Surface chemistry of metal oxide nanoparticles: NMR and TGA quantification.

Surface functionalization is widely used to control the behavior of nanomaterials for a range of applications. However, methods to accurately quantify surface functional groups and coatings are not yet routinely applied to nanomaterial characterization. We have employed a combination of quantitative NMR (qNMR) and thermogravimetric analysis (TGA) to address this problem for commercial cerium, nickel, and iron oxide nanoparticles (NPs) that have been modified to add functional coatings with (3-aminopropyl)triethoxysilane (APTES), stearic acid, and polyvinylpyrrolidone (PVP). The qNMR method involves quantification of material that is released from the NPs and quantified in the supernatant after removal of NPs. Removal of aminopropylsilanes was accomplished by basic hydrolysis whereas PVP and stearic acid were removed by ligand exchange using sodium hexametaphosphate and pentadecafluorooctanoic acid, respectively. The method accuracy was confirmed by analysis of NPs with a known content of surface groups. Complementary TGA studies were carried out in both air and argon atmosphere with FT-IR of evolved gases in argon to confirm the identity of the functional groups. TGA measurements for some unfunctionalized samples show mass loss due to unidentified components which makes quantification of functional groups in surface-modified samples less reliable. XPS provides information on the presence of surface contaminants and the level of surface hydroxylation for selected samples. Despite the issues associated with accurate quantification using TGA, the TGA estimates agree reasonably well with the qNMR data for samples with high surface loading. This study highlights the issues in analysis of commercial nanomaterials and is an advance towards the development of generally applicable methods for quantifying surface functional groups.

Silver Nanoparticles Anchored on Single-Walled Carbon Nanotubes via a Conjugated Polymer for Enhanced Sensing Applications.

Single-walled carbon nanotubes (SWCNTs) are candidate matrices for loading metal nanoparticles (NPs) for sensor and catalytic applications owing to their high electron conductivity and mechanical strength, larger surface area, excellent chemical stability, and ease of surface modification. The performance of the formed NP/SWCNT composites is dependent on the NP size, the physical and chemical interactions between the components, and the charge transfer capabilities. Anchoring metal complexes onto the surface of SWCNTs through noncovalent interactions is a viable strategy for achieving high-level metal dispersion and high charge transfer capacities between metal NPs and SWCNTs. However, traditional metal complexes have small molecular sizes, and their noncovalent interactions with SWCNTs are limited to provide excellent sensing and catalytic capability with restricted efficiency and durability. Here, we selected poly(9,9-di-n-dodecylfluorenyl-2,7-diyl-alt-2,2'-bipyridine-5,5') (PFBPy) to increase the noncovalent interactions between silver nanoparticles (AgNPs) and SWCNTs. A silver triflate (Ag-OTf) solution was added into a PFBPy-wrapped SWCNT solution to form Ag-PFBPy complexes on the nanotube surface, after which Ag+ was photoreduced to AgNPs to form a Ag-PFBPy/SWCNT composite in the solution. In various feeding molar ratios of Ag-OTf over the BPy unit (0.4-50), the size of the formed AgNPs may be well-controlled at sub-nm levels to provide them with an energy level comparable to that of the SWCNTs. Additionally, the 2,2'-bipyridine (BPy) unit of the polymer provided a coordinating interaction with Ag+ and the formed AgNPs as well. The 5,5'-linage of BPy with the fluorene unit in PFBPy ensured a straight main chain structure to retain strong π-π interactions with nanotubes before and after Ag+ chelation. All of these factors confirmed a tight contact between the formed AgNPs and SWCNTs, promoting the charge transfer between them and enhancing the sensing capabilities with a 5-fold increase in humidity sensing sensitivity.

A Multi-Method Approach for Quantification of Surface Coatings on Commercial Zinc Oxide Nanomaterials.

