Kinetic switching between two modes of bisurea surfactant self-assembly.

The size and shape of a surfactant aggregate could be altered by using supersaturation like in crystal growth, rather than applying common laws that drive surfactant aggregate formation.

Insights into templated supramolecular polymerization: binding of naphthalene derivatives to ssDNA templates of different lengths.

We report on two diaminotriazine-equipped naphthalene derivatives that bind reversibly to a single-stranded DNA template or "tape-measure molecule" via hydrogen bonding, yielding monodisperse double-stranded DNA hybrids with one strand consisting of a supramolecular naphthalene backbone. These assemblies have been investigated extensively, both experimentally and theoretically. The structure and the templated self-assembly process of the complex have been characterized with UV-vis spectroscopy, circular dichroism spectroscopy, molecular dynamics simulations, cryo-transmission electron microscopy, liquid atomic force microscopy, electrospray ionization mass spectrometry, light scattering, and 1H NMR and infrared spectroscopy. We have found that the DNA hybrid complexes have a right-handed helical arrangement stabilized by pi-pi interactions and hydrogen bonds. The hydrophilic hydroxyl group at the end of the ethylene glycol of the guest molecule suppressed both the nontemplated self-assembly of the naphthalene guest molecules and the further aggregation of the entire DNA hybrid complex. Through the use of a theoretical mass-action model for the templated self-assembly, the host-guest and guest-guest interaction energies were estimated by fitting to the spectroscopic data. The differently estimated values of the interaction energies and thermodynamic parameters vary within experimental error, showing the self-consistency of the model. From the obtained correlation between the positions of the guest molecules bound on the template, we have obtained a qualitative theoretical picture of the way in which the guests are physically distributed on the templates. For short templates, the templates are filled one-by-one, even at moderate fractions of bound sites. For larger templates, the templates first have alternating sequences of filled and empty sections, after which, at large fractions of bound sites, virtually all of the binding sites for all template lengths are filled.

Electron tomography shows molecular anchoring within a layer-by-layer film.

The layer-by-layer self-assembly of thin films consisting of alternating layers of DNA and bis-urea nanoribbons prevents diffusion of the components within the film and allows the anchoring of biotinylated molecules through molecular recognition in a predetermined layer of the film. Electron tomography demonstrates with nanometer precision the location of gold-labeled streptavidin bound to the incorporated biotinylated molecules.

Molecular recognition controls the organization of mixed self-organized bis-urea-based mineralization templates for CaCO(3).

To investigate the role and importance of nondirectional electrostatic interactions in mineralization, we explored the use of Langmuir monolayers in which the charge density can be tuned using supramolecular interactions. It is demonstrated that, in mixed Langmuir monolayers of bis-ureido surfactants containing oligo(ethylene oxide) and ammonium head groups associated with matching or nonmatching spacers between the two urea groups, the organization is controlled by molecular recognition. These different organizations of the molecules lead to different nucleation behavior in the mineralization of calcium carbonate. The formation of modified calcite and vaterite crystals was induced selectively by different phases of mixed monolayers, and they were characterized by SEM, TEM, and SAED. To understand the influence of the mixed Langmuir monolayers on the crystallization process, we studied the mixtures by means of (pi-A) isotherms and Brewster angle microscopy observations. Infrared reflection-absorption spectroscopy experiments were also performed on Langmuir-Schaefer films. From these results, we conclude that the local organization of the two systems discussed here gives rise to differences in both charge density and flexibility that together determine not only polymorph selection and the nucleation face but also the morphology of the resulting crystals.

Stepwise noncovalent synthesis leading to dendrimer-based assemblies in water.

We provide detailed insight into complex supramolecular assembly processes by fully characterizing a multicomponent model system using dynamic light scattering, cryogenic transmission electron microscopy, atomic force microscopy, and various NMR techniques. First, a preassembly of a host molecule (the fifth-generation urea-adamantyl poly(propylene imine) dendrimer) and 32 guest molecules (a water- and chloroform-soluble ureidoacetic acid guest) was made in chloroform. The association constant in chloroform is concealed by guest self-association and is therefore higher than 10(3) M(-1). Via the neat state the single-host complex was transferred to water, where larger dendrimer-based assemblies were formed. The core of these assemblies, consisting of multiple host molecules (on average three), is kinetically trapped upon dissolution in water, and its size is constant irrespective of the concentration. The guest molecules forming the corona of the assemblies, however, stay dynamic since they are still in rapid exchange on the NMR time scale, as they were in chloroform. A stepwise noncovalent synthesis provides a means to obtain metastable dynamic supramolecular assemblies in water, structures that cannot be formed in one step.

