Tris-Functionalized Hybrid Anderson Polyoxometalates: Synthesis, Characterization, Hydrolytic Stability and Inversion of Protein Surface Charge
Tris-Functionalized Hybrid Anderson Polyoxometalates: Synthesis, Characterization, Hydrolytic Stability and Inversion of Protein Surface Charge
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DOI：
10.1002/chem.201405644
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发表时间：
2015-03-16
影响因子：
4.3
通讯作者：
Rompel, Annette
中科院分区：
文献类型：
--
作者：
Blazevic, Amir;Al-Sayed, Emir;Rompel, Annette
以Ga-III和Fe-III为中心杂原子，采用温和的两步合成法，在水溶液中合成了单面和双面功能化的有机-无机杂化安德森多钼酸盐。化合物1-4以水合盐形式分离，[TBA]（3）[GaMo 6 O 18（OH）（3）{（OCH 2）（3）CCH 2 OH}] x12 H（2）O（1）（TBA=四丁基铵），Na-3[FeMo 6 O 18 {（OCH 2）（3）CCH 2 OH}（2）] x11 H（2）O（2），[TMA]（2）[GaMo 6 O 18（OH）（3）{（OCH 2）（3）CNH 3}] x7 H（2）O（3）（TMA=四甲基铵）和Na[TMA]（2）[FeMo 6 O 18（OH）（3）{（OCH 2）（3）CNH 3}]（OH）x6 H（2）O（4）。通过X射线单晶衍射（SXRD）、红外光谱（FTIR）、紫外/维斯光谱（UV/Vis）、热重分析、电喷雾质谱（ESI-MS）、核磁共振（NMR）和元素分析等手段对所合成的化合物进行了表征。化合物1也用两种较小的有机阳离子结晶，得到[TMA]（3）[GaMo 6 O 18（OH）（3）{（OCH 2）（3）CCH 2 OH}]xnH（2）O（5）和[GDM]（3）[GaMo 6 O 18（OH）（3）{（OCH 2）（3）CCH 2 OH}]xnH（2）O（6）（GDM=胍），并基于UV/维斯、NMR、FTIR和元素分析进行表征。这些化合物作为添加剂在大分子晶体学中的用途通过使用ESI-MS在pH 4至9的范围内检查它们的水解稳定性来研究。十二烷基硫酸钠-聚丙烯酰胺凝胶电泳（SDS-PAGE）分析表明，在20 ℃下，BSA在含有100当量1或4的溶液中保持完整超过4天。Zeta电位测量表明，1-4在BSA（1 mgmL（-1））的带正电荷表面上诱导电荷反转，对于具有最高负表面电荷的化合物1和2，其浓度开始低至1.29mM。
Single- and double-sided functionalized hybrid organic-inorganic Anderson polyoxomolybdates with Ga-III and Fe-III positioned as central heteroatoms have been synthesized in a mild, two-step synthesis in an aqueous medium. Compounds 1-4 were isolated as hydrated salts, [TBA](3)[GaMo6O18(OH)(3){(OCH2)(3)CCH2OH}]x12H(2)O (1) (TBA=tetrabutylammonium), Na-3[FeMo6O18{(OCH2)(3)CCH2OH}(2)]x11H(2)O (2), [TMA](2)[GaMo6O18(OH)(3){(OCH2)(3)CNH3}]x7H(2)O (3) (TMA=tetramethylammonium), and Na[TMA](2)[FeMo6O18(OH)(3){(OCH2)(3)CNH3}](OH)x6H(2)O (4). All the compounds were characterized based on single-crystal X-ray diffraction (SXRD), FTIR, UV/Vis, thermogravimetric, ESI-MS, NMR, and elemental analyses. Compound 1 was also crystallized with two smaller organic cations, giving [TMA](3)[GaMo6O18(OH)(3){(OCH2)(3)CCH2OH}]xnH(2)O (5) and [GDM](3)[GaMo6O18(OH)(3){(OCH2)(3)CCH2OH}]xnH(2)O (6) (GDM=guanidinium) and were characterized based on UV/Vis, NMR, FTIR, and elemental analyses. The use of these compounds as additives in macromolecular crystallography was investigated by examining their hydrolytic stability by using ESI-MS in a pH range of 4 to 9. Sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE) analysis showed that BSA remains intact in a solution containing up to 100equivalents of 1 or 4 over more than four days at 20 degrees C. Zeta potential measurements demonstrate that 1-4 induce charge inversions on the positively charged surface of BSA (1mgmL(-1)) with concentrations starting as low as 1.29mM for compounds 1 and 2, which have the highest negative surface charge.