Ligand exchange of hydrophilic molecules on the surface of hydrophobic iron oxide nanoparticles produced via thermal decomposition of chelated iron precursors is a common method for producing aqueous suspensions of particles for biomedical applications. Despite the wide use, relatively little is understood about the efficiency of ligand exchange on the surface of iron oxide nanoparticles and how much of the hydrophobic ligand is removed. To address this issue, we utilized a radiotracer technique to track the exchange of a radiolabeled (14)C-oleic acid ligand with hydrophilic ligands on the surface of magnetite nanoparticles. Iron oxide nanoparticles functionalized with (14)C-oleic acid were modified with poly(ethylene glycol) with terminal functional groups including, L-3,4-dihydroxyphenylalanine, a nitrated L-3,4-dihydroxyphenylalanine, carboxylic acid, a phosphonate, and an amine. Following ligand exchange, the nanoparticles and byproducts were analyzed using liquid scintillation counting and inductively coupled plasma mass spectroscopy. The labeled and unlabeled particles were further characterized by transmission electron microscopy and dynamic light scattering to determine particle size, hydrodynamic diameter, and zeta potential. The unlabeled particles were characterized via thermogravimetric analysis and vibrating sample magnetometry. Radioanalytical determination of the (14)C from (14)C-oleic acid was used to calculate the amount of oleic acid remaining on the surface of the particles after purification and ligand exchange. There was a significant loss of oleic acid on the surface of the particles after ligand exchange with amounts varying for the different functional binding groups on the poly(ethylene glycol). Nonetheless, all samples demonstrated some residual oleic acid associated with the particles. Quantification of the oleic acid remaining after ligand exchange reveals a binding hierarchy in which catechol derived anchor groups displace oleic acid on the surface of the nanoparticles better than the phosphonate, followed by the amine and carboxylic acid groups. Furthermore, the results show that these ligand exchange reactions do not necessarily occur to completion as is often assumed, thus leaving a residual amount of oleic acid on the surface of the particles. A thorough analysis of ligand exchange is required to develop nanoparticles that are suitable for their desired application.
Ligand exchange on the surface of hydrophobic iron oxide nanoparticles is a common method for controlling surface chemistry for a desired application. Furthermore, ligand exchange with small-molecule ligands may be necessary to obtain particles with a specific size or functionality. Understanding to what extent ligand exchange occurs and what factors affect it is important for the optimization of this critical procedure. However, quantifying the amount of exchange may be difficult because of the limitations of commonly used characterization techniques. Therefore, we utilized a radiotracer technique to track the exchange of a radiolabeled C-oleic acid ligand with hydrophilic small-molecule ligands on the surface of iron oxide nanoparticles. Iron oxide nanoparticles functionalized withC-oleic acid were modified with small-molecule ligands with terminal functional groups including catechols, phosphonates, sulfonates, thiols, carboxylic acids, and silanes. These moieties were selected because they represent the most commonly used ligands for this procedure. The effectiveness of these molecules was compared using both procedures widely found in the literature and using a standardized procedure. After ligand exchange, the nanoparticles were analyzed using liquid scintillation counting (LSC) and inductively coupled plasma-mass spectrometry. The labeled and unlabeled particles were further characterized by transmission electron microscopy (TEM) and dynamic light scattering (DLS) to determine the particle size, hydrodynamic diameter, and zeta potential. The unlabeled particles were characterized via attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) and vibrating sample magnetometry (VSM) to confirm the presence of the small molecules on the particles and verify the magnetic properties, respectively. Radioanalytical determination of C-oleic acid was used to calculate the total amount of oleic acid remaining on the surface of the particles after ligand exchange. The results revealed that the ligand-exchange reactions performed using widely cited procedures did not go to completion. Residual oleic acid remained on the particles after these reactions and the reactions using a standardized protocol. A comparison of the ligand-exchange procedures indicated that the binding moiety, multidenticity, reaction time, temperature, and presence of a catalyst impacted the extent of exchange. Quantification of the oleic acid remaining after ligand exchange revealed a binding hierarchy in which catechol-derived anchor groups displace the most oleic acid on the surface of the nanoparticles and the thiol group displaces the least amount of oleic acid. Thorough characterization of ligand exchange is required to develop nanoparticles suitable for their intended application.
Superfine powdered activated carbon (S-PAC) is an adsorbent material with particle size between roughly 0.1-1 μm. This is about an order of magnitude smaller than conventional powdered activated carbon (PAC), typically 10-50 μm. S-PAC has been shown to outperform PAC for adsorption of various drinking water contaminants. However, variation in S-PAC production methods and limited material characterization in prior studies lead to questions of how S-PAC characteristics deviate from that of its parent PAC. In this study, a wet mill filled with 0.3-0.5 mm yttrium-stabilized zirconium oxide grinding beads was used to produce S-PAC from seven commercially available activated carbons of various source materials, including two coal types, coconut shell, and wood. Particle sizes were varied by changing the milling time, keeping mill power, batch volume, and recirculation rate constant. As expected, mean particle size decreased with longer milling. A lignite coal-based carbon had the smallest mean particle diameter at 169 nm, while the wood-based carbon had the largest at 440 nm. The wood and coconut-shell based carbons had the highest resistance to milling. Specific surface area and pore volume distributions were generally unchanged with increased milling time. Changes in the point of zero charge (pH(PZC)) and oxygen content of the milled carbons were found to correlate with an increasing specific external surface area. However, the isoelectric point (pH(IEP)), which measures only external surfaces, was unchanged with milling and also much lower in value than pH(PZC). It is likely that the outer surface is easily oxidized while internal surfaces remain largely unchanged, which results in a lower average pH as measured by pH(PZC).
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