Effect of pH on optical sensing with poly-L-lysine-modified nanodiamonds

Nitrogen-vacancy (NV) centers are crystallographic defects which provide diamonds with unique physical properties. The centers are known for their intensive, time-stable fluorescence, and an electron spin, which exhibits long coherence time and may be manipulated using external stimuli. Nanodiamonds containing the NV centers are promising tools in biolabeling, biosensing, and drug delivery due to the aforementioned properties of the defects combined with a chemical inertness of a core and an easily functionalized surface of the diamond. Many biochemical reactions are pH-sensitive, therefore, in order to utilize the NV centers for monitoring of such processes, the pH-dependency of the properties of the nanodiamonds needs to be well-understood. Functionalization of the nanodiamonds’ surfaces with biological molecules undergoing pH-triggered changes of conformation, e.g. poly-L-lysine, could not only increase the particles’ biocompatibility and promote cell adhesion, but also possibly enhance pH-sensitivity. In the present study, an impact of pH on the fluorescence, a zeta potential, and a contact angle of the NV centers-containing nanodiamonds dispersed in liquid media is examined. The suspensions were made of commercially available, fluorescent diamond particles in an as-received, unmodified state, and after the poly-L-lysine had been attached to their surfaces via two different procedures – in aqueous, and anhydrous environment. Values of pH of dispersion media were specifically chosen to induce diverse conformation of the poly-L-lysine: from a fully relaxed conformation, through a state of being neither wholly extended, nor helical, to a complete α-helix conformation. The intensity of the photoluminescence emitted by the NV centers has been found to depend on the pH-triggered conformation of the poly-L-lysine attached to the surfaces of the nanodiamonds. The impact of the conformation of the poly-L-lysine on the electric charge of the nanoparticles has also been analyzed. This study confirms the potential of the nitrogen-vacancy centers for optical sensing of pH-triggered processes.