Abstract
Depending on all element contents, speciation, and dose, chemical elements and their compounds, including molecular ions and complexes, might exert quite diverse effects on (given, it does matter which one is concerned) living beings. Apart from the rather trivial fact `that overdoses of almost everything are toxic to fatal, roles of elements are closely related to their specific chemical features (which permit to identify and distinguish them). Concerning the set of metals involved in biocatalysis, it was shown that, while appearing to be very diverse and different in their properties, these metals actually do share certain quantitative features in their interactions with potential ligands, such as both amino acid side chains in the proteins to which they belong, and possible substrates of biochemical transformations. The two dimensions—one belonging to “intrinsic” strength of binding between metal ions and ligands of different kinds and the other describing effects of (ex-)changing ligands with one another—do both influence chance and range (also taxonomical range) of positive element-biomass interactions.
This is a preview of subscription content, log in via an institution to check access.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
Notes
- 1.
Compared to both S–Se- and Se–Se bonds; the latter are insignificant here as they cannot form inside proteins because there is only a single selenocystein residue at most in any protein so far investigated.
- 2.
Experiments on hormone activity of thyroxine derivatives showed that this function depends just on bulky substituents at the phenoxyphenyl group and lacks relationship to chemical properties of iodobenzenes; actually, the big iodine substituents can be replaced by even more sterically demanding yet halogen-free alkyl groups like isopropyl or neopentyl (Kaim and Schwederski 1993)!
- 3.
It should be noted that Li administration is highly dangerous if combined with antipsychotic drugs like haloperidol or fluphenazine (causing toxic encephalopathy and sometimes irreversible brain damage Gille et al. 1997; Colvard et al. 2013), that is, compounds interacting with the dopamin (rather than serotonin) system.
- 4.
Due to extreme hydratation and displaying some lipophily as well, Li+ is even much bigger in aqueous media than either Na or Cs cations.
- 5.
In fact, it even was discovered in a sample of mineral water.
- 6.
Lignin is a CC-linked network of alkyl benzene and phenol groups while Bakelite was prepared from phenol and aqueous HCHO, making CH2 bridges among the phenols to produce either rings (cyclodextrines) or a polymeric resin which was the first popular and widely applied synthetic polymer in the 1920s (invented in 1911).
- 7.
Accordingly the local food chain does considerably differ from that in both marine and other limnetic biocoenoses: while small crustacean zooplankton is key in the latter, providing food to an entire guild of fishes as well as to young larvae of bigger fishes, here fishes try to make food from insects and fruits falling into water, or consuming algae or even wood (submerged roots). All of these provide just a modest supply of trace metals, while loss of them via gill membranes or renal excretion would be critical, limiting the length of food chains.
- 8.
Fränzle (2010).
- 9.
As for “primitive” animals having just three or four different kinds of cells, sponges can be dispersed down to the cellular level. Of course, one can then mix suspensions of cells of different species of sponges. When such a mixture is left alone for a few days, the unlike cells will unmix again to reconstruct little sponges each of which consists of cells taken from just one of these species. Obviously the cells already bear an immunological signature which here causes them to separate (and gather with their closest relatives, reconstituting the individual organs and species) rather than to agglutinate. Both trace metal (e.g. accumulation of Ti [outside the SiO2 needles fortifying the entire structure]) and organic biochemistry (formation of terpenoid isocyanides, -isothiocyanates, -formamides etc.) of marine sponges are noteworthy and peculiar. Probably isocyanides R-NC (R = terpene residue) do not just produce a disagreeable smell but also peculiar heavy metal ion enrichments in marine sponges.
- 10.
The entire argument relies on morphology and histology exclusively: DNA, of course, is unique from the very moment of conception while kind and series of gene activation will differ (or not) in different animal larvae producing the above results.
- 11.
These Ca to Ni nuclides soon after (the entire “equilibrium process” takes a few days at most) are either ejected in a supernova or “swallowed” and locked up forever into the ultradense central “wreck” of such a star (neutron star or stellar black hole).
- 12.
