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Chemical Elements in Plant and Soil: Parameters Controlling Essentiality pp 17–130Cite as

Autocatalytic Processes and the Role of Essential Elements in Plant Growth

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Part of the book series: Tasks for Vegetation Science ((TAVS,volume 45))

Abstract

There is no direct relationship between essentiality patterns of chemical elements and analytical data for biological materials: while any organism selects some (dozens of) chemical elements for running its biochemical functions, several of these may be present, both required and tolerable at very low concentration levels only (V, Se) though essential whereas there are substantial amounts of non-essential metal ions in the same organism (Al, Rb, Sr, Ti, etc.). There are also differences with respect to biochemical effects. In additions, elements do interact during uptake: regardless whether an element is essential by itself, it may influence the uptake of another – regardless whether essential or non-essential – one, e.g. by competing for the same carriers. There also are changes of effects (Fig. 1.2) which can be detected by changes of plant growth rates.

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Notes

  1. 1.

    Apparently this difference of some 2–3 units is a simple charge effect, corresponding to the “electrostatic part” of M-L-binding, cp. the difference between c values of H, Tl, R3Sn monocations vs. similar (isoelectronic, similar radii) dications (Be2+, Pb2+, R2Sn2+).

  2. 2.

    Conversely, either chelating or linkage-isomeric behavior in a ligand with very different EL(L) of the possible donor sites points to x1d ≈ 0, e.g. with acrylate ion complexes (either behaving as an olefin p-ligand [side-on-bound] or as a carboxylate) of Pt(II).

  3. 3.

    Note that there is a difference in effective EL(L) of different ages in spruce needles.

  4. 4.

    For example, from Lever`s formalism it can be directly calculated that Ru(II/III) redox potentials for derivatives formed by neutral ligand attack on the chlorobridges in ([Ru(CO)3Cl2]2) are similar to that of molecular fluorine (!).

  5. 5.

    Proton–proton fusion chain reactions (Bethe and Critchfield 1938): the first long-lived intermediate of nuclear fusion in lowmass stars, 3He, adds to one 4He to yield (radioactive) 7Be which eventually produces two 4He by capture of another proton and radioactive decay of 8B (pp-III chain) or vice versa along the 7Be decay product 7Li + p (pp-II).

  6. 6.

    “Strategy” here corresponds to some “evolutionary stable strategy” (ESS) as derived from biological applications of game theory (Szathmary, Maynard Smith).

  7. 7.

    As a rule, there are neither covalent metal–metal bonds nor oganometal species in biology, the only “dimer” kinds directly linked to each other covalently being formed by C–C- or S–S- bonds. Usually, two identical metals are rather bridged by hydroxo-, chloro- or carboxylato ligands (e.g., in haemerythrin), with other μ-ligands like hydride or O2, N2 to be considered as intermediates of catalytic cycles or transport tasks. As often metal ions liable to condensation (valve metals, V, Fe) are located close to the “surface” of some protein structure, formation of such dimers will not be precluded by the matrix. Moreover thioferrate clusters also facilitate linking. The thermodynamic and physicochemical (SNA and beyond) implications of this tendency in biochemistry remain to be fully understood.

  8. 8.

    As this “problem”, which e.g. precludes transfer of Sm3+ and several other REEs into wheat grains almost completely (that is, down to detection limits, Emsley 2001), occurs likewise with all the REEs and other “citratophilic” metals (Al, Ga) in a given plant species, non-fractionation (identical BCF, here thus small, usually BCF < 0.02 for these metals in terrestrial plants) does imply that effects occurring elsewhere during respeciation cancel each other or do not differ either. Thus the determination of an effective electrochemical ligand parameter based on identical BCF among these and other elements remains valid; in addition, multi-element approaches provide rather identical EL(L)eff values for the same plant analyzing REE and transition metal BCF data (cp. Table 2.19).

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    Stefan Fränzle

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Fränzle, S. (2010). Autocatalytic Processes and the Role of Essential Elements in Plant Growth. In: Chemical Elements in Plant and Soil: Parameters Controlling Essentiality. Tasks for Vegetation Science, vol 45. Springer, Dordrecht. https://doi.org/10.1007/978-90-481-2752-8_2

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