Functionalization of carbon nanotubes

Carbon nanotubes have unique properties that make them attractive for different engineering applications. However, because of their chemical inertness, carbon nanotubes have to be functionalized in order to acquire additional physico-chemical properties. Large multiwalled carbon nanotubes are different from fullerenes and singlewalled nanotubes because the stresses in their walls are almost relaxed while most chemical methods for fullerene functionalization exploit this effect of stressed bonds. The objective of this work is to develop new methods for functionalization of multiwalled carbon nanotubes. This work is dedicated to study two functionalization methods. The first deals with physico-chemical functionalization by filling the nanotube interior with colloidal suspensions. Irreversible adsorption of functional nanoparticles on the nanotube wall leads to the nanotube functionalization. The second method is purely chemical functionalization, which uses the reaction of cyclopropanation to break [pi] -bonds in the benzene rings of the nanotubes with formation of new [sigma]-bonds with deprotonated malonate. This so-called Bingel reaction has been used in fullerene chemistry and in this work was applied for the first time to functionalize multiwalled carbon nanotubes. While capillary filling of carbon nanotubes was known long ago, the research community was skeptical about possibility of engulfing nanoparticles into nanotubes by capillary forces. We developed and implemented capillary method to fill nanotubes with different nanoparticles. Using this method, magnetic carbon nanotubes were produced for the first time. Synthesized nanotubes have very high magnetic moment and allow to manipulate them by magnetic field. These magnetic nanotubes have been successfully used in fabrication of carbon nanotube-tipped pipettes for biological probes. The Bingel reaction was studied on three sets of multiwalled carbon nanotubes with diameters: 20nm, 100nm, and 300nm. To estimate the degree of Bingel functionalization, the chemical tagging of gold nanoparticles to the malonated nanotubes was used. Gold was attached using the sulfur-gold bridges formed after the reaction of transesterification of malonated tubes with 2(methylthio)ethanol. We found that the critical size for Bingel reaction to occur along the whole nanotube wall is less than 200 nm. Larger nanotubes could be also Bingel modified, but their chemical activity is mostly observed at the nanotube ends.