Surface functionalization is a key factor for determining the performance of nanomaterials in a range of applications and their fate when released to the environment. Nevertheless, it is still relatively rare that surface groups or coatings are quantified using methods that have been carefully optimized and validated with a multi-method approach. We have quantified the surface groups on a set of commercial ZnO nanoparticles modified with three different reagents ((3-aminopropyl)-triethoxysilane, caprylsilane and stearic acid). This study used thermogravimetric analysis (TGA) with Fourier transform infrared spectroscopy (FT-IR) of evolved gases and quantitative solution 1H nuclear magnetic resonance (NMR) for quantification purposes with 13C-solid state NMR and X-ray photoelectron spectroscopy to confirm assignments. Unmodified materials from the same suppliers were examined to assess possible impurities and corrections. The results demonstrate that there are significant mass losses from the unmodified samples which are attributed to surface carbonates or residual materials from the synthetic procedure used. The surface modified materials show a characteristic loss of functional group between 300-600 °C as confirmed by analysis of FT-IR spectra and comparison to NMR data obtained after quantitative release/extraction of the functional group from the surface. The agreement between NMR and TGA estimates for surface loading is reasonably good for cases where the functional group accounts for a relatively large fraction of the sample mass (e.g., large groups or high loading). In other cases TGA does not have sufficient sensitivity for quantitative analysis, particularly when contaminants contribute to the TGA mass loss. X-ray photoelectron spectroscopy and solid state NMR for selected samples provide support for the assignment of both the functional groups and some impurities. The level of surface group loading varies significantly with supplier and even for different batches or sizes of nanoparticles from the same supplier. These results highlight the importance of developing reliable methods to detect and quantify surface functional groups and the importance of a multi-method approach.

The impact of processing on the cytotoxicity of graphene oxide.

In-house prepared graphene oxide (GO) was processed via base washing, sonication, cleaning and combinations of these processing techniques to evaluate the impact on the flake morphology, composition and cytotoxicity of the material. The flakes of unprocessed GO were relatively planar, but upon base washing, the flakes became textured exhibiting many folds and creases observed by AFM. In addition to the pronounced effect on the topography, base washing increased the C/O ratio and increased the cytotoxicity of GO on all four cell lines studied determined via the WST-8 assay. Sonicating the unprocessed and base washed samples resulted in smaller flakes with a similar topography; the base washed flakes lost the texture previously observed upon sonication. The sonicated samples were more toxic than the unprocessed sample, attributed to the smaller flake size, but were interestingly less toxic than the base washed, unsonicated sample despite the base washed unsonicated sample having a larger flake size. This unexpected finding was confirmed by a second analyst using the same, and a different source of GO and resulted in the conclusion that the morphology of GO greatly impacts the cytotoxicity. Cleaning the GO reduced the amount of nitrogen and sulfur impurities in the sample but had no significant impact on the cytotoxicity of the material. It was observed that nutrient depletion via nanomaterial adsorption was not the route of cytotoxicity for the GO samples studied.

Quantification of amine functional groups on silica nanoparticles: a multi-method approach.

Surface chemistry is an important factor for quality control during production of nanomaterials and for controlling their behavior in applications and when released into the environment. Here we report a comparison of four methods for quantifying amine functional groups on silica nanoparticles (NPs). Two colorimetric assays are examined, ninhydrin and 4-nitrobenzaldehyde, which are convenient for routine analysis and report on reagent accessible amines. Results from the study of a range of commercial NPs with different sizes and surface loadings show that the assays account for 50-100% of the total amine content, as determined by dissolution of NPs under basic conditions and quantification by solution-state 1H NMR. To validate the surface quantification by the colorimetric assays, the NPs are modified with a trifluoromethylated benzaldehyde probe to enhance sensitivity for quantitative 19F solid state NMR and X-ray photoelectron spectroscopy (XPS). Good agreement between the assays and the determination from solid-state NMR is reinforced by elemental ratios from XPS, which indicate that in most cases the difference between total and accessible amine content reflects amines that are outside the depth probed by XPS. Overall the combined results serve to validate the relatively simple colorimetric assays and indicate that the reactions are efficient at quantifying surface amines, by contrast to some other covalent modifications that have been employed for functional group quantification.