Organic
molecules control calcite growth and crystal morphology,
influence biomineralization processes, and offer clues for optimizing
antiscalants for industry. Here we quantified the effect of amino
acid monomers, aspartic acid (Asp1), and glycine (Gly1), and their polymers (Aspn, Asp5, and
Gly5), on calcite growth rate, in a constant composition
setup. Asp1 and its polymers inhibit growth, with rate
decreasing as amino acid chain length increases. For 2 mM Asp1, fractional inhibition (FI, where 1 represents complete inhibition)
was 0.54; for 0.0012 mM Aspn, FI = 0.94. Gly1 and Gly5 only marginally affect growth (−0.1 <
FI < 0.1); indeed, they slightly promote growth at most tested
concentrations. Fitting of adsorption isotherms (Langmuir, Langmuir–Freundlich,
Flory–Huggins) confirmed that Asp polymers adsorb strongly,
explaining their strong control on calcite growth, but Gly1 and Asp1 adsorb less due to competition with carbonate
ions. ΔG
ads (Aspn) =
−39 kJ/mol; ΔG
ads (Asp5) = −50 kJ/mol; ΔG
ads (Asp1) = −21 kJ/mol; and ΔG
ads (Gly1) = −22 kJ/mol. The morphology
was equally affected. Crystal edges became rougher, and corners, more
rounded. Overall, the number of carboxyl groups and length of the
carbon chain correlated with the lowest growth rate.
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