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                    366                                     Biomimetics: Biologically Inspired Technologies

                    functional webs to entrap prey; (b) organic–inorganic composite structures found in sea shells to
                    form highly engineered, hard, tough materials; (c) surfaces such as shark skin to reduce hydro-
                    dynamic friction; (d) modes of ‘‘sticking’’ to surfaces used by the gecko to produce strong
                    adhesives; and (e) muscles in the human body to create highly engineered actuators. These
                    examples, optimized through evolution, provide a range of topics for inspiration in materials
                    designs and functions. They also provide generic insight into the underlying principles employed
                    by biological systems to achieve remarkable plasticity in materials structure and function.
                       Each of the topics listed above is reviewed with a focus on what is currently understood in
                    terms of structure and function, a mechanistic view of the system, and the current state of the art
                    in mimicking these systems. It will be obvious at the end of this chapter that the learning curve is
                    barely past the lag phase (microbial growth curve perspective). It is also worth considering that
                    we are inherently limited in gaining additional insight into these systems due to the complexity of
                    the biological systems of interest, our current limited understanding of their structure and
                    function, and our preconceived bias of how to understand these systems due to training or
                    perspective from more traditional materials science and engineering approaches. The excitement
                    with Nature as a guide to materials science and engineering is that this is only the beginning and
                    there is a lot to be learned in order to elucidate the ‘‘rules’’ that govern the processes involved.



                                    14.2  COMPARISONS: BIOLOGICAL MATERIALS
                               AND SYNTHETIC MATERIALS: SYNTHESIS AND ASSEMBLY

                    At the core of this chapter are the novel ‘‘rules’’ that govern materials formation in Nature. These
                    rules originate from the template-based synthesis driven by genetic blueprints. Furthermore, the
                    building blocks (e.g., amino acids, sugars, nucleic acids) are linked (via enzymatic coupling
                    reactions) into polymers with control of stereochemistry to affect regularity in chemistry and thus
                    higher order interactions (intra and interchain). These polymeric building blocks (proteins, poly-
                    saccharides, nucleic acids, and other biological macromolecules) are therefore ‘‘programmed’’
                    (chemically and physically) to self-organize into more complex materials through hierarchical
                    structural complexity that gives rise to novel materials performance. The control of this structural
                    hierarchy initiates with the regularity in structure at the individual monomer and chain levels, and is
                    propagated up length scales from the molecular (chains), through the mesoscopic (mesophases), and
                    finally to the macroscopic (material ultrastructure) level. Remarkably, these processes occur within a
                    complex mixture of small and large molecules inside and outside of the sites of synthesis (cells).
                    Compartmentalization helps in these processes, along with membrane interfaces. Most of the
                    details involved in these processes are largely unexplored territory scientifically. The entire materials
                    assembly process is governed by the interplay between genetic programs, environmental conditions
                    inside and outside of the cells, and the remarkable specificity and control achieved through enzym-
                    atic processes. Historically, these hierarchical interactions have been studied from the ‘‘top-down’’
                    or at the macro-scale, using electron microscopy to interrogate ultrastructure, or by testing mechan-
                    ical properties of the materials and using this to interpret structural organization. In recent years, the
                    focus of inquiry has shifted to the ‘‘bottom-up’’ paradigm, molecular-level interactions.
                       Polymer assembly as the basis for structural hierarchy and function in biology is most often
                    governed by many weak bonds (hydrogen bonding, van der Waal). It is the high frequency and
                    location of these types of bonds that allow assembly or disassembly of these material systems
                    within reasonable energy demands to permit functions (e.g., such as denaturation and renaturation
                    (replication fork) of DNA during semiconservative replication). These processes are mediated by
                    water, structure, and location, with respect to the organic components and features such as
                    hydrophobic hydration play a major role in the processes. General themes to consider that contrast
                    the process of materials formation and assembly in Nature vs. in the laboratory via synthetic
                    approaches are listed in Table 14.1.
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