Unusual Emission of Polystyrene-Based Alternating Copolymers Incorporating Aminobutyl Maleimide Fluorophore-Containing Polyhedral Oligomeric Silsesquioxane Nanoparticles
Unusual Emission of Polystyrene-Based Alternating Copolymers Incorporating Aminobutyl Maleimide Fluorophore-Containing Polyhedral Oligomeric Silsesquioxane Nanoparticles
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DOI：
10.3390/polym9030103
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发表时间：
2017-03
期刊：
影响因子：
5
通讯作者：
M. Mohamed;Yu-Ru Jheng;Shu-Ling Yeh;Tao Chen;S. Kuo
中科院分区：
文献类型：
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作者：
M. Mohamed;Yu-Ru Jheng;Shu-Ling Yeh;Tao Chen;S. Kuo
在这项研究中，我们合成了一种不寻常的2-氨基丁基马来酰亚胺多面体低聚倍半硅氧烷(MIPOSS-NHBu)单体，没有传统的荧光基团。然后，以偶氮二异丁腈为引发剂，四氢呋喃为溶剂，通过自由基共聚合制备了聚(苯乙烯-ALT-2-氨基丁基马来酰亚胺异丁基POSS)[聚(S-ALT-MIPOSS-NHBu)]和聚(4-乙酰氧基苯乙烯-ALT-2-氨基丁基马来酰亚胺异丁基POSS)[聚(AS-ALT-MIPOSS-NHBu)]共聚物。通过乙酰氧基肼解聚(AS-ALT-MIPOSS-NHBu)制备了聚(4-羟基苯乙烯-ALT-2-氨基丁基马来酰亚胺异丁基POSS)[Poly(HS-ALT-MIPOSS-NHBu)]共聚物。我们利用~1H、~(13)C和~(29)Si核磁共振光谱、傅里叶变换红外光谱、差示扫描量热法和光致发光光谱研究了单体和新型含POSS交替共聚物的结构、热性能和光学性能。氨基和二氢呋喃-2，5-二酮之间的分子内氢键以及MIPOSS-NHBu单元中POSS纳米粒子锁定的C=O基团的聚集限制了高分子链的分子内运动，使其显示出强烈的发光。因此，MIPOSS-NHBu单体和聚(AS-ALT-MIPOSS-NHBu)共聚物均具有良好的选择性，在金属离子检测中具有潜在的应用前景。
In this study, we synthesized an unusual 2-aminobutyl maleimide isobutyl polyhedral oligomeric silsesquioxane (MIPOSS-NHBu) monomer lacking conventional fluorescent groups. We then prepared poly(styrene-alt-2-aminobutyl maleimide isobutyl POSS) [poly(S-alt-MIPOSS-NHBu)] and poly(4-acetoxystyrene-alt-2-aminobutyl maleimide isobutyl POSS) [poly(AS-alt-MIPOSS-NHBu)] copolymers through facile free radical copolymerizations using azobisisobutyronitrile as the initiator and tetrahydrofuran as the solvent. A poly(4-hydroxystyrene-alt-2-aminobutyl maleimide isobutyl POSS) [poly(HS-alt-MIPOSS-NHBu)] copolymer was prepared through acetoxyl hydrazinolysis of poly(AS-alt-MIPOSS-NHBu). We employed 1H, 13C, and 29Si nuclear magnetic resonance spectroscopy; Fourier transform infrared spectroscopy; differential scanning calorimetry; and photoluminescence spectroscopy to investigate the structures and the thermal and optical properties of the monomers and novel POSS-containing alternating copolymers. Intramolecular hydrogen bonding between the amino and dihydrofuran-2,5-dione group and clustering of the locked C=O groups from the POSS nanoparticles in the MIPOSS-NHBu units restricted the intramolecular motion of the polymer chain, causing it to exhibit strong light emission. As a result, the MIPOSS-NHBu monomer and the poly(AS-alt-MIPOSS-NHBu) copolymer both have potential applicability in the detection of metal ions with good selectivity.