Al does co-catalyse (along MnCO3) the transformation of molten glycine into some vast array of “significant” compounds whereas Ti (as either titanous sand, or perovskite CaTiO3) was probably involved in early photoelectrochemical processing producing amino acids and other compounds (see before). Yet neither was introduced into biochemistry of any known organism, although Ti would have offered a possible entrance into primitive photosynthesis.
- 13.
Of course, catalysis works either way round (enhancing rates of both forward and backward reactions as to keep equilibrium position identical to that observed without any catalyst at same conditions [T, p, pH and so on]): if there are dehydrating agents or conditions, like cyanate or polyphosphate ions or NaCl brines, Cu(II) complexes of amino acids and peptides will promote peptide chain prolongation.
- 14.
Note how simple it is to prepare apoenzymes by having metalloproteins interact with effective chelating ligands such as EDTA (Vallee and Williams 1968); afterwards the apoprotein can be supplied with some other metal ion. In porphyrines this is a spontaneous process, replacing Mg from chlorophyll with e.g. Ni2+, VO2+ (Treibs’s red geoporphyrin), In3+, and other ions of appropriate diameters.
- 15.
Besides the famous (Alvarez et al. 1980) iridium and osmium enrichments which were directly attributed to contents of a ≈ 10 km-large impactor, there are significant changes in amounts of e.g. V, Cr, Sr, Mn and other elements in both sediments and biosamples (late dinosaur eggs) some of which are involved in metabolism. However, the isotopic composition of Ir from the KT boundary layer matches that of common terrestrial samples deposited before or afterwards, including native alloys like iridosmium, ruthenoiridosmium or minerals like (Fe, Ru, Ir)As2 (some 63 % 191Ir, remainder 193Ir).
- 16.
The rather small Tunguska event of 1908 produced so much nitrogen oxides in the stratosphere as to reduce the ozone levels—then measured by obtaining blank spectra of nighttime skies—by some 50 % for several years (Toon et al. 1992).
- 17.
It is an open matter whether brains of arthropods, mollusks (especially, cephalopods which are quite bright), and vertebrates are homologous organs, given that the probably last common ancestors still lacked anything of the kind. Nevertheless, brain function requires a highly developed common action of quaternary ammonium ions (acetyl choline, in synaptic gap), Na and K cations, Cu proteins (oxidizing indoles and benzenoid aromatics to produce neurotransmitter phenols and indophenols) and Zn ions, peptides, possibly also others such as Li+.
- 18.
Although, in terms of essentiality, one must distinguish between functions of some element in enzymes or cofactors such as cobalamine (Co), molybdopterin (Mo; this complex is the only speciation from of Mo higher animals can absorb to obtain “enzymatically useful”, active Mo in e.g. oxidoreductases or aldehyde oxidase), selenocystein and structural, osmotic and other features, formation of such fortification fibers (much like in glass- or carbon fiber-reinforced plastics) requires passing some well-defined element to a certain location within some biopolymer sample.
- 19.
As far as hydroxylation is induced by direct electron transfer from an aromatic or PAH or hetero-PAH compound towards Cu(II), no weaker oxidant than O2 (or nitrate, nitrite at best) can induce the e- transfer cascade, and the series of increasingly difficult 1e-oxidation (increasing redox half-wave potential) is aniline < phenol < fluorene < biphenyl < carbazol≪alkyl- or halobenzenes (Lund 1957; Miller et al. 1972).
- 20.
ρarag = 2.73 g/cm3, ρcalcite = 2.93 g/cm3 which means a contraction of some 7 % takes place during change of crystal structures which, moreover, are not closely related but imply a substantial rearrangement of ions. Ostwald’s famous phase rule then means, if there was calcite in Archaeocyatha, like in bones and teeth of today’s vertebrates, biomineralization was effected either slowly, including catalysis of the said rearrangement, or it was done in a manner which was entirely different from that in mollusks. Be it as it was, Archaeocyatha were the first organisms to produce reefs, yet were replaced by sponges already some 516 mio. years BP while likewise “primitive” reef-builders like cnidaria even made it until today (unlike rudites) through several periods of ocean acidification by increased CO2 (implied by thermal history of ocean waters during the times from Ordovician till today)—which should not be taken as an advice to be clumsy or reckless on CO2 enrichment in both troposphere and ocean: obviously some kinds of coral-forming polyps can live isolated, without a stable exoskeleton, in the same manner as Hydra does, but we would soon painfully notice the effects—from fishery turnover breakdowns to catastrophic attack on shorelines by tropical storms—if the large reefs East of Australia and Belize and all the smaller ones would get dissolved by acidification!
