表面类固醇基团对介孔有机硅吸附胆汁酸盐的影响

N. V. Roik, L. Belyakova
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摘要

调节人体内胆汁酸的肠肝循环是克服心血管疾病的实际任务。这项工作的目的是创造生物相容性吸附剂与改善的胆汁酸的吸附能力。在模板十六烷基三甲基溴化铵存在下,正硅酸四乙酯与功能硅烷通过溶胶-凝胶缩合得到了3 -氨基丙基和甾体基接枝的MCM - 41型介孔有机硅。通过低温氮吸附-解吸和X射线衍射分析对合成有机硅的孔隙结构进行了表征。形成典型的为MCM - 41六边形排列的圆柱形介孔。计算了合成二氧化硅材料的结构参数。以胆盐(胆酸钠和牛磺胆酸钠)为例,研究了表面类固醇基团对有机硅吸附能力的影响与接触时间、介质酸度和平衡浓度的关系。对Lagergren模型和Ho-McKey模型估计的吸附动力学参数的分析证实了伪二阶过程的进行。在pH ~ 5和pH ~ 2时,胆酸钠和牛磺胆酸钠的吸附效果最佳,3 -氨基丙基质子化和胆汁酸解离的pH区发生重叠。利用Freundlich、Redlich - Peterson和BET模型对实验得到的等温线进行了分析。研究发现,在pH值1 ~ 8范围内,合成的氨基硅酸原水解产物的主要吸附中心是质子化氨基。在溶胶-凝胶合成过程中,在表层引入类固醇基团导致胆盐的吸附增加,这是由于有机二氧化硅表层形成超分子结构的协同相互作用。所得结果证明了具有表面类固醇基团的有机硅吸附剂用于调节人体内胆汁酸含量的前景。
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Influence of surface steroid groups on sorption of salts of bile acids by mesoporous organosilicas
Regulation of enterohepatic circulation of bile acids in human body is actual task to overcome cardiovascular diseases. The aim of this work was to create biocompatible sorbents with improved sorption ability in relation to bile acids. Mesoporous organosilicas of MCM‑41 type with chemically grafted 3‑aminopropyl and steroid groups were obtained by sol‑gel condensation of tetraethyl orthosilicate and functional silanes in the presence of template cetyltrimethylammonium bromide. Porous structure of synthesized organosilicas was characterized by low‑temperature nitrogen adsorption–desorption and X‑ray diffraction analysis. Formation of typical for MCM‑41 hexagonal arrangement of cylindrical mesopores was confirmed. Structural parameters of synthesized silica materials were calculated. The influence of surface steroid groups on sorption ability of organosilicas was studied on example of bile salts (sodium cholate and taurocholate) in dependence of duration of contact, acidity of medium, and equilibrium concentration. Analysis of kinetic parameters of sorption estimated by Lagergren and Ho-McKey models confirms the proceeding of pseudo-second order process. The most effective sorption of sodium cholate and taurocholate was observed at pH ~ 5 and pH ~ 2, respectively, where the ovterlapping of pH regions of 3‑aminopropyl groups protonation and bile acids dissociation takes place. Analysis of experimentally obtained isotherms by use of Freundlich, Redlich‑Peterson, and BET models was carried out. It has been found that protonated amino groups are the main sorption centers of bile acids protolytic forms by synthesized aminosilica in pH range from 1 to 8. Introduction of steroid groups in surface layer at sol-gel synthesis leads to the increase of bile salts sorption due to the cooperative interactions with formation of supramolecular structures in the surface layer of organosilica. Obtained results prove prospects of usage of organosilica sorbents with surface steroid groups for regulation of bile acids content in human body.
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