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Effect of peptide secondary structure on adsorption and adsorbed film properties on end-grafted polyethylene oxide layers

机译:肽二级结构对末端接枝聚环氧乙烷层吸附和吸附膜性能的影响

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Poly-l-lysine (PLL), in α-helix or β-sheet configuration, was used as a model peptide for investigating the effect of secondary structures on adsorption events to poly(ethylene oxide) (PEO) modified surfaces formed using θ solvents. Circular dichroism results showed that the secondary structure of PLL persisted upon adsorption to Au and PEO modified Au surfaces. Quartz crystal microbalance with dissipation (QCM-D) was used to characterize the chemisorbed PEO layer in different solvents (θ and good solvents), as well as the sequential adsorption of PLL in different secondary structures (α-helix or β-sheet). QCM-D results suggest that chemisorption of PEO 750 and 2000 from θ solutions led to brushes 3.8 ± 0.1 and 4.5 ± 0.1 nm thick with layer viscosities of 9.2 ± 0.8 and 4.8 ± 0.5 cP, respectively. The average number of H2O per ethylene oxides, while in θ solvent, was determined as ~0.9 and ~1.2 for the PEO 750 and 2000 layers, respectively. Upon immersion in good solvent (as used for PLL adsorption experiments), the number of H2O per ethylene oxides increased to ~1.5 and ~2.0 for PEO 750 and 2000 films, respectively. PLL adsorbed masses for α-helix and β-sheet on Au sensors was 231 ± 5 and 1087 ± 14 ng cm-2, with layer viscosities of 2.3 ± 0.1 and 1.2 ± 0.1 cP, respectively; suggesting that the α-helix layer was more rigid, despite a smaller adsorbed mass, than that of β-sheet layers. The PEO 750 layer reduced PLL adsorbed amounts to ~10 and 12% of that on Au for α-helices and β-sheets respectively. The PLL adsorbed mass to PEO 2000 layers dropped to ~12% and 4% of that on Au, for α-helix and β-sheet respectively. No significant differences existed for the viscosities of adsorbed α-helix and β-sheet PLL on PEO surfaces. These results provide new insights into the fundamental understanding of the effects of secondary structures of peptides and proteins on their surface adsorption.
机译:以α-螺旋或β-折叠结构的聚l-赖氨酸(PLL)用作模型肽,用于研究二级结构对使用θ溶剂形成的聚环氧乙烷(PEO)改性表面的吸附事件的影响。圆二色性结果表明,PLL的二级结构在吸附到Au和PEO改性的Au表面上时仍然存在。带有耗散的石英晶体微天平(QCM-D)用于表征在不同溶剂(θ和良好溶剂)中化学吸附的PEO层的特性,以及在不同二级结构(α-螺旋或β-折叠)中PLL的顺序吸附。 QCM-D结果表明,PEO 750和2000从θ溶液中的化学吸附导致刷厚度为3.8±0.1和4.5±0.1 nm,层粘度分别为9.2±0.8和4.8±0.5 cP。在θ溶剂中,PEO 750和2000层的每环氧乙烷中H2O的平均数分别确定为〜0.9和〜1.2。浸入良好的溶剂(用于PLL吸附实验)后,PEO 750和2000薄膜的每环氧乙烷中的H2O数分别增加至〜1.5和〜2.0。在Au传感器上,用于α螺旋和β片的PLL吸附质量为231±5和1087±14 ng cm-2,层粘度分别为2.3±0.1和1.2±0.1 cP。这表明尽管吸附质量较小,但α-螺旋层比β-折叠层更坚硬。对于α-螺旋和β-片层,PEO 750层减少的PLL吸附量分别为Au上的〜10和12%。对于α-螺旋和β-片层,PLL吸附到PEO 2000层的质量分别下降到Au的〜12%和4%。 PEO表面吸附的α-螺旋和β-sheetPLL的粘度没有显着差异。这些结果为对肽和蛋白质的二级结构对其表面吸附的影响的基本理解提供了新的见解。

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