Surface PEGylation of Silver Nanoparticles: Kinetics of Simultaneous Surface Dissolution and Molecular Desorption

A quantitative study of the stability of silver nanoparticles (AgNPs) conjugated with thiolated polyethylene glycol (SH-PEG) was conducted using gas-phase ion-mobility and mass analyses. The extents of aggregation and surface dissolution of AgNPs, as well as the amount of SH-PEG adsorption and desorption, were able to be characterized simultaneously for the kinetic study. The results show that the SH-PEG with a molecular mass of 6 kg/mol (SH-PEG6K) was able to adsorb to the surface of AgNP to form PEG6K-HS-AgNP conjugates, with the maximum surface adsorbate density of ∼0.10 nm^–2. The equilibrium binding constant for SH-PEG6K on AgNPs was calculated as ∼(4.4 ± 0.9) × 10⁵ L/mol, suggesting a strong affinity due to thiol bonding to the AgNP surface. The formation of SH-PEG6K corona prevented PEG6K-HS-AgNP conjugates from aggregation under the acidic environment (pH 1.5), but dissolution of core AgNPs occurred following a first-order reaction. The rate constant of Ag dissolution from PEG6K-HS-AgNP was independent of the starting surface packing density of SH-PEG6K on AgNP (σ₀), indicating that the interactions of H⁺ with core AgNP were not interfered by the presence of SH-PEG6K corona. The surface packing density of SH-PEG6K decreased simultaneously following a first-order reaction, and the desorption rate constant of SH-PEG6K from the conjugates was proportional to σ₀. Our work presents the first quantitative study to illustrate the complex mechanism that involves simultaneous aggregation and dissolution of core AgNPs in combination with adsorption and desorption of SH-PEG. This work also provides a prototype method of coupled experimental scheme to quantify the change of particle mass versus the corresponding surface density of functional molecular species on nanoparticles

Quantifying Nanosheet Graphene Oxide Using Electrospray-Differential Mobility Analysis

We report a high-resolution, traceable method to quantify number concentrations and dimensional properties of nanosheet graphene oxide (N-GO) colloids using electrospray-differential mobility analysis (ES-DMA). Transmission electron microscopy (TEM) was employed orthogonally to provide complementary data and imagery of N-GOs. Results show that the equivalent mobility sizes, size distributions, and number concentrations of N-GOs were able to be successfully measured by ES-DMA. Colloidal stability and filtration efficiency of N-GOs were shown to be effectively characterized based on the change of size distributions and number concentrations. Through the use of an analytical model, the DMA data were able to be converted into lateral size distributions, showing the average lateral size of N-GOs was ∼32 nm with an estimated thickness ∼0.8 nm. This prototype study demonstrates the proof of concept of using ES-DMA to quantitatively characterize N-GOs and provides traceability for applications involving the formulation of N-GOs

Protein–Silver Nanoparticle Interactions to Colloidal Stability in Acidic Environments

We report a kinetic study of Ag nanoparticles (AgNPs) under acidic environments (i.e., pH 2.3 to pH ≈7) and systematically investigate the impact of protein interactions [i.e., bovine serum albumin (BSA) as representative] to the colloidal stability of AgNPs. Electrospray-differential mobility analysis (ES-DMA) was used to characterize the particle size distributions and the number concentrations of AgNPs. Transmission electron microscopy was employed orthogonally to provide visualization of AgNPs. For unconjugated AgNPs, the extent of aggregation, or the average particle size, was shown to be increased significantly with an increase of acidity, where a partial coalescence was found between the primary particles of unconjugated AgNP clusters. Aggregation rate constant, <i>k</i>_D, was also shown to be proportional to acidity, following a correlation of log­(<i>k</i>_D) = −1.627­(pH)–9.3715. Using ES-DMA, we observe BSA had a strong binding affinity (equilibrium binding constant, ≈ 1.1 × 10⁶ L/mol) to the surface of AgNPs, with an estimated maximum molecular surface density of ≈0.012 nm^–2. BSA-functionalized AgNPs exhibited highly-improved colloidal stability compared to the unconjugated AgNPs under acidic environments, where both the acid-induced interfacial dissolution and the particle aggregation became negligible. Results confirm a complex mechanism of colloidal stability of AgNPs: the aggregation process was shown to be dominant, and the formation of BSA corona on AgNPs suppressed both particle aggregation and interfacial dissolution of AgNP samples under acidic environments