Biological surface science

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”.     

Numerical Quadrature over the Surface of a Sphere

Large‐scale simulations in spherical geometries require associated quadrature formulas. Classical approaches based on tabulated weights are limited to specific quasi‐uniform distributions of relatively low numbers of nodes. By using a radial basis function‐generated finite differences (RBF‐FD)‐based approach, the proposed algorithm creates quadrature weights for N arbitrarily scattered nodes in only operations.     

Asymmetric nitroaldol reaction using nitromethane labeled with C

Nitro[¹¹C]methane produced from [¹¹C]O₂ reacted with several aldehydes in the presence of chiral metal catalyst prepared from LaLi₃{tris(binaphtoxide)}, n-BuLi, H₂O, and (R)-binaphtol. The molar ratios of La, Li, and binaphtol for effective catalysis in the ¹¹C-labeling were 1/4/4.5 and 1/4/6, respectively. The ¹¹C-nitroaldol products were obtained in 3-25% radiochemical yields with 39-51% ee within 20 min starting from the preparation of nitro[¹¹C]methane.     

Phospholipid membranes decorated by cholesterol-based oligonucleotides as soft hybrid nanostructures

DNA monomers and oligomers are currently showing great promise as building blocks for supramolecular arrays that can self-assemble in a fashion preprogrammed by the base pairing code. The design and build-up of hybrid DNA/amphiphilic self-assemblies can expand the range of possible architectures and enhance the selectivity toward a well-specified geometry. We report on the self-assembly properties in aqueous solution of a cholesteryl-tetraethylenglycol single stranded 18-mer oligonucleotide (ON 1TEG-Chol) and on its spontaneous insertion in fluid phospholipid membranes. Up to 500 units of these lipophilic ss-oligonucleotides can be incorporated in the outer leaflet of 350 A radius POPC vesicle. The insertion and hybridization with the complementary oligonucleotide are monitored through light scattering as an increase of hydrodynamic thickness, which is interpreted in terms of average distance between anchoring sites. The conformation of the ss-oligonucleotidic portion is strongly dependent on surface coverage, passing from a quasi-random coil to a more rigid configuration, as concentration increases. Interestingly, conformational details affect in a straightforward fashion the hybridization kinetics. Liposomes with single- and double-strand decorations remain stable within the experimental time window (about one week). The structure represents an example of successful and stable amphiphile/DNA supramolecular hybrid, where a DNA guest is held in a membrane by hydrophobic interactions. The lipophilic oligonucleotide under investigation is therefore a suitable building block that can effectively serve as a hydrophobic anchor in the fluid bilayer to assemble supramolecular constructs based on the DNA digital code.     

Retinoid chromophores as probes of membrane lipid order

There is a great need for development of independent methods to study the structure and function of membrane-associated proteins and peptides. Polarized light spectroscopy (linear dichroism, LD) using shear-aligned lipid vesicles as model membranes has emerged as a promising tool for the characterization of the binding geometry of membrane-bound biomolecules. Here we explore the potential of retinoic acid, retinol, and retinal to function as probes of the macroscopic alignment of shear-deformed 100 nm liposomes. The retinoids display negative LD, proving their preferred alignment perpendicular to the membrane surface. The magnitude of the LD indicates the order retinoic acid > retinol > retinal regarding the degree of orientation in all tested lipid vesicle types. It is concluded that mainly nonspecific electrostatic interactions govern the apparent orientation of the retinoids within the bilayer. We propose a simple model for how the effective orientation may be related to the polarity of the end groups of the retinoid probes, their insertion depths, and their angular distribution of configurations around the membrane normal. Further, we provide evidence that the retinoids can sense subtle structural differences due to variations in membrane composition and we explore the pH sensitivity of retinoic acid, which manifests in variations in absorption maximum wavelength in membranes of varying surface charge. Based on LD measurements on cholesterol-containing liposomes, the influence of membrane constituents on bending rigidity and vesicle deformation is considered in relation to the macroscopic alignment, as well as to lipid chain order on the microscopic scale.     

Carrier concentration and shallow electron states in Sb-doped hydrothermally grown ZnO

In order to obtain p-type ZnO, the incorporation of group-V elements on oxygen sites has received lots of attention. Recently, the implantation of Sb+ ions into ZnO has been shown to lead to reduced n-type conduction. However, a compensating effect due to implantation damage could not be ruled out. Therefore, single-crystal ZnO has been hydrothermally grown with additional Sb₂O₃, Sb₂O₅, and K(SbO)C₄H₄O₆ in the solution. Schottky barrier contacts have been deposited onto the () face. Capacitance–voltage measurements and thermal admittance spectroscopy have been used for electrical characterization, and secondary ion mass spectrometry was used to measure the Sb content in the samples. Clearly, all samples exhibited n-type conduction. A competition between the incorporation of oxygen and antimony is suggested.     

Dμ—A new concept in industrial low-energy electron dosimetry

Irradiation with low-energy electrons (100–300 keV) results in dose gradients across the thickness of the dosimeters that are typically used for dose measurement at these energies. This leads to different doses being measured with different thickness dosimeters irradiated at the same electron beam, resulting in difficulties in providing traceable dose measurements using reference dosimeters. In order to overcome these problems a new concept is introduced of correcting all measured doses to the average dose in the first micrometer—D_μ. We have applied this concept to dose measurements with dosimeters of different thickness at two electron accelerators operating over a range of energies. The uncertainties of the dose measurements were evaluated, and it was shown that the dose in terms of D_μ was the same at each energy for all dosimeters within the measurement uncertainty. Using the concept of D_μ it is therefore possible to calibrate and measure doses from low-energy electron irradiations with measurement traceability to national standards.     

Two-photon absorption of metal-organic DNA-probes

We report remarkable multiphoton absorption properties of DNA intercalating ruthenium complexes: (1) [Ru(phen)(2)dppz](2+); (2) [(11,11'-bidppz)(phen)(4)Ru(2)](4+); (3) [11,11'-bipb(phen)(4)Ru(2)](4+). Two-photon spectra in the range from 460 to 1100 nm were measured using the Z-scan technique. In particular, complex 2 was found to exhibit very strong two- and three-photon absorption properties, which could be an effect of symmetric charge transfer from the ends towards the middle of the conjugated dimeric orbital system. We propose that these molecules could provide a new generation of DNA binding nonlinear chromophores for wide applications in biology and material science. The combination of a large two-photon cross section and strong luminescence quantum yields for the molecules when intercalated makes the compounds uniquely bright and photo-stable probes for two-photon luminescence imaging and also promising as enhanced photosensitizers in two-photon sensitizing applications.