Department of Chemistry, Duke University , Durham, North Carolina, 27708-0346, United States.
J Am Chem Soc. 2013 Oct 2;135(39):14504-7. doi: 10.1021/ja406609s. Epub 2013 Sep 19.
Boron in the ocean is generally considered a nonbiological element due to its relatively high concentration (0.4 mM) and depth independent concentration profile. Here we report an unexpected role for boron in the iron transport system of the marine bacterium Marinobacter algicola. Proteome analysis under varying boron concentrations revealed that the periplasmic ferric binding protein (Mb-FbpA) was among the proteins whose expression was most affected, strongly implicating the involvement of boron in iron utilization. Here we show that boron facilitates Fe(3+) sequestration by Mb-FbpA at pH 8 (oceanic pH) by acting as a synergistic anion (B(OH)4(1-)). Fe(3+) sequestration does not occur at pH 6.5 where boric acid (B(OH)3; pK(a) = 8.55) is the predominant species. Borate anion is also shown to bind to apo-Mb-FbpA with mM affinity at pH 8, consistent with the biological relevance implied from boron's oceanic concentration (0.4 mM). Borate is among those synergistic anions tested which support the strongest Fe(3+) binding to Mb-FbpA, where the range of anion dependent affinity constants is log K'(eff) = 21-22. Since the pKa of boric acid (8.55) lies near the pH of ocean water, changes in oceanic pH, as a consequence of fluctuations in atmospheric CO2, may perturb iron uptake in many marine heterotrophic bacteria due to a decrease in oceanic borate anion concentration.
海洋中的硼通常被认为是非生物元素,因为其浓度相对较高(0.4mM)且不受深度影响。在这里,我们报告了硼在海洋细菌 Marinobacter algicola 的铁运输系统中的一个意外作用。在不同硼浓度下进行的蛋白质组分析表明,周质铁结合蛋白(Mb-FbpA)是受表达影响最大的蛋白质之一,强烈暗示硼参与了铁的利用。在这里,我们表明硼通过作为协同阴离子(B(OH)4(1-))促进 Mb-FbpA 在 pH 8(海洋 pH)下螯合 Fe(3+)。在 pH 6.5 下不会发生 Fe(3+)螯合,因为硼酸(B(OH)3;pK(a) = 8.55)是主要物种。硼酸盐阴离子也被证明在 pH 8 下以毫摩尔亲和力与 apo-Mb-FbpA 结合,这与硼在海洋中的浓度(0.4mM)所暗示的生物学相关性一致。在测试的协同阴离子中,硼酸盐是支持与 Mb-FbpA 最强结合的 Fe(3+)的阴离子之一,其中阴离子依赖性亲和常数的范围为 log K'(eff) = 21-22。由于硼酸的 pKa(8.55)接近海水的 pH,由于大气 CO2 的波动导致海洋 pH 的变化,可能会由于海洋硼酸盐阴离子浓度的降低而干扰许多海洋异养细菌的铁吸收。