Cold-induced metabolic conversion of haptophyte di- to tri-unsaturated C37 alkenones used as palaeothermometer molecules

Abstract

<jats:title>Abstract</jats:title><jats:p>The cosmopolitan marine haptophyte alga <jats:italic>Emiliania huxleyi</jats:italic> accumulates very long-chain (C<jats:sub>37</jats:sub>-C<jats:sub>40</jats:sub>) alkyl ketones with two to four <jats:italic>trans</jats:italic>-type carbon-carbon double bonds (alkenones). These compounds are used as biomarkers of haptophytes and as palaeothermometers for estimating sea-surface temperatures in biogeochemistry. However, the biosynthetic pathway of alkenones in algal cells remains enigmatic, although it is well known that the C<jats:sub>37</jats:sub> tri-unsaturated alkenone (K<jats:sub>37:3</jats:sub>) becomes dominant at low temperatures, either by desaturation of K<jats:sub>37:2</jats:sub> or by a separate pathway involving the elongation of tri-unsaturated alkenone precursors. Here, we present experimental evidence regarding K<jats:sub>37:3</jats:sub> synthesis. Using the well-known cosmopolitan alkenone producer <jats:italic>E</jats:italic>. <jats:italic>huxleyi</jats:italic>, we labelled K<jats:sub>37:2</jats:sub> with <jats:sup>13</jats:sup>C by incubating cells with <jats:sup>13</jats:sup>C-bicarbonate in the light at 25 °C under conditions of little if any K<jats:sub>37:3</jats:sub> production. After stabilisation of the <jats:sup>13</jats:sup>C-K<jats:sub>37:2</jats:sub> level by depleting <jats:sup>13</jats:sup>C-bicarbonate from the medium, the temperature was suddenly reduced to 15 °C. The <jats:sup>13</jats:sup>C-K<jats:sub>37:2</jats:sub> level rapidly decreased, and the <jats:sup>13</jats:sup>C-K<jats:sub>37:3</jats:sub> level increased, whereas the total <jats:sup>13</jats:sup>C-K<jats:sub>37</jats:sub> level—namely [K<jats:sub>37:2</jats:sub> + K<jats:sub>37:3</jats:sub>]—remained constant. These <jats:sup>13</jats:sup>C-pulse-chase-like experimental results indicate that <jats:sup>13</jats:sup>C-K<jats:sub>37:2</jats:sub> is converted directly to <jats:sup>13</jats:sup>C-K<jats:sub>37:3</jats:sub> by a desaturation reaction that is promoted by a cold signal. This clear-cut experimental evidence is indicative of the existence of a cold-signal-triggered desaturation reaction in alkenone biosynthesis.</jats:p>

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