Effects of pH and temperature on dimerization rate of glycine: Evaluation of favorable environmental conditions for chemical evolution of life

To evaluate favorable environmental conditions for the chemical evolution of life, we studied the effects of pH and temperature on the dimerization rate of glycine (Gly: NH(2)-CH(2)-COOH), one of the simplest amino acids. Gly dimerizes to form glycylglycine (GlyGly), and GlyGly further reacts to form diketopiperazine (DKP). Gly solutions with pH ranging from 3.1 to 10.9 were heated for 1-14 days at 140 degrees C, and changes in concentrations of Gly, GlyGly, and DKP were evaluated. At pH 9.8, the experiments were conducted at 120, 140, 160, and 180 degrees C. The dimerization rate of Gly was nearly constant at pH 3-7 and increased with increasing pH from 7 to 9.8 and then decreased with further increases in pH. To elucidate the reason for this pH dependency, we evaluated the role of the three dissociation states of Gly (cationic state: Gly(+), zwitterionic state: Gly(+/-), and anionic state: Gly(-)). For pH >6, the dominant forms are Gly(+/-) and Gly(-), and the molar fraction of Gly(+/-) decreases and that of Gly(-) increases with increasing pH. The dimerization rate was determined for each dissociation state. The reaction between Gly(+/-) and Gly(-) was found to be the fastest; the rate constant of the reaction between Gly(+/-) and Gly(-) was 10 times the size of that between Gly(-) and Gly(-) and 98 times that between Gly(+/-) and Gly(+/-). The dimerization rate became greatest at pH 9.8 because the molar fractions of Gly(+/-) and Gly(-) are approximately equal at this pH. The dimerization rate increased with temperature, and an activation energy of 88 kJ mol(-1) was obtained. Based on these results and previous reports on the stability of amino acids under hydrothermal conditions, we determined that Gly dimerizes most efficiently under alkaline pH (similar to 9.8) at about 150 degrees C. (C) 2010 Elsevier Ltd. All rights reserved.