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化学学报
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化学学报 ›› 2009, Vol. 67 ›› Issue (11): 1195-1200. 上一篇    下一篇

研究论文

(NH3CH2CHNH2CH3)2[WVIO2(OC6H4O)2]的合成、晶体结构及其与ATP相互作用的NMR性质研究

宋富根a,b 鲁晓明*,a 喻 冲a 史旭东a 陈俞有a
毕研刚a 池子翔a 叶朝辉c

  

  1. (a首都师范大学化学系 北京 100037)
    (b中国科学院青海盐湖研究所 810008)
    (c中国科学院武汉物理研究所 武汉 430071)

  • 投稿日期:2008-07-18 修回日期:2008-12-05 发布日期:2009-06-14
  • 通讯作者: 鲁晓明

Synthesis, Crystal Structure of (NH3CH2CHNH2CH3)3[WVIO2- (OC6H4O)2] and Its NMR Studies on the Interaction with ATP

Song, Fugen a,b Lu, Xiaoming a Yu, Chong a Shi, Xudong a Chen, Yuyou a
Bi, Yangang a Chi, Zixiang a Ye, Chaohui c

  

  1. (a Department of Chemistry, Capital Normal University, Beijing 100037)
    (b Qinghai Institute of Salt Lakes, Chinese Academy of Sciences, Xining 810008)
    (c Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences, Wuhan 430071)
  • Received:2008-07-18 Revised:2008-12-05 Published:2009-06-14
  • Contact: Lu, Xiaoming

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在室温下, 选用具有手性特征的1,2-丙二胺(1,2-propanediamine)为对阳离子, 由正四丁基铵十钨酸盐和邻苯二酚反应, 得到了钨酶活性结构因子仿生配合物(NH3CH2CHNH2CH3)2[WVIO2(OC6H4O)2], 用单晶X射线衍射测定了其晶体结构, 晶体属单斜晶系, 空间群为P21/n, a＝1.1099(3) nm, b＝1.0416(3) nm, c＝1.8874(6) nm, β＝96.492(6)°, V＝2.1679(11) nm3, z＝4, R1＝0.0445, wR2＝0.0682; 并对它进行了IR, 1H NMR和UV-Vis谱学表征. 利用NMR研究了其与三磷酸腺苷(ATP)的相互作用, 结果发现手性特征的1,2-丙二胺及邻苯二酚苯环的1H化学位移在与ATP混合前后均呈现出较大的差异, 分析得出: 配合物中的金属离子在D2O中大多数均以W(V)价态存在, 但在与ATP共存时转化为W(VI), 并与配体发生了解离.

关键词: 钨氧转移酶活性结构因子仿生配合物, 晶体结构, ATP, 1H NMR

Cis-dioxo-catecholatotungsten (VI) complex (NH3CH2CHNH2CH3)2[WVIO2(OC6H4O)2] is obtained with chiral protonated 1,2-propanediamine by the reaction of tetrabutyl ammonium decatungstate with catechol in the mixed solvent of CH3OH, CH3CN at room temperature. The crystal structure of complex was determined by X-ray diffraction structural analysis. The results show that complex belongs to monoclinic system with space group P21/n, a＝1.1099(3) nm, b＝1.0416(3) nm, c＝1.8874(6) nm, β＝96.492(6)°, V＝2.1679(11) nm3, z＝4, R1＝0.0445, wR2＝0.0682; and studied by IR, 1H NMR and UV-Vis. The NMR studies on the interaction of the title complex with adenosine-triphosphate (ATP) reveal that 1H chemical shifts of 1,2-propanediamine and catechol with and without ATP exhibit distinct difference, the reduction of W(VI) to W(V) occurs when the title complex is dissolved in D2O and the W(V) is oxidized again when ATP solution is mixed with original solution and the hydrolysis of the catecholato ligand take places at mean time being monitored by 1H NMR.

Key words: biomimetic complex of the cofactor of tungstoenzyme, crystal structure, ATP, 1H NMR