Production of potentially prebiotic condensed phosphates by phosphorus redox chemistry
Production of potentially prebiotic condensed phosphates by phosphorus redox chemistry
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DOI：
10.1002/anie.200802145
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发表时间：
2008-01-01
影响因子：
16.6
通讯作者：
Lunine, Jonathan I.
中科院分区：
文献类型：
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作者：
Pasek, Matthew A.;Kee, Terence P.;Lunine, Jonathan I.
芬顿化学：使用浓度为0.001 M至0.1 M的Na 2 HPO 3或NaH 2 PO 2、浓度为0.001 M至0.1 M的铁（以FeCl 2 × 4 H2O或FeSO 4计）和浓度为0.002 M至0.5 M的H2 O2（表S1）制备一系列溶液，除非另有说明，否则各溶液的起始pH值均为7±1。最后加入过氧化物以促进反应。一个实验是用浓度为1.2M的甲醛作为还原剂进行的。将溶液搅拌1-20天，提取每种溶液的2 mL等分试样，并置于2 mL 10 M NaOH溶液和D2 O的1：1混合物中以淬灭反应，沉淀FeIII并制备样品用于NMR分析。在先前的工作之后[6a，c]，在Varian 300四核探针FT-NMR光谱仪上在121.43 MHz和24.5 ºC下使用31 P NMR分析倾析样品，扫描256至6000次，或在Bruker Avance 500四核FT-NMR系统上在25 C和202.46 MHz下操作磷，扫描400-9000次。在1H-去耦和耦合模式下获得光谱。根据与已知标准品和先前工作的比较，确定峰，并根据峰面积确定丰度。[6，15]从这些数据中，我们确定约34.5%的还原P被氧化为浓缩P（图S1，见下文）。用pH为13的起始溶液制备一些溶液。在这些实验中，Fe II沉淀成绿色锈并且不促进任何芬顿化学。这些溶液还显示还原化合物没有氧化。从这些实验中，我们确定通过向溶液中加入碱来淬灭反应，因此加入NaOH不会促进磷物质的进一步反应。
Fenton Chemistry: A series of solutions were prepared with Na2HPO3 or NaH2PO2 in concentrations between 0.001 M to 0.1 M, iron (as FeCl2× 4H2O or as FeSO4) concentrations between 0.001 M to 0.1 M, and H2O2 concentrations between 0.002 M to 0.5 M (Table S1), each with a starting pH of 7±1, unless otherwise noted. Peroxide was added last to promote the reactions. One experiment was performed with a formaldehyde concentration of 1.2 M to act as a reductant. The solutions were stirred for 1-20 days, a 2 mL aliquot of each solution was extracted and placed in 2 mL of a 1: 1 mixture of 10 M NaOH solution and D2O to quench the reaction, precipitate FeIII and prepare the sample for analysis by NMR. Decanted samples were analyzed using 31P NMR on a Varian 300 four-nucleus probe FT-NMR spectrometer at 121.43 MHz and 24.5 ºC for 256 to 6000 scans following prior work [6a, c], or on a Bruker Avance 500 four-nucleus FT-NMR system operating at 25 C and 202.46 MHz for phosphorus with 400-9000 scans. Spectra were acquired in both 1H-decoupled and coupled modes. The peaks were identified based on comparison to known standards and previous work, with abundances determined from peak areas.[6, 15] From these data, we determine that approximately 34.5% of reduced P becomes oxidized to condensed P (Fig. S1, vide infra). Some solutions were prepared with a starting solution pH of 13. In these experiments, the FeII precipitated to green rust and did not promote any Fenton chemistry. These solutions also showed no oxidation of reduced compounds. From these experiments, we determined that the reactions were quenched by addition of base to the solution, hence the addition of NaOH does not promote further reaction of phosphorus species.