首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >A speciation study of the aqueous H~+/H_2VO_4~-/H_2O_2/L-alpha-alanyl-L-serine system
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A speciation study of the aqueous H~+/H_2VO_4~-/H_2O_2/L-alpha-alanyl-L-serine system

机译:H〜+ / H_2VO_4〜-/ H_2O_2 /L-α-丙氨酰-L-丝氨酸体系的形态研究

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A detailed study of the quaternary aqueous H~+/H_2VO_4~- /H_2O_2/L-alpha-alanyl-L-serine(Alaser)system has been performed at 25 deg C in 0.150 M Na(Cl)medium,representing the ionic strength of human blood,using quantitative ~51V NMR and potentiometric data(glass electrode).Data were evaluated with the computer program LAKE,which is able to treat combined EMF and NMR data.The pK_a-values for Alaser were determined as 8.04(+-)0.01 and 3.07(+-)0.01.The errors given are 3sigma.In the ternary H~+/H_2VO_4~-/Alaser system,two complexes,(H~+)_p(H_2VO_4~-)_q-(Alaser)_r,having(p,q,r)values(0,1,1)and(-1,1,1)with logbeta_(0,1,1)= 2.42(+-)0.01 and logbeta_(-1,1,1)= -5.80(+-)0.05 explain all data in the pH region 2.5-9.5.Equilibrium conditions are illustrated in distribution diagrams and structure proposals are given based on ~1H and ~13C NMR investigations.In the quaternary H~+/H_2VO_4~/H_2O_2/Alaser system,six complexes could be found in addition to all binary and ternary complexes over the pH region 2.6-11.1,four with a V/X/Alaser ratio 1:1:1 and two with a ratio 1 :2 :1(X = peroxo ligand).The formation of the monoperoxo vanadium species is very slow,requiring up to 10 days for complete equilibrium.Significant decomposition of peroxide occurs only in acidic solutions.Chemical shifts,compositions and formation constants for the six quaternary complexes are given,and equilibrium conditions are illustrated in distribution diagrams.The H~+/H_2VO_4~-/ H_2O_2/Alaser/Alahis system,where Alahis denotes L-alpha-alanyl-L-histidine,was briefly investigated and no mixed ligand species were detected.
机译:在25°C下于0.150 M Na(Cl)介质中对季铵盐H〜+ / H_2VO_4〜-/ H_2O_2 /L-α-丙氨酰-L-丝氨酸(Alaser)体系进行了详细研究,这表明离子强度使用〜51V NMR定量数据和电位计数据(玻璃电极)测定血样。使用计算机程序LAKE评估数据,该程序能够处理EMF和NMR数据的组合.Alaser的pK_a值确定为8.04(+- )0.01和3.07(+-)0.01。给定的误差为3sigma。在三元H〜+ / H_2VO_4〜-/ Alaser系统中,有两个复合物(H〜+)_ p(H_2VO_4〜-)_ q-(Alaser)_r ,具有(p,q,r)值(0,1,1)和(-1,1,1),其中logbeta_(0,1,1)= 2.42(+-)0.01和logbeta _(-1,1, 1)= -5.80(+-)0.05解释了pH值在2.5-9.5范围内的所有数据。在分布图中说明了平衡条件,并基于〜1H和〜13C NMR研究给出了结构方案。在四元H〜+ / H_2VO_4〜/ H_2O_2 / Alaser系统,除pH值以外的所有二元和三元络合物外,还发现了六种络合物离子2.6-11.1,四个V / X /激光比为1:1:1,两个为1:2:1(X =过氧配体)。单过氧钒物质的形成非常缓慢,最高需要完全平衡需要10天。过氧化物仅在酸性溶液中才会发生明显分解。给出了六元季化合物的化学位移,组成和形成常数,并在分布图中说明了平衡条件.H〜+ / H_2VO_4〜-/ H_2O_2简要研究了/ Alaser / Alahis系统,其中Alahis表示L-α-丙氨酰基-L-组氨酸,未检测到混合的配体物种。

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