Dynamic light scattering is a method that depends on the interaction of light with particles. This method can be used for measurements of narrow particle size distributions especially in the range of 2–500 nm. Sample polydispersity can distort the results, and we could not see the real populations of particles because big particles presented in the sample can screen smaller ones. Although the theory and mathematical basics of DLS technique are already well known, little has been done to determine its limits experimentally. The size and size distribution of artificially prepared polydisperse silver nanoparticles (NPs) colloids were studied using dynamic light scattering (DLS) and ultraviolet‐visible (UV‐Vis) spectroscopy. Polydisperse colloids were prepared based on the mixture of chemically synthesized monodisperse colloids well characterized by atomic force microscopy (AFM), transmission electron microscopy (TEM), DLS, and UV‐Vis spectroscopy. Analysis of the DLS results obtained for polydisperse colloids reveals that several percent of the volume content of bigger NPs could screen completely the presence of smaller ones. The presented results could be extremely important from nanoparticles metrology point of view and should help to understand experimental data especially for the one who works with DLS and/or UV‐Vis only.

This paper describes the influence of the chain length and the functional group steric accessibility of thiols modifiers on the phase transfer process efficiency of water synthesized gold nanoparticles (AuNPs) to toluene. The following thiols were tested: 1-decanethiol, 1,1-dimethyldecanethiol, 1-dodecanethiol, 1-tetradecanethiol and 1-oktadecanethiol. Nanoparticles (NPs) synthesized in water were precisely characterized before the phase transfer process using Atomic Force Microscopy (AFM) and Transmission Electron Microscopy (TEM). The optical properties of AuNPs before and after the phase transfer were studied by the UV-Vis spectroscopy. Additionally, the particle size and size distribution before and after the phase transfer of nanoparticles were investigated using Dynamic Light Scattering (DLS). It turned out that the modification of NPs surface was not effective in the case of 1,1-dimethyldecanethiol, probably because of the difficult steric accessibility of the thiol functional group to NPs surface. Consequently, the effective phase transfer of AuNPs from water to toluene did not occur. In toluene the most stable were nanoparticles modified with 1-decanethiol, 1-dodecanethiol and 1-tetradecanethiol.