Park Hye Jin, Kim Junkyung, Chang Ji Young, Theato Patrick
Department of Materials Science and Engineering, Seoul National University, Seoul, Korea.
Langmuir. 2008 Sep 16;24(18):10467-73. doi: 10.1021/la801341t. Epub 2008 Aug 21.
A multilayered film was prepared by layer-by-layer (LBL) assembly of active ester modified multiwalled carbon nanotubes (MWCNTs) and poly(allylamine hydrochloride) (PAH). For this purpose, carboxylic groups on the surface of the oxidized MWCNTs were converted to the acyl chlorides by their reaction with thionyl chloride. Subsequent reaction of the acyl chlorides with pentafluorophenol formed the active esters. These active ester modified MWCNTs (MWCNTs-COOC(6)F(5)) were air-stable and moisture resistant, but showed a high reactivity toward primary or secondary amines resulting in amide bonds. For the preparation of a multilayered film, the surface of a quartz slide was first activated and sacrificial double layers of PAH and poly(sodium 4-styrene sulfonate) (PSS) were deposited. Subsequently, LBL assembly of MWCNTs-COOC(6)F(5) and PAH was then conducted on these double layers [(PAH/PSS)2]. In the process of the assembly, a reaction occurred between the active ester on the surface of MWCNTs and the amine groups of polyallylamine yielding amide bonds, which resulted in a mechanically stable thin film. A free-standing film was obtained after dissolving the sacrificial layer [(PAH/PSS)2] in a concentrated aqueous NaOH solution. The surface resistance of the multilayered film with 20 bilayers decreased to around 10 kOmega while remaining a reasonable transparency (70% at 500 nm).
通过活性酯修饰的多壁碳纳米管(MWCNTs)和聚(烯丙胺盐酸盐)(PAH)的逐层(LBL)组装制备了多层膜。为此,将氧化的MWCNTs表面的羧基通过与亚硫酰氯反应转化为酰氯。酰氯随后与五氟苯酚反应形成活性酯。这些活性酯修饰的MWCNTs(MWCNTs-COOC(6)F(5))具有空气稳定性和防潮性,但对伯胺或仲胺表现出高反应性,从而形成酰胺键。为了制备多层膜,首先对石英载玻片的表面进行活化,并沉积PAH和聚(4-苯乙烯磺酸钠)(PSS)的牺牲双层。随后,在这些双层膜[(PAH/PSS)2]上进行MWCNTs-COOC(6)F(5)和PAH的LBL组装。在组装过程中,MWCNTs表面的活性酯与聚烯丙胺的胺基之间发生反应,生成酰胺键,从而得到机械稳定的薄膜。将牺牲层[(PAH/PSS)2]溶解在浓氢氧化钠水溶液中后,得到了独立的薄膜。具有20个双层的多层膜的表面电阻降至约10 kΩ,同时保持合理的透明度(在500 nm处为70%)。