As with all nanomaterials, a large fraction of the atoms in carbon nanotubes (CNTs) reside at or near the surface. Consequently, surface chemistry will play a crucial role in determining the fate and transport of CNTs in aquatic environments. Frequently, oxygen-containing functional groups (surface oxides) are deliberately grafted into the CNT surface to promote colloidal stability. To study the influence that both the oxygen concentration and the oxygen functional-group distribution have on the colloidal stability of multiwalled carbon nanotubes (MWCNTs), a suite of oxidized MWCNTs (O-MWCNTs) were created using different oxidizing agents and reaction conditions. Stable colloidal suspensions were prepared by low-power sonication of O-MWCNT powders in Milli-Q water. Results from TEM, AFM, DLS, and XPS measurements revealed that, irrespective of the surface chemistry, the colloidal suspensions were composed of individual nanotubes with comparable length distributions. The critical coagulation concentrations (CCC) of O-MWCNTs that exhibited different surface chemistries were measured with time-resolved dynamic light scattering (TR-DLS) using NaCl as the electrolyte. Over a range of environmentally relevant pH values, linear correlations were found to exist between the CCC, total oxygen concentration, and surface charge of O-MWCNTs. In contrast to surface charge, electrophoretic mobility did not prove to be a useful metric of colloidal stability. Information obtained from chemical derivatization studies, carried out in conjunction with XPS, revealed that the distribution of oxygen-containing functional groups also influences the colloidal stability of O-MWCNTs, with carboxylic acid groups playing the most important role. This study highlights the fact that quantitative relationships can be developed to rationalize the influence of surface chemistry on the behavior of nanomaterials in aquatic environments. Full Article

Grafting oxygen-containing functional groups onto carbon nanotubes (CNTs) by acid treatment improves their dispersion in aqueous solutions, but there is a lack of quantitative information on the colloidal properties of oxidized CNTs. We have studied the influence that pH and electrolytes have in determining the colloidal stability of oxidized multiwalled carbon nanotubes (O-MWCNTs), prepared by refluxing pristine MWCNTs in nitric acid. The acid-treated MWCNTs contained oxygen predominantly in the form of carboxyl groups. Colloidal suspensions of O-MWCNTs were prepared by low-power sonication and contained negatively charged, individual MWCNTs with an average length of approximately 650 nm. Time-resolved dynamic light scattering revealed that the aggregation rate of O-MWCNTs exhibited both reaction and mass-transport limited regimes in the presence of different electrolytes and as a function of pH. Particle stability profiles constructed from aggregation rate data allowed for the determination of critical coagulation concentrations (CCC), a metric of colloidal stability. The CCC values of O-MWCNTs varied with counterion concentration and valence in a manner consistentwith DLVO theory. Potentiometric measurements of surface charge correlated well with the observed pH-dependent variations in the O-MWCNT's colloidal stability. Electrophoretic mobility was also a diagnostic of particle stability, but only in neutral and acidic conditions. Full Article

As greater quantities of carbon nanotubes (CNTs) enter the environment, they will have an increasingly important effect on the availability and transport of aqueous contaminants. As a consequence of purification, deliberate surface functionalization, and/or exposure to oxidizing agents after release to the environment, CNTs often contain surface oxides (i.e., oxygen containing functional groups). To probe the influence that surface oxides exert on CNT sorption properties, multiwalled CNTs (MWCNTs) with varying oxygen concentrations were studied with respect to their sorption properties toward naphthalene. For pristine (as-received) MWCNTs, the sorption capacity was intermediate between that of a natural char and a granular activated carbon. Sorption data also reveal that a linear relationship exists between the oxygen content of MWCNTs and their maximum adsorption capacity for naphthalene, with 10% surface oxygen concentration resulting in a roughly 70% decrease in maximum adsorption capacity. The relative distribution of sorption energies, as characterized by Freundlich isotherm exponents was, however, unaffected by oxidation. Thus, the data are consistent with the idea that incorporated surface oxides create polar regions that reduce the surface area available for naphthalene sorption. These results highlight the important role of surface chemistry in controlling the environmental properties of CNTs. Full Article

The microscopic structure of carbonaceous surfaces exposed to natural organic matter (NOM) under aqueous conditions has been explored using atomic force microscopy (AFM). Dismal Swamp Water was used as the NOM source, while highly ordered pyrolytic graphite (HOPG) served as a surrogate for the graphene sheets that characterize the surface of many carbonaceous materials in aquatic environments. Under acidic conditions, the HOPG surface was covered with a densely packed monolayer of NOM molecules. In some cases, aggregates of well-defined, individual NOM molecules were observed that exhibited a degree of registry with respect to the HOPG substrate. This suggests that adsorbate-substrate interactions play a role in moderating the structure of the adsorbate layer. As the pH increased, the concentration of adsorbed NOM decreased systematically because of increasingly repulsive interactions between adsorbates. Increasing the ionic strength produced a modest increase in the concentration of adsorbed NOM. Ca2+ ions exerted a more pronounced influence on both the surface coverage of adsorbed NOM molecules and the size of individual adsorbates because of the effects of intermolecular complexation. In contrast to the spherical structures observed by AFM under aqueous conditions, adsorbed NOM formed a mixture of "ringlike" assemblies and larger aggregates upon drying. Full Article

A biologically active, high-strength tissue adhesive is needed for numerous medical applications in tissue engineering and regenerative medicine. Integration of biomaterials or implants with surrounding native tissue is crucial for both immediate functionality and long-term performance of the tissue. Here, we use the biopolymer chondroitin sulphate (CS), one of the major components of cartilage extracellular matrix, to develop a novel bioadhesive that is readily applied and acts quickly. CS was chemically functionalized with methacrylate and aldehyde groups on the polysaccharide backbone to chemically bridge biomaterials and tissue proteins via a twofold covalent link. Three-dimensional hydrogels (with and without cells) bonded to articular cartilage defects. In in vitro and in vivo functional studies this approach led to mechanical stability of the hydrogel and tissue repair in cartilage defects. Full Article