Selective adsorption of biladien-ab-one and zinc biladien-ab-one to mesoporous silica
Selective adsorption of biladien-ab-one and zinc biladien-ab-one to mesoporous silica
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DOI：
10.1016/j.micromeso.2008.11.025
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发表时间：
2009-04
影响因子：
5.2
通讯作者：
H. Akasaka;H. Yukutake;Y. Nagata;T. Funabiki;T. Mizutani;Hideki Takagi;Y. Fukushima;L. Juneja;Hironobu Nanbu;K. Kitahata
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文献类型：
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作者：
H. Akasaka;H. Yukutake;Y. Nagata;T. Funabiki;T. Mizutani;Hideki Takagi;Y. Fukushima;L. Juneja;Hironobu Nanbu;K. Kitahata
研究了苯溶液中孔直径分别为2.3、2.7、4.0和7.0 nm的介孔二氧化硅对线性四氢吡咯和卟啉的吸附。作为直链四吡咯，1，15，21，22-tetrahydro-19-benzoyl-5，10，15-triphenyl-15-hydroxybilin-1-one(双二烯-ab-酮，1a)，其锌配合物(2和3)，1，15，21，22-tetrahydro-19-(4-hexyloxybenzoyl)-5，10，15-tri(4-hexyloxy)phenyl-15-hydroxybilin-1-one(C6-双二烯酮，1b)，1，15，21，22-tetrahydro-19-(4-nonyloxybenzoyl)-5，10，15-tri(4-nonyloxy)phenyl-15-hydroxybilin-1-one(C9-双二烯酮，1c)，1，15，使用21，22-tetrahydro-19-(4-dodecyloxybenzoyl)-5，10，15-tri(4-dodecyloxy)phenyl-15-hydroxybilin-1-one(C12-胆二烯酮，1D)和1，15，21，22-tetrahydro-19-(3，5-didodecyloxybenzoyl)-5，10，15-tri(3，5-二十二氧基-苯基-15-羟基胆碱-1-酮(1E)。作为卟啉，使用5，10，15，20-四苯基卟啉(4a)和5，10，15，20-四(4-甲氧基苯基)卟啉(4b)。测定了中孔二氧化硅的等温吸附曲线，发现1a>；1b>；1c>；1d>；2的吸附顺序为：1a>；1b>；1d>；2，而1e、4a和4b均未被介孔二氧化硅吸附。直径为4.0 nm的介孔二氧化硅吸附的双二烯酮最多。在四氢呋喃、丙酮和乙醇中未观察到吸附。孔径为2.3 nm的介孔二氧化硅对1C和1D均无吸附作用。这些结果表明，吸附是由氢键等极性相互作用驱动的，即使是具有柔性烷基链的分子也观察到了尺寸排斥效应。随着温度从25℃升高到35℃，吸附的双二烯酮的量增加。在80℃时，由于介孔二氧化硅的酸性，吸附导致双二烯-AB-酮脱水为双二烯-ABC-酮。
The adsorption of linear tetrapyrroles and porphyrins to mesoporous silicas with pore diameters of 2.3, 2.7, 4.0, and 7.0nm from a benzene solution was investigated. As linear tetrapyrroles, 1,15,21,22-tetrahydro-19-benzoyl-5,10,15-triphenyl-15-hydroxybilin-1-one (biladien-ab-one, 1a), its zinc complexes (2 and 3), 1,15,21,22-tetrahydro-19-(4-hexyloxybenzoyl)-5,10,15-tri(4-hexyloxy)phenyl-15-hydroxybilin-1-one (C6-biladienone, 1b), 1,15,21,22-tetrahydro-19-(4-nonyloxybenzoyl)-5,10,15-tri(4-nonyloxy)phenyl-15-hydroxybilin-1-one (C9-biladienone, 1c), 1,15, 21,22-tetrahydro-19-(4-dodecyloxybenzoyl)-5,10,15-tri(4-dodecyloxy)phenyl-15-hydroxybilin-1-one (C12-biladienone, 1d), and 1,15,21,22-tetrahydro-19-(3,5-didodecyloxybenzoyl)-5,10,15-tri(3, 5-di-dodecyloxy)phenyl-15-hydroxybilin-1-one (1e) were employed. As porphyrins, 5,10,15,20-tetraphenylporphyrin (4a) and 5,10,15,20-tetra(4-methoxyphenyl)porphyrin (4b) were used. The isothermal adsorption curves were determined, showing that the amount of adsorption decreases in the order, 1a>1b>1c>1d>2, while neither 1e, 4a, nor 4b were adsorbed to mesoporous silicas. Mesoporous silica with the diameter of 4.0nm adsorbed the largest amounts of biladienones. The adsorption was not observed in THF, acetone or ethanol. Neither 1c nor 1d was adsorbed to mesoporous silica with the pore diameter of 2.3nm. These results indicate that the absorption is driven by polar interactions such as hydrogen bonding, and size exclusion effects are observed even for a molecule with flexible alkyl chains. The amount of adsorbed biladienone increased as the temperature was raised from 25 to 35°C. The adsorption of biladien-ab-ones at 80°C caused dehydration of biladien-ab-one to bilatrien-abc-one due to the acidity of the mesoporous silica.