Two-photon activated two-photon fluorescence and binding of azidocoumarin in a gelatin matrix.

We study the creation of fluorescence patterns inside a gelatin gel by way of two-photon photoactivation of 7-azido-4-trifluoromethyl-1,2-benzopyrone (azidocomarin 151) contained in the gel matrix. As ultrafast light pulses are focused into the gel, onset of two-photon fluorescence, highly nonlinear in the applied optical power, is observed as azidocoumarin is converted into a fluorescent dye that binds to the gelatin. We fit the time dependence of the fluorescence to a model that incorporates the competition between coumarin photoactivation and photobleaching as well as the gradual degradation of the gel when it is exposed to the high intensity laser light. The model predicts that the initial rate of fluorescence onset should scale as the P (4), where P is laser power, while the signal at long exposure time should scale as P (3/2). The observed exponents are 4.18 and 1.34, respectively. The model allows us to estimate the cross section and quantum yield of two-photon induced photobleaching of azidocoumarin 151. The numerous technical uses of gelatin and the collagen from which it derives in areas ranging from photography to tissue engineering provide possible applications for the techniques described in this paper.

Amine-rich polyelectrolyte multilayers for patterned surface fixation of nanostructures.

We describe a lithographic method for directly patterning the adhesive properties of amine-rich layer-by-layer assembled polymer films, useful for positioning metal and other nanostructures. The adhesive properties of the films are sufficiently robust that the films can be patterned with standard as opposed to soft lithographic methods. We perform the patterning with a lithographically defined evaporated aluminum mask which protects selected regions of the substrate, passivating adhesion in the exposed regions with acetic anhydride. When the aluminum is removed with a HCl etch, the protected regions retain their adhesion, whereas particle adsorption is almost completely eliminated in the passivated areas, making it possible to guide adsorption to the protected areas. The high degree of adhesion comes about because of uncoordinated amine groups that pervade the film. Cycling the pH from high values to low and back causes the amines to be rearranged, rejuvenating the adhesive properties of the surface, which is the likely origin of the robustness of the adhesive properties to processing. pH adjustment also causes reversible swelling and deswelling of the film, so that the vertical position and dielectric environment of the nanostructure can be dynamically adjusted, which can be particularly beneficial for tuning the plasmonic resonances of metallic structures.

Restricted meniscus convective self-assembly.

Convective (or evaporation-induced) self-assembly is a standard technique for depositing uniform, poly-crystalline coatings of nanospheres across multiple square centimeters on the timescale of minutes. In this paper, we present a variation of this technique, where the drying meniscus is restricted by a straight-edge located approximately 100 microm above the substrate adjacent to the drying zone. Surprisingly, we find this technique to yield films at roughly twice the growth rate compared to the standard technique. We attribute this to differing rates of diffusion of vapor from the drying crystal in the two cases. We also investigate the crystal growth rate dependence on ambient relative humidity and find, contrary to some previous reports, that the growth rate depends strongly on the humidity. We introduce a model which indicates that while the length of the drying zone may increase with humidity, this alone cannot compensate for the simultaneous reduction in evaporation rate, so a lower humidity must always lead to a higher growth speed. Comparing the model to our experimental results, we find that the length of the drying zone is constant and mostly independent of parameters such as humidity and surface tension.