In vitro and in vivo effects of deoxyribonucleic acid-based coatings funtionalized with vascular endothelial growth factor.

Vascularization is important in wound healing and essential for tissue ingrowth into porous tissue-engineering matrices. Furthermore, peri-implant tissue vascularization is known to be important for the functionality of subcutaneously implanted biosensors (e.g., glucose sensors). As a first exploration of the use of deoxyribonucleic acid (DNA)-based coatings for the optimization of biosensor functionality, this study focused on the effect of DNA-based coatings functionalized with vascular endothelial growth factor (VEGF) on in vitro endothelial cell behavior and vascularization of the peri-implant tissue in vivo. To that end, DNA-based coatings consisting of poly-D-lysine and DNA were functionalized with different amounts of VEGF (25 and 250 ng) and compared to non-coated controls and non-functionalized DNA-based coatings. The results demonstrated the superiority of VEGF-functionalized DNA-based coatings in increasing endothelial cell proliferation and migration in vitro over non-coated controls and non-functionalized DNA-based coatings. In vivo, a significant increase in vascularization of the peri-implant area was observed for VEGF-functionalized DNA-based coatings. Because no dosage-dependent effects were observed, future experiments should focus on optimizing VEGF concentration for this purpose. Additionally, the administration of VEGF in combination with other (pro-angiogenic) factors should be considered.

Fabrication, characterization, and biological assessment of multilayered DNA-coatings for biomaterial purposes.

This study describes the fabrication of two types of multilayered coatings onto titanium by electrostatic self-assembly (ESA), using deoxyribosenucleic acid (DNA) as the anionic polyelectrolyte and poly-d-lysine (PDL) or poly(allylamine hydrochloride) (PAH) as the cationic polyelectrolyte. Both coatings were characterized using UV-vis spectrophotometry, atomic force microscopy (AFM), X-ray photospectroscopy (XPS), contact angle measurements, Fourier transform infrared spectroscopy (FTIR), and for the amount of DNA immobilized. The mutagenicity of the constituents of the coatings was assessed. Titanium substrates with or without multilayered DNA-coatings were used in cell culture experiments to study cell proliferation, viability, and morphology. Results of UV-vis spectrophotometry, AFM, and contact angle measurements clearly indicated the progressive build-up of the multilayered coatings. Furthermore, AFM and XPS data showed a more uniform build-up and morphology of [PDL/DNA]-coatings compared to [PAH/DNA]-coatings. DNA-immobilization into both coatings was linear, and approximated 3microg/cm(2) into each double-layer. The surface morphology of both types of multilayered DNA-coatings showed elevations in the nanoscale range. No mutagenic effects of DNA, PDL, or PAH were detected, and cell viability and morphology were not affected by the presence of either type of multilayered DNA-coating. Still, the results of the proliferation assay revealed an increased proliferation of primary rat dermal fibroblasts on both types of multilayered DNA-coatings compared to non-coated controls. The biocompatibility and functionalization of the coatings produced here, will be assessed in subsequent cell culture and animal-implantation studies.

The bis-urea motif as a tool to functionalize self-assembled nanoribbons.

Here we present a surfactant molecule (1) containing an ammonium headgroup, in which a bis-ureido group is incorporated in its hydrocarbon chain. Due to strong hydrogen bonding interactions, 1 forms well-defined highly ordered ribbon-like aggregates in water. Moreover, we demonstrate that these ribbons can be functionalized via a modular approach through molecular recognition of other bis-urea containing molecules. The dye disperse orange and biotin were coupled to matching bis-ureido groups and incorporated into the ribbon structure. The anchoring of different functionalities in a modular approach proved to be possible using the molecular recognition capabilities of the bis-ureido moiety, thereby opening possibilities to a wide range of applications.