pH-Sensitive Dispersion and Debundling of Single-Walled Carbon Nanotubes: Lysozyme as a Tool

• Published in: Small (Weinheim an der Bergstrasse, Germany) Vol. 2; no. 3; pp. 406 - 412
• Main Authors: Nepal, Dhriti, Geckeler, Kurt E.
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 01.03.2006; WILEY‐VCH Verlag
• Subjects: carbon nanotubes; Colloids - chemistry; Crystallization - methods; dispersion; Hydrogen-Ion Concentration; Macromolecular Substances - chemistry; Materials Testing; Molecular Conformation; Muramidase - chemistry; Nanotechnology - methods; Nanotubes, Carbon - chemistry; Nanotubes, Carbon - ultrastructure; Particle Size; pH sensitivity; Phase Transition; photoluminescence; protein design
• ISSN: 1613-6810; 1613-6829
• DOI: 10.1002/smll.200500351

Highly dispersed and debundled carbon nanotubes were prepared in an aqueous solution of lysozyme using a combination of ultrasonication and ultracentrifugation. The product is a pH‐sensitive dispersion, which remains in a highly dispersed state at pH<8 and pH>11, but in an aggregated state at pH 8–11. Photoluminescence measurements show that by changing the pH value, a reversible conversion of the highly dispersed state to the aggregated state (or vice versa) could be observed. Circular dichromism analysis confirmed that the secondary structure, as well as the majority of the tertiary structure, remains intact. Some lysozyme molecules were irreversibly bound to the nanotubes, which is possibly due to π–π or hydrophobic interactions. However, these interactions alone are not enough to produce fine dispersions of the nanotubes. Protonated amine interactions on the defect sites of the nanotubes play a vital role in the stabilization of the nanotubes below the isoelectric point and amine adsorption on the sidewalls of nanotubes occurs in cases where the pH value is higher than the isoelectric point. Lysozyme‐stabilized carbon nanotubes are highly disperse in aqueous solution, and exhibit pH‐sensitive emission. At pH 12.5, a typical emission pattern for individual, isolated nanotubes is obtained, which is not observed at pH 9.0 (see Figure). However, readjusting the pH value back at 12.5 recovered the emission properties. Such pH‐sensitive reversibility in the dispersions holds great promise in the development of optical pH sensors.