In situ photopolymerization of a polymerizable poly(ethylene glycol)-covered phospholipid monolayer on a methacryloyl-terminated substrate.
In situ photopolymerization of a polymerizable poly(ethylene glycol)-covered phospholipid monolayer on a methacryloyl-terminated substrate.
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DOI：
10.1021/la049959g
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发表时间：
2004-05
期刊：
影响因子：
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通讯作者：
Kwangmeyung Kim;K. Shin;Hyun-Kyoung Kim;Chulhee Kim;Y. Byun
中科院分区：
文献类型：
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作者：
Kwangmeyung Kim;K. Shin;Hyun-Kyoung Kim;Chulhee Kim;Y. Byun
我们已经制备了一个化学锚定单分子层的聚乙二醇（聚（乙二醇））和磷脂混合物（PEG/磷脂）的甲基丙烯酰基封端的基板上通过原位光聚合。分别用12-（丙烯酰氧基）-1-十二烷酸和12-（丙烯酰氧基）-1-十二醇对磷脂和聚乙二醇进行改性，合成了单丙烯酰磷脂（丙烯酰-PC，1-棕榈酰-2-[12-（丙烯酰氧基）十二烷酰基]-sn-甘油-3-磷酸胆碱）和单丙烯酰聚乙二醇（丙烯酰-PEG，12-（丙烯酰氧基）十二烷酰基-PEG）。表面压力-面积（pi-A）等温线表明，丙烯酰-PEG分子在磷脂单层中是稳定的，并且它们可以在空气/水界面处均匀地插入磷脂单层中。将10 mol %的丙烯酰-PEG加入磷脂囊泡中，通过囊泡融合3 h，可在甲基丙烯酰封端的基底上形成PEG/磷脂单层膜。然后，这种可聚合的PEG/磷脂单层原位光聚合到甲基丙烯酰基封端的基板与曙红Y/三乙醇胺作为共引发剂。从囊泡融合时间和辐照时间两方面确定了最佳囊泡融合和辐照条件。如通过原子力显微镜和X射线反射率研究所证实的，聚合的PEG/磷脂表面形成了PEG覆盖的磷脂单层，对于基础磷脂单层和覆盖PEG层，厚度分别为3和6 nm。用X射线光电子能谱法测定了聚乙二醇和磷脂分子在甲醇洗涤前后的表面相对碳数比，结果表明聚乙二醇和磷脂分子的化学锚定效率为98%。由于牢固的化学锚定到固体表面，该聚合的PEG/磷脂单层在有机溶液中显示出良好的稳定性。
We have prepared a chemically anchored monolayer of PEG (poly(ethylene glycol)) and phospholipid mixture (PEG/phospholipid) on a methacryloyl-terminated substrate by in situ photopolymerization. Both monoacryloyl phospholipid (acryloyl-PC, 1-palmitoyl-2-[12-(acryloyloxy)dodecanoyl]-sn-glycero-3-phosphocholine) and monoacryloyl PEG (acryloyl-PEG, 12-(acryloyloxy)dodecanoyl-PEG) were synthesized by modifyingphospholipid and PEGwith 12-(acryloyloxy)-1-dodecanoic acid and 12-(acryloyloxy)-1-dodecanol, respectively. The surface pressure-area (pi-A) isotherm showed that acryloyl-PEG molecules were stable in the phospholipid monolayer and that they could be evenly inserted into a phospholipid monolayer at the air/water interface. By adding 10 mol % acryloyl-PEG into phosholipid vesicles, we could produce a PEG/phosholipid monolayer on methacryloyl-terminated substrates using vesicle fusion for 3 h. Then, this polymerizable PEG/phospholipid monolayer was in situ photopolymerized onto a methacryloyl-terminated substrate with eosin Y/triethanolamine as co-initiators. Optimal vesicle fusion and irradiation condition were determined with respect to the vesicle fusion time and duration of irradiation. As confirmed by atomic force microscopy and X-ray reflectivity studies, the polymerized PEG/phosholipid surface formed a PEG-covered phospholipid monolayer with thicknesses of 3 and 6 nm for the base phospholipid monolayer and the covering PEG layer, respectively. The chemical anchoring efficiency ofpolymerized PEG and phospholipid molecules, which was calculated by the relative carbon ratio of each surface before and after methanol washing using X-ray photoelectron spectroscopy, was 98%. This polymerized PEG/phosholipid monolayer showed good stability in organic solution due to firm chemical anchoring to a solid surface.