Modified multi-walled carbon nanotubes potentially suitable for intracellular pH measurements

Carboxylic acid functionalized multi-walled carbon nanotubes (COOH-MWCNTs) have been studied as macromolecular carriers for pH indicators to be used inside cells. The activation of carboxylic groups with thionyl chloride (SOCl2) followed by the reaction with a family of fluorescein ethylen glycol derivatives led to dyes covalently anchored to the MWCNT surface. Such a functionalization was found to preserve wholly the fluorescence properties of the dye ultimately providing higher water solubility to the modified macromolecular systems. Moreover, the use of a polyether spacer between the dye and the MWCNT surface preserved from undesired florescence quenching effects. The pH dependence of the modified nanotubes was investigated interrogating a solution of MWCNTs, the pH of which was adjusted in the range 4-9 pH units by adding drops of hydrochloric acid and sodium hydroxide. Light from LED was suitably filtered at 480 nm with a high pass-band filter and coupled to an optical fiber which illuminates the solution containing the fluorescein-functionalised MWCNTs. An optical fiber, at 90° with respect to the LED illumination, is connected with a Hamamtsu spectrum analyzer for the recording of the fluorescence spectra. The modified MWCNTs exhibited linear pH dependence in the range between 6 and 8 pH units with a sensitivity less than 0.1 pH units.