- 21.
E.g. CO2 for plants and cyanobacteria where there are both 13C and 17;18O or sugars for which the same holds. In amino acids and peptides, there is 15N additionally, while methanotrophic organisms would perform better in 12;13C isotopic separation as D (2H) is much rarer (about 0.016 %) than the above heavier C, N, and O isotopes. Biogenic metal (Mg, Fe, Zn, Cr, U) isotopic fractionation is feasible for the same reason: “exotic” isotopes (25;26Mg, 66;68Zn, 54;57Fe, 235U) use to be much more abundant than 17;18O or 15N, meaning that biological processing of stable complexes which do not undergo complete M-ligand separation in digestion will fairly efficiently enrich or deplete the above nuclides in biomass thereafter, provided there is but partial resorption, as is quite common. 58Fe, 234U, or 54Cr are too rare for this to be observed.
- 22.
Of course, one then must distinguish between the phases produced during such treatment (the effect can only occur during partial, incomplete dissolution): upon acidic etching of calcite, CO2 (gas) will be depleted in 13C, meaning a relative enrichment of this heavier carbon isotope in both dissolved HCO3 - (liquid) and remaining calcite solid. The calcium isotopes behave similarly, with 40Ca becoming enriched in the supernatant whereas heavy isotopes 43;44;48Ca tend to stay in the solid (normally, the ratio 40Ca/44Ca [46.47 in isotopic standard] is measured, while the tiny traces of 46Ca in the mixture [≈0.004 %] escape precise determination of isotopic shifts and 42Ca is omitted and use of 43Ca [about 0.14 % of mixture] additionally allows for NMR investigation of this fractionation). To give another example, H2O2 oxidations of both elemental sulfur and certain heavy metal sulfides produce 34S/32S or 36S/32S fractionations which are identical to those observed in biological sulfur redox metabolism, and thus—given photochemical formation of H2O2 in palaeoatmosphere and its corresponding presence in rainwater—hence it is impossible to tell when sulfate bioreduction commenced in Archaic times.
- 23.
Unless pH and carbonate content of ocean water then were about the same as today. In the latter case, siderite FeCO3 and iron(II)hydroxides would limit dissolved Fe considerably, in addition Fe(II) photooxidation and H2 release would rapid occur upon UV exposure of the solids (the exactly stoichiometric solids are white but turn green to olive to reddish soon under illumination if solid) reducing Fe availability even before gaseous O2 was present.
- 24.
“Positive exceptions” are mainly centered around certain elements, in particular Cu (hydroxylation of aromatics, peptide/polyamide linking) and V.
- 25.
One of the few cases of a name reaction in inorganic (rather than organic) chemistry.
- 26.
The same happens during induction of metallothionein biosynthesis: once heavy metals or other electrophilic agents like halocarbons react with some specific segment of DNA, gene expression does take place, producing MT which may or may not scavenge the toxic reagents. Some ions, like Bi3+, are so effective in inducing MT as to render them essentially harmless (except if biomethylation takes place), while others including mercury will compromise this mechanism as to product outmost damage.
- 27.
Even though the ionic radius of Be2+ is much smaller than those of either Mg or Zn, there are similarities with Zn and Al pertinent to bioinorganic chemistry: e.g. heating of carboxylates or nitrates produces tetrahedral unpolar molecules with an M4O center and the oxoligands bridging the six edges of the tetrahedron giving [M4O(μ2-RCOO)6] (M=Be or Zn) which are not just lipophilic but do even dissolve in certain hydrocarbons (Cotton and Wilkinson 1982). Neither Al nor Mg nor Ca form similar compounds.
- 28.
Given this, it is blunt nonsense to administer Mo e.g. as ammonium heptamolybdate as is usually done in preparations of multimineral food augmentation tablets (this author possesses samples of this kind); here molybdenum would only be toxic but not at all employed.
