Dispersion stability, ligand structure and conformation, and SERS activities of 1-alkanethiol (C n H 2n+1 SH, n = 2−14) functionalized gold and silver nanoparticles (AuNPs and AgNPs) were studied as a function of alkanethiol carbon chain length and nanoparticle (NP) type and size. The dispersion stability of alkanethiol functionalized NPs in water increases with increasing alkanethiol chain length and NP size, and the stabilities of the alkanethiol-containing AuNPs are higher than their AgNP counterparts. C 3 H 7 SH and longer alkanethiols are highly ordered on AgNPs but disordered on AuNPs. The SERS intensity of the C−S stretch band for the model alkanethiols on AgNPs and AuNPs decays exponentially (I = I 0 exp(−N c /N 0 )) with increasing number of carbon atoms (N c ). The empirical decay length N 0 , in terms of the number of the carbon atoms, is 1.29, 0.53, and 0.10 for AgNPs with diameters of 50, 30, and 10 nm, respectively. This decay length is less than 1 for AuNPs of difference sizes. These results show that changing the NP gap size by a distance equivalent to a single chemical bond can have a significant impact on the NP integrated SERS activities.

Studies of protein and organothiol interactions with silver nanoparticles (AgNPs) are important for understanding AgNP nanotoxicity, antimicrobial activity, and material fabrications. Reported herein is a systematic investigation of the effects of both reduced and oxidized protein cysteine residues on protein interactions with AgNPs. The model proteins included wild-type and mutated protein GB3 variants that contain 0, 1, or 2 reduced cysteine residues, respectively. Bovine serum albumin (BSA) that contains a total of 34 oxidized (disulfide-linked) cysteine residues and one reduced cysteine residue was also included. Protein cysteine content has no detectable effect on the kinetics of protein/AgNP binding. However, only proteins that contain reduced cysteine residues induce significant AgNP dissolution. Proteins can slow down, but do not prevent the AgNP dissolution induced by subsequently added organothiols. The insights provided in this work are important to the mechanistic understanding of AgNP stability in biofluids that are rich in proteins and amino acid thiols.

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Previous researchers proposed that thiolated poly(ethylene glycol) (PEG-SH) adopts a “mushroom-like” conformation on gold nanoparticles (AuNPs) in water. However, information regarding the size and permeability of the PEG-SH mushroom caps and surface area passivated by the PEG-SH mushroom stems are unavailable. Reported herein is our finding that AuNPs that are covered by saturation packed PEG-SHs all have large fractions of AuNP surface area available for ligand adsorption and exchange. The model ligands adenine and 2-mercaptobenzimidazole (2-MBI) can rapidly penetrate the PEG-SH overlayer and adsorb onto the AuNP surface. Most of the ligand adsorption and exchange occurs within the first minutes of the ligand addition. The fraction of AuNP surface area passivated by saturation packed model PEG-SHs are ∼25%, ∼20%, and ∼9% for PEG-SHs with molecular weights of 2000, 5000, and 30 000 g/mol, respectively. Localized surface plasmonic resonance and dynamic light scattering show that the PEG-SH overlayer is drastically more loosely packed than the protein bovine serum albumin on AuNPs. Studies investigating the effect of aging the AuNP/PEG-SH mixtures on subsequent adenine adsorption onto the pegylated AuNPs revealed that PEG-SHs reach approximately a steady-state binding on AuNPs within 3 h of sample incubation. This work sheds new insights into the kinetics, structures, and conformations of PEG-SHs on AuNPs and demonstrates that pegylated AuNPs can be used as an important platform for studying ligand interaction with AuNPs. In addition, it also opens a new avenue for fabrication of multicomponent functionalized nanoparticles.

Determination of the true surface areas, concentrations, and particle sizes of gold nanoparticles (AuNPs) is a challenging issue due to the nanoparticle morphological irregularity, surface roughness, and size distributions. A ligand adsorption-based technique for determining AuNP surface areas in solution is reported. Using a water-soluble, stable, and highly UV-vis active organothiol, 2-mercaptobenzimidazole (MBI), as the probe ligand, we demonstrated that the amount of ligand adsorbed is proportional to the AuNP surface area. The equivalent spherical AuNP sizes and concentrations were determined by combining the MBI adsorption measurement with Au(3+) quantification of aqua regia-digested AuNPs. The experimental results from the MBI adsorption method for a series of commercial colloidal AuNPs with nominal diameters of 10, 30, 50, and 90 nm were compared with those determined using dynamic light scattering, transmission electron microscopy, and localized surface plasmonic resonance methods. The ligand adsorption-based technique is highly reproducible and simple to implement. It only requires a UV-vis spectrophotometer for characterization of in-house-prepared AuNPs.