Based on tunable properties, engineered nanoparticles (NPs) hold significant promise for water treatment technologies. Motivated by concerns regarding toxicity and non-biodegradability of some nanoparticles, we explored engineered magnetite (Fe 3 O 4 ) nanoparticles with a biocompatible coating. These were prepared with a coating of rhamnolipid, a biosurfactant primarily obtained from Pseudomonas aeruginosa . By optimizing synthesis and phase transfer conditions, particles were observed to be monodispersed and stable in water under environmentally relevant pH and ionic strength values. These materials were evaluated for U( vi ) removal from water at varying dissolved inorganic carbon and pH conditions. The rhamnolipid-coated iron oxide nanoparticles (IONPs) showed high sorption capacities at pH 6 and pH 8 in both carbonate-free systems and systems in equilibrium with atmospheric CO 2 . Equilibrium sorption behavior was interpreted using surface complexation modeling (SCM). Two models (diffuse double layer and non-electrostatic) were evaluated for their ability to account for U( vi ) binding to the carboxyl groups of the rhamnolipid coating as a function of the pH, total U( vi ) loading, and dissolved inorganic carbon concentration. The diffuse double layer model provided the best simulation of the adsorption data and was sensitive to U( vi ) loadings as it accounted for the change in the surface charge associated with U( vi ) adsorption.
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Measurement of the surface hydrophobicity of engineered nanoparticles using an atomic force microscope
Determination of the surface hydrophobicity or wettability of nanomaterials and nanoparticles (NPs) is often challenged by the heterogeneous properties of NPs that vary with particle size, shape, surface charge, aggregation states, and surface sorption or coating. This study first summarized inherent limitations of the water contact angle, octanol–water partition coefficient ( K ow ) and surface adsorption of probe molecules in probing nanomaterial hydrophobicity. Then, we demonstrated the principle of a scanning probe method based on atomic force microscopy (AFM) for the local surface hydrophobicity measurement. Specifically, we measured the adhesion forces between functionalized AFM tips and self-assembled monolayers (SAMs) to establish a linear relationship between the adhesion forces and water contact angles based on the continuum thermodynamic approach (CTA). This relationship was used to determine the local surface hydrophobicity of seven different NPs ( i.e. , TiO 2 , ZnO, SiO 2 , CuO, CeO 2 , α-Fe 2 O 3 , and Ag), which agreed well with bulk contact angles of these NPs. Some discrepancies were observed for Fe 2 O 3 , CeO 2 and SiO 2 NPs, probably because of surface hydration and roughness effects. Moreover, the solution pH and ionic strength had negligible effects on the adhesion forces between the AFM tip and MWCNTs or C 60 , indicating that the hydrophobicity of carbonaceous nanomaterials is not influenced by pH or ionic strength (IS). By contrast, natural organic matter (NOM) appreciably decreased the hydrophobicity of MWCNTs and C 60 due to surface coating of hydrophilic NOM. This scanning probe method has been proved to be reliable and robust toward the accurate measurement of the nanoscale hydrophobicity of individual NPs or nanomaterials in liquid environments.
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- NSF-PAR ID:
- 10100822
- Date Published:
- Journal Name:
- Physical Chemistry Chemical Physics
- Volume:
- 20
- Issue:
- 37
- ISSN:
- 1463-9076
- Page Range / eLocation ID:
- 24434 to 24443
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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To unravel fouling and defouling mechanisms of protein, saccharides and natural organic matters (NOM) on polymeric membrane during filtration, this study investigated filtration characteristics on polyvinyl chloride (PVC) ultrafiltration membranes with bovine serum albumin, dextran, humic acid as model foulants. Membrane fouling and defouling performances were analyzed through monitoring the flux decline during filtration and flux recovery during physical backwash. Physico-chemical properties (e.g., hydrophobicity and surface charge) of PVC membrane and foulants were characterized, which were used in the extended Derjaguin–Landau–Verwey–Overbeek (EDLVO) theory to calculate the interaction energies between membrane foulant and foulant-foulant. The results showed that at the later filtration stages the fouling rate was strongly correlated with the deposition rate, which was determined by the interaction energy profile calculated by EDLVO. Moreover, the adhesion forces of membrane–foulant and foulant–foulant were further measured by atomic force microscopy (AFM) with modified colloidal probes. A positive correlation (R2 =0.845) between particle detachment rate (determined by adhesion force) and defouling rate was developed for BSA and HA foulants that led to cake layer formation. By contrast, dextran defouling rate was off this correlation as dextran partially clogged membrane pores due to its smaller size.more » « less
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Abstract The pathogenicity and antimicrobial properties of engineered nanomaterials (ENMs) are relatively well studied. However, less is known regarding the interactions of ENMs and agriculturally beneficial microorganisms that affect food security. Nanoceria (CeO2nanoparticles (NPs)), multiwall carbon nanotubes (MWCNTs), graphene nanoplatelets (GNPs), and carbon black (CB) have been previously shown to inhibit symbiotic N2fixation in soybeans, but direct rhizobial susceptibility is uncertain. Here,
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- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/c8cp04676j