- 29.
The toxicity increases observed with Mo, Cd, Zn or Ni show that Se is not reduced to HSe− ion and thus cleaved as metal selenide but takes another biochemically active form the activity of which is increased by addition of “hard” heavy metal ions.
- 30.
This is why hearts can be transplanted at all without microsurgically connecting them to the recipients nervous system: fitting to arteria and venes will do.
References
Cotton FA, Wilkinson G (1982) Anorganische Chemie: eine zusammenfassende Darstellung für Fortgeschrittene. Verlag Chemie, Weinheim
Abelson P (1959) Geochemistry of organic substances. In: Abelson P (ed) Researchers in geochemistry. Wiley, New York, pp 79–103
Alvarez LW, Alvarez W, Asaro F, Michel HV (1980) Extraterrestrial cause for the cretaceous-tertiary extinction. Science 208:1095–1108
Lee DH, Granja JR, Martinez JA, Severin K, Ghadiri MR (1996) A self-replicating peptide. Nature 382:525–528
Anke M, Arnhold W, Groppel B, Krause U (1990) The biological importance of lithium. In: Schrauzer G, Klippel K (eds) Lithium in biology and medicine. VCH, Weinheim, pp 148–167
Arnon D, Stout P (1939) The essentiality of certain elements in minute quantity for plants with special reference to copper. Plant Physiol 14(2):371–375
Berridge M, Downes C, Hanley M (1989) Neural and developmental actions of lithium: a unifying hypothesis. Cell 59:411–419
Braterman PG, Cairns-Smith AG, Sloper RW (1983) Photooxidation of hydrated Fe2+—significance for banded iron formations. Nature 303:163–164
Cade J (1949) Lithium salts in the treatment of psychotic excitements. Med J Aust 2:349–352
Collman JP (1977) Synthetic models for the oxygen-binding hemoproteins. Acc Chem Res 10:265–274
Crowe S, Døssing L, Beukes N, Bau M, Kruger S, Frei R, Canfield D (2013) Atmospheric oxygenation three billion years ago. Nature 501:535–538
Cvetkovic A, Menon AL, Thorgersen MP, Scott JW, Poole FL, Jenney FE, Lancaster WA, Praissman JL, Shanmukh S, Vaccaro BJ, Trauger SA, Kalisiak E, Apon JV, Siuzdak G, Yannone SM, Tainer JA, Adams MWW (2010) Microbial metalloproteomes are largely uncharacterized. Nature 466:779–782
Daley A, Edgecombe G (2014) Morphology of Anomalocaris canadensis from the Burgess Shale. J Paleontol 88(1):68–91
Danovaro R, Dell’ Anno A, Pusceddu A, Gambi C, Heiner I, Kristensen RM (2010) The first metazoan living in permanently anoxic conditions. BMC Biol 8:26–30
Dose K, Rauchfuß H (1975) Chemische evolution. Wissenschaftliche Verlagsgesellschaft, Stuttgart
Droser ML, Gehling JG, Jensen S (2006) Assemblage palaeoecology of the Ediacara biota: unabridged edition? Paleogeogr Palaeoclimatol Palaeoecol 232:131–147
DuBois K, Moxon A, Olson O (1940) Further studies on the effectiveness of arsenic in preventing selenium poisoning. J Nutr 19:477–482
Egami F (1974) Minor elements and evolution. J Mol Evol 4:113–120
Eglinton G, Brassell SC, Howell V, Maxwell JR (1983) The role of organic geochemistry in the deep sea drilling project (DSDP/IPOD). In: Bjoroy M et al (eds) Advances in geochemistry 1981. Wiley, Chichester, pp 391–400
Ekmekcioglu C (2006) Lithium. In: Ekmekciolgu C, Marktl W (eds) Essenzielle Spurenelemente. Springer, Wien, pp 173–177
Erdmann J, Marlett E, Hanson W (1956) Survival of amino-acids in marine sediments. Science 124:1026
Feldmann J (1999) Determination of Ni(CO)4, Fe(CO)5, Mo(CO)6, and W(CO)6 in sewage gas by cryotrapping gas chromatography inductively coupled plasma mass spectrometry. J Environ Monit 1:33–37
