Gram-scale fractionation of nanodiamonds by density gradient ultracentrifugation

摘要

Size is a defining characteristic of nanopartides; it influences their optical and electronic properties as well as their interactions with molecules and macromolecules. Producing nanopartides with narrow size distributions remains one of the main challenges to their utilization. At this time, the number of practical approaches to optimize the size distribution of nanopartides in many interesting materials systems, including diamond nanocrystals, remains limited. Diamond nanocrystals synthesized by detonation protocols - so-called detonation nanodiamonds (DNDs) - are promising systems for drug delivery, photonics, and composites. DNDs are composed of primary particles with diameters mainly <10 nm and their aggregates (ca. 10-500 nm). Here, we introduce a large-scale approach to rate-zonal density gradient ultracentrifugation to obtain monodispersed fractions of nanopartides in high yields. We use this method to fractionate a highly concentrated and stable aqueous solution of DNDs and to investigate the size distribution of various fractions by dynamic light scattering, analytical ultracentrifugation, transmission electron microscopy and powder X-ray diffraction. This fractionation method enabled us to separate gram-scale amounts of DNDs into several size ranges within a relatively short period of time. In addition, the high product yields obtained for each fraction allowed us to apply the fractionation method iteratively to a particular size range of particles and to collect various fractions of highly monodispersed primary particles. Our method paves the way for in-depth studies of the physical and optical properties, growth, and aggregation mechanism of DNDs. Applications requiring DNDs with specific particle or aggregate sizes are now within reach.