2D "soap"-assembly of nanoparticles via colloid-induced condensation of mixed Langmuir monolayers of fatty surfactants.

We describe a new type of colloidal 2D gels formed in mixed Langmuir monolayers of stearic acid and octadecylamine on a surface of gold hydrosol. The adsorption of gold nanoparticles on the mixed monolayer led to an increase of interactions between oppositely charged surfactants giving a "soap" of mixed fatty salt. The observed effect is equivalent to a virtual "cooling" of floating monolayer, which undergoes rapid condensation on a surface of aqueous colloid. The consequent shrinking and rearrangement of the monolayer resulted in aggregation of nanoparticles into colloidal 2D "soap"-gels, which represented arrested colloidal phases within nonadsorbing organic medium. When sequentially deposited onto solids by Langmuir-Blodgett technique, the 2D "soap"-gels separated into organic and colloidal phases and gave dendrite-like bilateral organic crystallites coated with gold nanoparticles. The reported colloidal "soap"-assembly can offer a new opportunity to design 2D colloidal systems of widely variable chemistry and structures.

Hydrogen-bond-guided self-assembly of nucleotides on a receptor-array surface.

The hydrogen-bond-guided self-assembly of 5'-ribonucleotides bearing adenine(A), cytosine (C), uracil (U), or guanine (G) bases from aqueous solution on a lipid-like surface decorated with synthetic bis(Zn(II)-cyclen) (cyclen=1,4,7,10-tetraazacyclodododecane) metal-complex receptor sites is described. The process was studied by using surface plasmon resonance spectroscopy. The data show that the mechanism of nucleotide binding to the 2D template is influenced by the chemistry of the bases and the pH value of the solution. In a neutral solution of pH 7.5, the process is cooperative and selective with respect to Watson-Crick pairs (A-U and C-G), which form stable double planes in accordance with the Chargaff rule. In a more acidic solution at pH 6.0, the interactions between complementary partners become non-cooperative and the surface also stabilizes mismatched and wobble pairs due to the pH-induced changes in the receptor coordination state. The results suggest that hydrogen bonding plays a key role in the self-assembly of complementary nucleotides at the lipid-like interface, and the cooperative character of the process stems from the ideal matching of the orientation and chemistry of all the interacting components with respect to each other in neutral solution.

Lateral 2D-3D phase segregation in fatty acid/fatty amine monolayers induced by langmuir-blodgett deposition.

We describe the formation of lateral 2D-3D patterns in mixed multilayer LB films of stearic acid (SA) and octadecylamine (ODA) deposited from aqueous subphases at a basic pH. The 3D particles of SA constituting the micrometer-scale linear assemblies in the LB film are assumed to segregate at the three-phase contact line in the course of film deposition. This 2D-3D phase separation of the two-component system presumably originates from the substrate-induced lowering of the collapse point of SA that leads to spontaneous 3D condensation of an acid on a solid support. The morphology of SA/ODA LB patterns is sensitively influenced by the deposition speed and surface pressure, while the chemistry of the solid support does not affect the resulting structures. The possible mechanism that controls the specific orthogonal arrangement of the 3D phase of SA in the LB film through wettability oscillations is suggested.

Two-dimensional arrays of amphiphilic Zn2+-cyclens for guided molecular recognition at interfaces.

The sterically guided molecular recognition of nucleobases, phosphates, adenosine, and uridine nucleotides on Langmuir monolayers and Langmuir-Blodgett monolayers of amphiphilic mono- or bis(Zn2+-cyclen)s assembled on thiolated surfaces was investigated. The stepwise selective binding of metal ions, uracil, or phosphate by dicetyl cyclen monolayers with variously tuned structures at the air/water interface was corroborated by the measurements of the corresponding LB films deposited onto quartz crystals. Two types of recognition surfaces were fabricated from Zn2+-dicetyl cyclen. The surface covered with a complex preformed in the Langmuir monolayer was capable both of imide and of phosphate binding. The similar complex formed directly in an LB film on thiolated gold was inactive with respect to imide. The surface plasmon resonance measurements evidenced the stepwise assembly of complementary nucleotides on SAM/LB templates through consecutive phosphate-Zn2+-cyclen coordination. Base pairing between nucleotides resulted in a formation of A-U bilayers comprising two complementary monolayers. Finally, we report on SAM/LB patterns designed for divalent molecular recognition of uridine phosphate by amphiphilic bis(Zn2+-cyclen).