Feng DF, Cho G, Doolittle RF (1997) Determining divergence times with a protein clock: update and reevaluation. Proc Natl Acad Sci USA 94:13028–13033
Fisher S, Heacock A, Agranoff B (1992) Inositol lipids and signal transduction in the nervous system: an update. J Neurochem 58:18–38
Fränzle S (2010) Chemical elements in plants and soil. Springer, Berlin
Fränzle S, Markert B (2002a) The biological system of the elements (BSE)—a brief introduction into historical and applied aspects with special reference on “ecotoxicological identity cards” for different element species (e.g. As and Sn). Environ Pollut 120(1):27–45
Fränzle S, Markert B (2002b) Three ways ashore: where did terrestrial plants, arthropods and vertebrates come from? Are essentiality patterns of chemical elements living bio(-geo)chemical “fossisl”?—Interferences from essentialitiy patterns and the biological system of elements. In: Towarzystwo chemii I InzynierII Ekologicznej: Chemia I Inzynieria Ekologiczna. Ecological Chemistry and Engineering, Opole, pp 949–967
Garstang W (1922) The theory of recapitulation: a critical restatement of the biogenetic law. J Linn Soc Zool 35:81–101
Gould T, Quiroz J, Singh J, Zarate C, Manji H (2004) Emerging experimental therapeutics for bipolar disorder: insights from the molecular and cellular actions of current mood stabilizers. Mol Psychiatry 9:734–755
Griffiths M (1983) Lactation in monotremata and speculations concerning the nature of lactation in cretaceous multituberculata. Acta Paleontol Pol 28:93–102
Horvath O, Stevenson KL (1992) Charge transfer photochemistry of coordination compounds. VCH, Weinheim
Irgolic KJ (1986) Arsenic in the environment. In: Xavier AV (ed) Frontiers in bioinorganic chemistry. VCH, Weinheim, pp 399–408
Janvier P (2013) Palaeontology: inside-out turned upside-down. Nature 502:457–458
Johnson MK, Rees DC, Adams MWW (1996) Tungstoenzymes. Chem Rev 96:2817–2839
Kaim W, Schwederski B (1993) Bioanorganische Chemie. Teubner, Stuttgart
Kapusta ND, Mossaheb N, Etzersdorfer E, Hlavin G, Thau K, Willeit M, Praschak-Rieder N, Sonneck G, Leithner-Dziubas K (2011) Lithium in drinking water and suicide mortality. Br J Psychiatry 198(5):346–350
Kolditz L (1986) Anorganische Chemie. Deutscher Verlag der Wissenschaften, Berlin
Lardy H, Moxon A (1939) The effect of selenium and arsenic at various ratios on the fermentation of glucose by baker's yeast. So Dak Acad Sci 19:109
Lund H (1957) Electroorganic preparations. IV. Oxidation of aromatic hydrocarbons. Acta Chem Scand 11:1323–1130
MacAlester AL (1982) Die Geschichte des Lebens. Geowissen kompakt, vol 6. Enke, Stuttgart
Magaritz M, Kaufmann A, Levy Y, Fink D, Meirav O, Paul M (1986) 36Cl in a halite layer from the bottom of the Dead Sea. Nature 320:256–257
Majerus P (1992) Inositol phosphate biochemistry. Annu Rev Biochem 61:225–250
Markert B, Wünschmann S, Fränzle S, Figueiredo AMG, Van der Meer A, Wolterbeek B (2013d) Thallium distribution in plants. In: Kretsinger R, Permyakov E, Uversky V (eds) Encyclopedia of metalloproteins. Springer, New York, pp 2188–2193
McLendon G, Harris W, Martell AE (1976) Dioxygen complexation by cobalt amino acid and peptide complexes. I Stoichiometry and equilibria. J Am Chem Soc 98:8379–8386
Mentel M, Martin W (2010) Anaerobic animals from an ancient, anoxic ecological niche. BMC Biol 8:32–37
