Understanding amine catalyzed silica polymerization : diatoms as bioarchitects
Current state-of-the-art biomimetic methodologies employed worldwide for the realization of self-assembled nanomaterials are adequate for certain unique applications, but a major breakthrough is needed if these nanomaterials are to obtain their true promise and potential. These routes typically utilize a 'top-down' approach in terms of controlling the nucleation, growth, and deposition of structured nanomaterials. Most of these techniques are inherently limited to primarily 2D and simple 3D structures, and are therefore limited in their ultimate functionality and field of use. Zeolites, one of the best-known and understood synthetic silica structures, typically possess highly ordered silica domains over very small length scales. The development of truly organized and hierarchical zeolites over several length scales remains an intense area of research world wide. Zeolites typically require high-temperature and complex synthesis routes that negatively impact certain economic parameters and, therefore, the ultimate utility of these materials. Nonetheless, zeolite usage is in the tons per year worldwide and is quickly becoming ubiquitous in its applications. In addition to these more mature aspects of current practices in materials science, one of the most promising fields of nanotechnology lies in the advent and control of biologically self-assembled materials, especially those involved with silica and other ceramics such as hydroxyapatite. Nature has derived, through billions of years of evolutionary steps, numerous methods by which fault-tolerant and mechanically robust structures can be created with exquisite control and precision at relatively low temperature ranges and pressures. Diatoms are one of the best known examples that exhibit this degree of structure and control known that is involved with the biomineralization of silica. Diatoms are eukaryotic algae that are ubiquitous in marine and freshwater environments. They are a dominant form of phytoplankton critical to global carbon fixation. The silicified cell wall of the diatom is called the frustule, and the intricate silica structure characteristic of a given species is known as the valve. There are two general classes of diatoms, based on their overall morphologies, the pennate and centric. Diatoms achieve their silicified structures in exact fashion through genetically inspired design rules coupled with precisely directed biochemistry occurring at temperatures ranging from a few degrees Celsius (polar species) to temperatures just over room temperature (tropical species). Different species of diatoms produce markedly different structures. To start with, there are two basic types of frustule macromorphologies: pennate diatoms display bilateral symmetry and centric diatoms show radial symmetry. There are thousands of permutations of these two basic forms and the micromorphology of the valve can be quite complex with all types of pore arrangements and morphologies (Figure 1.1). The detailed morphology of the cell wall of a given diatom species is reproduced with exactness, because the process is genetically encoded. Three types of cell wall proteins have been identified in diatoms; the frustulins, pleuralins, and silaffins. Frustulins are cell wall proteins that form an organic coat to protect the silica structures from dissolution into the aqueous environment. Pleuralins are associated with a specific subcomponent of the frustule during cell division, and play a role in hypotheca-epitheca development. Silaffins from Cylindrotheca fusiformis are short chain-length peptides that play a direct role in the silica polymerization process, and possess unique biochemical post-translation functionalization. Larger proteins with silaffin activity have recently been described in Thalassiosira pseudonana. Frustulins and pleuralins play no role in silica polymerization or structure formation in diatoms, whereas the silaffins are one of the primary polymerization determinants. In addition to the silaffins, a class of long-chain polyamines associated with diatom silica has been identified, and shown to also be involved in the silica polymerization process. The silaffins and polyamines are likely to be the two major determinants of silica polymerization in diatoms. Their involvement in the formation of higher order structure is unclear; there have been suggestions that they self-assemble in various combinations to form the final frustule structure but these are highly speculative as there is no substantial data to support this. It is clear from a long history of electron microscopic observations that a major determinant of silica structure in diatoms is generated by growth and molding of the silica deposition vesicle (SDV), the specialized intracellular compartment were the frustule is made. Diatoms are the focus of research activity on several fronts, including the processes by which their distinct silica frustules are formed.