L-苏糖酸与生命必需金属元素化合物的研究

【作者】 俱战锋；

【导师】 高胜利； 陈三平；

【作者基本信息】 西北大学 ， 无机化学， 2003， 硕士

【摘要】 系统地探讨了L-苏糖酸金属化合物的合成方法，对文献已有的NaC₄H₇O₅·H₂O、KC₄H₇O₅·H₂O、Mg（C₄H₇O₅）₂·H₂O、Ca（C₄H₇O₅）₂、Zn（C₄H₇O₅）₂五种L-苏糖酸金属化合物的合成方法进行了改进和创新，并合成了未见文献报道的Mn（C₄H₇O₅）₂·H₂O、Co（C₄H₇O₅）₂·H₂O、Ni（C₄H₇O₅）₂·2H₂O、Cu（C₄H₆O₅）·0.5H₂O等四种L-苏糖酸金属化合物。 用化学分析及元素分析确定了九朴化合物的化学组成分别为：Na（C₄H₇O₅）·H₂O（1）；K（C₄H₇O₅）·H₂O（2）；Mg（C₄H₇O₅）₂·H₂O（3）；Ca（C₄H₇O₅）₂（4）；Mn（C₄H₇O₅）₂·H₂O（5）；Co（C₄H₇O₅）₂·H₂O（6）；Ni（C₄H₇O₅）₂·2H₂O（7）；、Cu（C₄H₆O₅）·0.5H₂O（8）；Zn（C₄H₇O₅）₂（9）；它们瓜光谱分析表明，化合物1、2表现为简单的羧酸盐特征，化合物3～8中，L-苏糖酸以羧基氧与金属配位，金属离子为sp³杂化，配位数为4，化合物（?）中，铜离子与羧基氧配位的同时与α位的醇羟基脱质子配位。由此推测了它们的可能结构；采用TG-DTG方法对这些化合物的热分解进行了研究，它们普遍具有较高的热稳定性，并推测了它们的热分解机理：一般是含有结晶水的先失去结晶水，然后再分步或直接分解，最终的产物为其氧化物。 采用RBC-Ⅱ型精密转动弹量热计测定了9种化合物的恒容燃烧能，Δ_cE，计算了它们的标准摩尔燃烧焓，Δ_cH_m^θ，和标准摩尔生成焓， A_fH_m^θ。结果分别为(kJ·mol^-1)：西北口悦学硕二七论文 一2 447.51士2.26（7）;一1 1 14.76士0.81（8）;一2 648.69士1.11（9）。 运用70一580K小样品全自动精密绝热量热计测定了化合物1和2的摩尔热 容，由热容一温度曲线可发现化合物1在（3H.441士0.221）K存在一固一固相变，相变 焙△凡计算结果为（5.753士0.006）kJ·mol一‘，相变嫡△氛计算结果为（一8.473士0.016） J.K-，·mol-，，其熔化温度几、为（371 .274士0.080）K，计算得到熔化焙△fusH和熔化嫡 △、:S分别为（15.353士0.027）KJ·:1飞01”不仁l（41.352土0.078）J·K一’·mol一‘。化合物2的熔化 温度几:为（380.524士0.093）K，计算得到熔化焙△。巧H和熔化嫡△。155分别为 （19.655士0.012）KJ·mol一’和（51.618士0.051）J·K‘’·mol一’。更多还原

【Abstract】 The methods on syntheses of compounds of L-threonic acid and metal ion were discussed in this paper. Based on the literature, the methods concerning the preparation of 5 metal L-threnate were developed and innovated, involving NaC4H7O5-H2O, KC4H7O5-H2O, Mg(C4H7O5)2-H,O, Ca(C4H7O5)2, Zn (C4H7O5)2. And four new compounds of Mn(C4H7O5)2-H2O, Co(C4H7O5)2-H2O, Ni(C4H7O5)2-2H2O, Cu(C4H6O5)-0.5H2O were prepared as well.The compositions of 9 compounds were identified as, by chemical and elemental analyses, Na(C4H7O5)-H2O (1); K(C4H7O5)-H2O (2); Mg(C4H7O5)2-H2O (3); Ca(C4H7O5)2 (4); Mn(C4H7O5)2-H2O (5); Co(C4H7O5)2-H2O (6); Ni(C4H7O5)2-2H2O (7); Cu(C4H6O5)-0.5H2O (8); Zn(C4H7O5)2 (9). The title compounds were characterized by IR and TG-DTG. The bonding characteristics of the compounds were discussed and their structure were speculated from the results of the IR analyses, compounds 1 and 2 can be assumed as the simple carboxylic salts. As for compounds 3 to 8, M2+ coordinates to oxygen atom of the carboxyl group, while the proton of the carboxyl group is dissociated. it was assumed that the coordination number of M2+ was 4. M2+ in Compound $ coordinated to oxygen atom of the carboxyl group and oxygen atom of a - hydroxy, while the proton of the a - hydroxy was dissociated. The thermo stability of the compounds was studied by TG-DTG. The result of TG-DTG indicated that all of the compounds were of good stability. Their possible decomposing processes were also investigated, the final products of the thermal decomposition of the compounds were metal oxides.The constant volume combustion energy, cE, of the compounds were determined byRBC- II precise rotating-bomb calorimeter, their standard enthalpies of combustion, and standard enthalpies of formation, were calculated respectively. The results are (kJ.mol-1) : cE: -1803.62± 0.91(1); -1 749.71 ±0.91 (2); -3384.30±1.21(3);-3133.12± 1.63(4); -3384.30±1.21(5); -3504.47 ±1.64(6);-3515.22±1.97(7); -1616.15± 0.72(8); -2 853.14±1.49 (9). : -1 802.38±0.91 (1); -1748.47 ± 0.91(2); -3383.07±1.21(3);-3 130.65±1.63 (4); -3383.07±1.21(5); -3 501.99± 1.64 (6);-3512.74±1.97(7); -1 616.77±0.72 (8); -2 850.66±1.49 (9). : -1 265.84± 1.06(1); -1292.56±1.06 (2); -2 571.68± 1.63 (3);-2653.34±1.08(4); -2 571.68±1.63 (5); -2 170.67±1.97 (6),--2 447.51±2.26 (7); -1 114.76±0.81 (8); -2 648.69±1.11 (9). The heat capacity of compounds 1 and 2 was precisely determined with a small sample precision automated adiabatic calorimeter over the temperature range from 70 to 580 K. It was found that there was a s-s phase transition in compound 1 at about (311.441 ±0.221) K from the experimental molar heat capacity curve of the compound 1 with temperature. The molar enthalpy, mH and entropy, mS of the phase transition were (5.753±0.006) kJ-mol-1, (18.473 ± 0.016) J.K-1.mol-1, which were calculated on the basis of the heat-capacity measurement. Its melting point was (371.274 ±0.080) K, the molar enthalpy, H, and entropy, fusS, of the phase transition were (15.353 ±0.027) kJ.mol-1, (41.352±0.078) J.K-1.mol-1. The experimental molar heat capacity curve of the compound 2 with temperature showed the melting point of compound 2 was (3 80.524± 0.093) K. According to the heat-capacity measurement, the molar enthalpy, , and molar entropy, fusS, of the phase transition were calculated to be (19.655 ±0.012) kJ-mol-1, (51.618 ± 0.051) J.K-1.mol-1, respectively.更多还原