stability and phase-separated nanoscale patterns in mixtures with nonfluorinated lipids. In order to understand the bilayer properties that are responsible for this behavior, we have analyzed the structure of solid-supported bilayers composed of 1,2-dipalmitoyl- sn-glycero-3-phosphocholine (DPPC) and of a DPPC analogue with 6 terminal perfluorinated methylene units (F6-DPPC). Polarized attenuated total reflection Fourier-transform infrared spectroscopy indicates that for F6-DPPC, the tilt of the lipid acyl chains to the bilayer normal is increased to 39 degrees as compared to 21 degrees for native DPPC, for both lipids in the gel phase. This substantial increase of the tilt angle is responsible for a decrease of the bilayer thickness from 5.4 nm for DPPC to 4.5 nm for F6-DPPC, as revealed by temperature-controlled imaging ellipsometry on microstructured lipid bilayers and solution atomic force microscopy. During the main phase transition from the gel to the fluid phase, both the relative bilayer thickness change and the relative area change are substantially smaller for F6-DPPC than for DPPC. In light of these structural and thermotropic data, we propose a model in which the higher acyl-chain tilt angle in F6-DPPC is the result of a conformational rearrangement to minimize unfavorable fluorocarbon-hydrocarbon interactions in the center of the bilayer due to chain staggering.

The phase transition of individually addressable microstructured lipid bilayers was investigated by means of noncontact imaging ellipsometry. Two-dimensional membrane compartments were created on silicon substrates by micromolding in capillaries and the phase transition of supported dimyristoylphosphadiylcholine (DMPC) and dipentadecoylphosphatidylcholine (DiC(15)PC) membranes was determined measuring area expansion and thickness of the bilayer as a function of temperature, ethanol concentration, and cholesterol content. Apart from measuring the thermotropic behavior of DMPC on glass slides and silicon wafers, the authors were able to visualize the reversible induction of an interdigitated phase by partitioning of ethanol into the microstructured lipid bilayers. Interdigitation induced by addition of ethanol was measured as a function of cholesterol content and shifts of the main phase transition temperature T(M) of microstructured DiC(15)PC were quantified as a function of ethanol concentration. They observed that cholesterol abolishes interdigitation at higher concentrations and found a biphasic behavior of T(M) as a function of ethanol concentration in good accordance to what is known from vesicles in solution.

Particles on the tube: Here, novel surface functionalization of WS2 nanotubes with polymeric ligands, by complexation with a combination of Ni2+ through a scorpionate-type nitrilotriacetic acid, and immobilization of TiO2 nanoparticles onto the surface of nanotubes is demonstrated (see schematic representation). The synthesis of the functional polymeric ligands was achieved through a reactive polymer precursor route.

The phase transition of individually addressable microstructured lipid bilayers was investigated by means of imaging ellipsometry. Microstructured bilayers were created on silicon substrates by micromolding in capillaries, and the thermotropic behavior of various saturated diacyl phosphatidylcholine (1,2-dipalmitoyl-sn-glycero-3-phosphocholine, 1,2-dipentadecoyl-sn-glycero-3-phosphocholine, and 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC)) bilayers as well as DMPC/cholesterol membranes was determined by measuring the area expansion and thickness of the bilayer as a function of temperature. We found an increase in the main phase transition temperature T(M) of 2-6 degrees C and a substantially reduced cooperativity compared to multilamellar vesicles. Measurements of lateral diffusion constants D employing fluorescence recovery after photobleaching revealed, however, only a marginal decrease in D compared to those found for vesicles and multibilayers. The known dependencies of T(M) both on the chain length of diacyl PC membranes and on the cholesterol content were reproduced on a solid support. Microstructured bilayers offer the unique advantage of integrating an internal standard of known thermotropic properties, which turned out to be important for reducing the measurement error and for ruling out the slightly changing impact of the surface on the phase transition behavior due to the surface pretreatment.

Functionalized, monocrystalline rutile TiO2 nanorods were prepared from TiCl4 in aqueous solution under acidic conditions in the presence of dopamine, followed by aging and hydrothermal treatment at 150 degrees C. The surface-bound organic ligand controls the morphology as well as the crystallinity and the phase selection of TiO2. The presence of monocrystalline rutile TiO2 was confirmed by X-ray powder diffraction and HRTEM investigations. The as-prepared nanorods are soluble in water at pH <3. The surface functionalization was analyzed by IR and 1H NMR, confirming the presence of dopamine on the surface. The surface amine groups can be tailored further with functional molecules such as dyes. Confocal laser scanning microscopy (CLSM) was used to characterize the binding of the fluorescent dye 4-chloro-7-nitrobenzofurazan (NBD) to the functionalized surface of the TiO2 nanorods.

The kinetics of annexin A I binding to solid-supported lipid bilayers consisting of 7-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC)/1-palmitoyl-2-oleoyl-sn-glycero-3-phosphoserine (POPS; 4:7) has been investigated as a function of the calcium ion concentration in the bulk phase. Quartz crystal microbalance measurements in conjunction with scanning force microscopy, fluorescence microscopy, and computer simulations indicate that at a given Ca2+ concentration annexin A1 adsorbs irreversibly on membrane domains enriched in POPS. By contrast, onnexinAl adsorbs reversibly on the POPC-enriched phase, which is composed of single POPS molecules embedded within a POPC matrix. The overall area occupied by the POPS-enriched phase is controlled by the CaCl2 concentration. Monte Carlo simulations suggest that the area of the POPS-enriched phase increases by a factor of 7 when the Ca2+ concentration is changed from 0.01 to I mM.

Drei in einem: TiO2-Nanopartikel wurden mit reaktiven polymeren Liganden funktionalisiert, die drei Arten von Gruppen enthalten: chelatisierende Dopamin-Ankergruppen, eine Bindungsstelle für funktionale Moleküle wie Fluoreszenzfarbstoffe (siehe Bild) sowie Gruppen, die es ermöglichen, die Löslichkeit der anorganischen Nanokristalle in unterschiedlichen Lösungsmitteln einzustellen. Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2001/2006/z502517_s.pdf or from the author. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.

Silicatein immobilised on self-assembled polymer layers using a histidine-tag chelating anchor group retains its hydrolytical activity for the formation of biosilica, and catalyses the formation of layered arrangements of biotitania and biozirconia.

Adhesion and spreading of negatively charged unilamellar vesicles composed of POPG/POPC and DPPG/DPPC on positively charged self-assembly monolayers of 11-amino-1-undecanethiol were monitored by means of thickness shear mode (TSM) resonators with a fundamental frequency of 5 MHz. Changes of frequency and motional resistance upon vesicle adsorption were recorded as a function of surface charge density and lyotropic phase state of the lipids. From the readout of the TSM resonator, changes of the shape of the vesicles as well as the formation of supported lipid bilayers can be inferred in a quantitative manner. Increasing surface charge densities on the vesicles, which are tunable by the POPG content, led to decreasing frequency and resistance changes. At very high PG content, a lower limit of 3-12 Hz was found, indicative of the formation of planar bilayers due to vesicle rupture induced by the strong electrostatic interaction forces. Vesicles composed of DPPG/DPPC were less susceptible to deformation and rupture, a fact that can be attributed to the higher bending rigidity of DPPG/DPPC liposomes. More than 70 mol% of DPPG were needed to induce adhesion-controlled rupture of surface-attached vesicles, while only 30-50% of POPG were sufficient to form planar lipid bilayers on the quartz.