Macka Miroslav, Yang Wen-Chu, Zakaria Philip, Shitangkoon Aroonsiri, Hilder Emily F, Andersson Per, Nesterenko Pavel, Haddad Paul R
Australian Centre for Research on Separation Science, School of Chemistry, University of Tasmania, Private Bag 75, Hobart 7001, Tasmania, Australia.
J Chromatogr A. 2004 Jun 11;1039(1-2):193-9. doi: 10.1016/j.chroma.2004.03.074.
Poly(tetrafluoroethylene) (PTFE) is a material widely known for its inertness and excellent electrical properties. It is also transparent in the UV region and has a reasonable thermal conductivity. These properties make PTFE a suitable material for the separation capillary in capillary electrophoresis. Differences in the chemistry of the capillary wall compared to fused silica (FS) can make PTFE an interesting alternative to FS for some special applications. In this work, properties of a commercial PTFE capillary of approx. 100 microm i.d. were investigated, including the dependence of electroosmotic flow (EOF) on pH for unmodified and dynamically modified PTFE, optical properties, and practical aspects of use. The main problems encountered for the particular PTFE capillary used in this study were that it was mechanically too soft for routine usage and the crystallinity of the PTFE caused light scattering, leading to high background absorbance values in the low UV region. The profile of the EOF versus pH for bare PTFE surprisingly showed significantly negative EOF values at pH < 4.2, with an EOF of -30 x 10(-9) m2 V(-1) s(-1) being observed at pH 2.5. This is likely to be caused by either impurities or additives of basic character in the PTFE, so that after their protonation at acidic pH they establish a positive charge on the capillary wall and create a negative EOF. A stable cationic semi-permanent coating of poly(diallyldimethylammonium chloride) (PDDAC) could be established on the PTFE capillary and led to very similar magnitudes of EOF to those observed with FS. A hexadecanesulfonate coating produced a cathodic EOF of extremely high magnitude ranging between +90 and +110 x 10(-9) m2 s(-1) V(-1), which are values high enough to allow counter-EOF separation of high mobility inorganic anions. In addition, pH-independent micellar electrokinetic capillary chromatography (MEKC) separations could be easily realised due to hydrophobic adsorption of sodium dodecylsulfate (used to form the micelles) on the wall of the PTFE capillary. The use of polymers that would be mechanically more robust and optically transparent in the low-UV region should make such CE capillaries an interesting alternative to fused silica.
聚四氟乙烯(PTFE)是一种因其惰性和优异电学性能而广为人知的材料。它在紫外区域也是透明的,并且具有合理的热导率。这些特性使得PTFE成为毛细管电泳中分离毛细管的合适材料。与熔融石英(FS)相比,毛细管管壁化学性质的差异使得PTFE在某些特殊应用中成为FS的一个有趣替代品。在这项工作中,研究了内径约100微米的商用PTFE毛细管的性能,包括未改性和动态改性PTFE的电渗流(EOF)对pH的依赖性、光学性质以及实际使用方面。本研究中使用的特定PTFE毛细管遇到的主要问题是,它在机械性能上对于常规使用来说太软,并且PTFE的结晶性导致光散射,从而在低紫外区域产生高背景吸光度值。裸PTFE的EOF与pH曲线令人惊讶地显示,在pH < 4.2时EOF值显著为负,在pH 2.5时观察到的EOF为 -30×10⁻⁹ m² V⁻¹ s⁻¹。这可能是由PTFE中碱性的杂质或添加剂引起的,以至于它们在酸性pH下质子化后在毛细管管壁上建立正电荷并产生负EOF。可以在PTFE毛细管上建立聚二烯丙基二甲基氯化铵(PDDAC)的稳定阳离子半永久性涂层,并且导致EOF的大小与在FS上观察到的非常相似。十六烷磺酸盐涂层产生了极高大小的阴极EOF,范围在 +90至 +110×10⁻⁹ m² s⁻¹ V⁻¹之间,这些值高到足以允许对高迁移率无机阴离子进行反EOF分离。此外,由于十二烷基硫酸钠(用于形成胶束)在PTFE毛细管管壁上的疏水吸附,可以很容易地实现与pH无关的胶束电动毛细管色谱(MEKC)分离。使用在机械性能上更强健且在低紫外区域光学透明的聚合物应该会使这种CE毛细管成为熔融石英的一个有趣替代品。