Miller LL, Nordblom GD, Mayeda EA (1972) A simple, comprehensive correlation of organic oxidation and ionization potentials. J Org Chem 37:916–918
Moxon A, DuBois K (1939) The influence of arsenic and certain other elements on the toxicity of seleniferous grains. J Nutr 18:447
Nachtigall W, Wisser A (2006) Ökophysik. Springer, Berlin
Nedin C (1999) Anomalocaris predation on mineralized and non-mineralized trilobites. Geology 27:987–990
Nriagu JO (ed) (1998) Thallium in the environment. Wiley, New York
Paquin R, Farley K, Santore R, Kavvadas C, Mooney K, Winfield R, Wu K, Ti Tore D (2003) Metals in aquatic systems: a review of exposure, bioaccumulation, and toxicity models. Society of Environmental Toxicology and Chemistry (SETAC), Pensacola, pp 61–90
Potter R, DuBois K, Moxon A (1939) A comparative study of liver glycogen values of control, selenium and selenium-arsenic rats. So Dak Acad Sci 19:99
Quiroz J, Gould T, Manji H (2004) Molecular effects of lithium. Mol Interv 4(5):259–272
Quiroz J, Machado-Vieira R, Zarate C, Manji H (2010) Novel insights into lithium’s mechanism of action: neurotrophic and neuroprotective effects. Neuropsychobiology 62(1):50–60
Rechenberg I, Küppers U, Scheel A, Mattheck C, Harzheim L (1998) Evolution und Optimierung. In: Nachtigall W (ed) Bionik. Grundlagen und Beispiele für Ingenieure und Naturwissenschaftler. Springer, Heidelberg, pp 245–269
Riedel E [ed.] (2010) Moderne Anorganische Chemie, 3rd edn. De Gruyter, Berlin and New York.
Schou M (1997) Forty years of lithium treatment. Arch Gen Psychiatry 54:9–13, discussion 14–15
Scott GT, deVoe R (1954) The reversible replacement of potassium by rubidium in Ulva lactuca. J Gen Physiol 37:249–253
Seilacher A (2008) Ediacara – Leben wie auf einem anderen Planeten. In: Betz O, Köhler H (eds) Die Evolution des Lebendigen. Attempto, Tübingen, pp 97–115
Sterner RW, Elser JJ (2002) Ecological stoichiometry. The biology of elements from molecules to the biosphere. Princeton University Press, Princeton
Strasburger E, Sitte P (1991) Lehrbuch der Botanik für Hochschulen, 33rd edn. Gustav Fischer, Stuttgart
Strasdeit H (2001) Das erste cadmiumspezifische Enzym. Angewandte Chemie 113:730–732
Toon G, Farmer C, Schaper P, Lowes L, Norton R (1992) Composition measurements of the 1989 Arctic winter stratosphere by airborne infrared solar absorption spectroscopy. J Geophys Res 97:7939–7970
Tottey S, Harvie DR, Robinson NJ (2005) Understanding how cells allocate metals using metal-sensors and metallochaperones. Acc Chem Res 38:775–783
Vallee BL, Williams RJP (1968) Metalloenzymes. The entatic nature of their active sites. Proc Natl Acad Sci USA 59:498–505
Williams RJP, Frausto Da Silva JJR (1996) The natural selection of the chemical elements. Clarendon, Oxford
Yiu SM, Man WL, Wang X, Lam WWY, Ng SM, Kwong HK, Lau KC, Lau TC (2011) Oxygen evolution from BF3/MnO4-. Chem Commun 47:4159–4161
Author information
Authors and Affiliations
Rights and permissions
Copyright information
© 2015 Springer International Publishing Switzerland
About this chapter
Cite this chapter
Markert, B., Fränzle, S., Wünschmann, S. (2015). Analysing the Biological Roles of Chemical Species. In: Chemical Evolution. Springer, Cham. https://doi.org/10.1007/978-3-319-14355-2_3
Download citation
DOI: https://doi.org/10.1007/978-3-319-14355-2_3
Published:
Publisher Name: Springer, Cham
Print ISBN: 978-3-319-14354-5
Online ISBN: 978-3-319-14355-2
eBook Packages: Chemistry and Materials ScienceChemistry and Material Science (R0)