Charles S. Cockell

Astrobiology


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many other aquatic organisms. However, it is worth considering briefly organisms that can tolerate freezing. Many microorganisms can resist freezing, and the wood frog (Lithobates sylvatica; Figure 4.16), in a similar way to other North American frogs that hibernate close to the surface in soil or leaf litter, can tolerate freezing temperatures. The frog transforms glycogen in its blood to the sugar glucose in response to internal ice formation at the beginning of winter. These molecules act as protectants against damaging ice crystal formation. Frogs can survive freezing during winter if no more than about 65% of the total body water freezes. Although the wood frog is an unusual example, it is clear that evolutionary strategies do exist to tolerate freezing, and although the physical attribute that ice has to float on water may appear to favor life underneath, it does not seem to be a fundamental requirement for life to exist. Life on Earth does not depend on having liquid water under ice to be able to persist. Nevertheless, the lower density of ice compared to liquid water has other important implications. Ice formed on the surface of a water body tends to trap energy underneath and thus maintain a liquid state over long time periods. If water ice sank, lakes, rivers, and other water bodies would freeze completely from the bottom up, which could mean a greater energy requirement to melt the ice seasonally. From a physical point of view, the property is important for understanding aspects of planetary habitability.

Image described by caption.

       Figure 4.16 The wood frog (Lithobates sylvatica). The frog can tolerate freezing temperatures by using glucose as an antifreeze protectant in its tissues.

      Source: Reproduced with permission of Brian Gratwicke, https://en.wikipedia.org/wiki/Wood_frog#/media/File:Lithobates_sylvaticus_(Woodfrog).jpg.

      The property of floating ice and its tendency to trap warmer water with its benefits for life raises a more fundamental question. Are the properties of water fine-tuned for life? Some people take this point of view, but it invites the problematic idea that someone or something has produced a solvent ideal for producing biology. A more evolutionary point of view is to see this from the opposite standpoint: Is life fine-tuned to use the properties of water? For example, the use of water as a proton wire and as part of the active site of enzymes can be understood as life evolving to use the beneficial properties of the water molecule that confer selective advantage, rather than water having an uncanny set of properties “just right” for life.

      Furthermore, as we have seen, the formation of some biological molecules, such as proteins, involves condensation reactions where water is removed from a bond, eliminating it from the chemistry. This is not a deleterious property of water as such, but it does show that chemistry conducive to forming the macromolecules of life involves the removal of water from molecules. We should be careful not to view water as a perfect solvent. However, of all possibilities, and despite some biochemically harmful properties in certain situations, water might be the best solvent for carrying out a large variety of chemical reactions in carbon-based life. We can revisit this question when we discuss alternative solvents later in the chapter.

      We have looked at the key requirements for building the macromolecules in life on Earth and the solvent, water, in which these macromolecules operate, but what about other possible chemistries? We have no empirical evidence to suggest that alternative chemistries can be used by life or that other life forms on some distant planet are using other chemistries, but to put the previous discussions into context, it is worthwhile to briefly consider what alternatives have been discussed.

      As the book progresses, you can consider for yourself whether our view that carbon as the ideal backbone element for life and water as the ideal solvent is a sensibly considered scientific conclusion or merely an Earth-centered prejudice.

      4.11.1 Alternative Core Elements

      What about alternative core elements other than carbon? One popular suggestion is silicon. As an element of group 14, below carbon in the Periodic Table, it shares many common chemical characteristics with carbon. The silicon atom has 14 electrons (1s22s22p63s23p2), compared to carbon's 6 (1s22s22p2). In both atoms, there are four electrons available in the outer shell to form bonds. The major difference is that the silicon atom has a larger atomic radius (111 pm) than carbon (70 pm).

      Silicon can be more reactive than carbon, which is attributed to three characteristics, all of which are related to its larger atomic radius. First, silicon, like carbon, typically forms four bonds, but unlike carbon it can more easily accept additional electrons and form five or six bonds (it can have a higher number of near neighbors than carbon). This allows some reactions to occur at lower energies. Second, many silicon bonds with other elements are weaker than in carbon, requiring less energy to break them. The SibondH bond strength (318 kJ mol−1) is lower than the CbondH bond strength (411 kJ mol−1). For example, silane (SiH4) combusts spontaneously in air even at 0 °C, whereas its carbon analog, methane (CH4), remains completely stable, even in pure oxygen, unless energy is imparted to it. Finally, silicon is more electropositive (a greater tendency to donate electrons) than carbon, leading to strongly polarized bonds with other non-metals that are much more susceptible to chemical reactions. Although the more reactive nature of silicon (at least in the absence of oxygen) may at first appear to be a disadvantage in any potential biochemistry, this high reactivity might make it more conducive to life in low-temperature environments, where the reaction rates would be slower.

      Silicon has some impressive properties. It forms stable covalent bonds with N, P, S, and many other elements. It can also form stable tetra-, penta-, and hexa-coordinated compounds with N, C, and O bonds, analogous to the generation of molecular diversity in carbon chemistry. Oligosilane structures are known to have many consecutive SibondSi bonds that resemble fatty acids in carbon-based membranes. Remarkably, amphiphilic silicon compounds with a charged end attached to an uncharged tail can be made that assemble in water to form vesicles like phospholipids. In Chapter 5, we explore the structure of cellular membranes in more detail. For now, you might like to note the potential to form similar structures using silicon as the core atom.

Structural formulas of silsesquioxane cage (top), silsesquioxane with attached organic side groups (middle), and polyphenylsilsesquioxane ladder repeating unit (bottom).

       Figure 4.17 Silicon can form extraordinarily complex structures, such as these silsesquioxane structures.

      Although there are similarities, carbon and silicon have some significant differences that affect compound formation. The larger radius of silicon compared to carbon accounts for its weaker bond strengths, which means that, despite some of the variety of complex compounds it can form, in general it less