A series of compounds with systematically varied molecular structures which exhibit very large effective two-photon cross sections has been synthesized and characterized in solution using a nonlinear transmission technique. The general structure of these compounds can be categorized into two basic structural families: acceptor/donor/donor/acceptor and donor/ bridge/acceptor. This study attempts to determine certain molecular structure/effective twophoton absorption relationships by careful characterization and as a function of systematically varied changes in the organic structure of the dye molecules. Such information can be useful in the design of more efficient two-photon dyes for imaging and power-limiting applications. The results of the study indicate that with the incorporation of certain combinations of structural elements, dyes can be synthesized which have greatly increased effective cross sections as high as 152.5 × 10 -48 cm 4 s/photon molecule in benzene solution at 800 nm using 8 ns pulses. This value is orders of magnitude higher than commercially available organic dyes measured at the same wavelength. Although the process is thought to involve a combination of two-photon absorption and excited state absorption phenomena, the information gathered from these new families of dyes has provided an important first step in producing improved materials for use in many different two-photon technology application.

Many biological organisms contain specialized structures composed of inorganic materials. Cellular processes in vivo facilitate the organized assembly of mineral building blocks into complex structures. The structural hierarchy and complexity across a range of length scales are providing new ideas and concepts for materials chemistry. Proteins that direct biomineralization can be used to control the production of nanostructured materials and facilitate the fabrication of new structures. Here, we demonstrate that some of the silica-binding peptides isolated from a combinatorial phage peptide display library can be used in precipitating silica from a solution of silicic acid. The results described in this report demonstrate that peptides displayed by phages act as templates in inorganic material synthesis and provide a means of understanding how some of the biological systems may be carrying out materials chemistry in vivo.

Biological organisms are able to direct the formation of patterned and hierarchical biomineral structures. Extractable organic materials have been found entrapped in diatom, sponge and plant biosilica, some of which have been isolated by selective chemical dissolution methods and their composition and structure studied. Information gained from the bioextracts has inspired materials chemists to design biomimetic analogues and develop bioinspired synthetic schemes for silica formation. The results obtained from bioinspired silicification investigations are hypothesised to arise from specific modes of action of the organic additives, which are described in this review. Specifically, additives in bioinspired silicification act either as catalysts, aggregation promoting agents or structure-directing agents or more typically, exhibit a combination of these behaviours.

Diatoms are of interest to the materials research community because of their ability to create highly complex and intricate silica structures under physiological conditions: what these single-cell organisms accomplish so elegantly in nature requires extreme laboratory conditions to duplicate-this is true for even the simplest of structures. Following the identification of polycationic peptides from the diatom Cylindrotheca fusiformis, simple silica nanospheres can now be synthesized in vitro from silanes at nearly neutral pH and at ambient temperatures and pressures. Here we describe a method for creating a hybrid organic/inorganic ordered nanostructure of silica spheres through the incorporation of a polycationic peptide (derived from the C. fusiformis silaffin-1 protein) into a polymer hologram created by two-photon-induced photopolymerization. When these peptide nanopatterned holographic structures are exposed to a silicic acid, an ordered array of silica nanospheres is deposited onto the clear polymer substrate. These structures exhibit a nearly fifty-fold increase in diffraction efficiency over a comparable polymer hologram without silica. This approach, combining the ease of processability of an organic polymer with the improved mechanical and optical properties of an inorganic material, could be of practical use for the fabrication of photonic devices.

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