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DNA monolayers are widely used in fundamental and applied genomics and are versatile experimental models for elucidating the behavior of charged polymers at interfaces. The physical behavior of these systems is to a large extent governed by their internal ionic microenvironment, which is investigated here for layers of end-tethered, single-stranded DNA oligonucleotides (DNA brushes). Retention of counterions by the DNA brush manifests as lowered susceptibility of the interfacial capacitance to external salt conditions. A physical model based on concepts adapted from polymer science was used to further elucidate the connection between monolayer organization and its charging behavior. The data indicate a reorganization of the monolayer with changes in ionic strength and strand coverage that is consistent with that expected for a polyelectrolyte brush. A method for electrochemical quantification of strand coverage, based on shift of reduction potential for redox counterions associated with the DNA monolayer, is also described. These results provide guidance for development of label-free electrochemical diagnostics employing DNA monolayers and formulate a description of monolayer behavior within a polymer science framework.

Photoelectron spectroscopy was used to explore changes in Fermi level alignment, within the pi-pi* gap, arising from modifications to the coupling chemistry of conjugated phenylene ethynylene oligomers to the Au surface. Self-assembled monolayers were formed employing either thiol (4,4'-ethynylphenyl-1-benzenethiol or OPE-T) or isocyanide (4,4'-ethynylphenyl-1-benzeneisocyanide or OPE-NC) coupling. The electronic density of states in the valence region of the two systems are nearly identical with the exception of a shift to higher binding energy by about 0.5 eV for OPE-NC. Corresponding shifts appear in C(1s) spectra and in the threshold near E(F). The lack of change in the optical absorption suggests that a rigid shift of the Fermi level within the pi-pi* gap is the major effect of modifying the coupling chemistry. Qualitative consideration of bonding in each case is used to suggest the influence of chemisorption-induced charge transfer as a potential explanation. Connections to other theoretical and experimental work on the effects of varying coupling chemistries are also discussed.

Modifying the surfaces of magnetic nanoparticles (MNPs) by the covalent attachment of biomolecules will enable their implementation as contrast agents for magnetic resonance imaging or as media for magnetically assisted bioseparations. In this paper we report both the surface coverage and the activity of IgG antibodies on MNPs. The antibodies were immobilized on gamma-Fe2O3 nanoparticles by conventional methods using aminopropyltriethoxy silane and subsequent activation by glutaraldehyde. Novel fluorescence methods were used to provide a quantitative evaluation of this well-known approach. Our results show that surface coverage can be stoichiometrically adjusted with saturated surface coverage occurring at approximately 36% of the theoretical limit. The saturated surface coverage corresponds to 34 antibody molecules bound to an average-sized MNP (32 nm diameter). We also show that the immobilized antibodies retain approximately 50% of their binding capacity at surface-saturated levels.

The molecular architecture of acridine-9-carboxylic acid (ACA) grown on Ag (111) by physical vapor deposition was characterized by using UHV-STM and XPS. At lower coverage, ACA molecules exist in a 2-d gas phase on the surface at room temperature. With increased coverage (0.4 ML), ACA molecules self-organize into distinctive adlayer structures that are correlated with underlying substrate morphology. On step-free Ag (111) regions, ACA molecules form large islands in coexistence with the 2-d ACA gas. These islands are commensurate with the Ag (111) substrate, indexed as (4 0, 2 4) in matrix notation, and can exceed 100 nm in size. There are two nonequivalent ACA molecules in each unit cell. XPS core level measurements reveal a hydrogen-bonding interaction between ACA molecules, with the ring nitrogen acting as the H-bond acceptor and the carboxyl proton acting as the H-bond donor. A structural model for this phase consists of chains of ACA molecules linked by head-to-tail hydrogen bonds along the substrate [10] direction. Alternating ACA tilting angles account for the two nonequivalent ACA molecules and the observed high packing density. Completely different molecular arrangements are observed on Ag (111) surface regions roughened by a higher density of crystallographic steps (terrace widthsor = 6 nm). Pairs of ACA molecules arrange in a zigzag pattern in a (12 2, 6 5) overlayer structure with a diluted packing density. The structural model for this lower density phase consists of carboxyl-carboxyl linked ACA dimers in a flat-lying molecular orientation.