A New Method for Dispersing Pristine Carbon Nanotubes Using Regularly Arranged S-Layer Proteins

Homogeneous and stable dispersions of functionalized carbon nanotubes (CNTs) in aqueous solutions are imperative for a wide range of applications, especially in life and medical sciences. Various covalent and non-covalent approaches were published to separate the bundles into individual tubes. In this context, this work demonstrates the non-covalent modification and dispersion of pristine multi-walled carbon nanotubes (MWNTs) using two S-layer proteins, namely, SbpA from Lysinibacillus sphaericus CCM2177 and SbsB from Geobacillus stearothermophilus PV72/p2. Both the S-layer proteins coated the MWNTs completely. Furthermore, it was shown that SbpA can form caps at the ends of MWNTs. Reassembly experiments involving a mixture of both S-layer proteins in the same solution showed that the MWNTs were primarily coated with SbsB, whereas SbpA formed self-assembled layers. The dispersibility of the pristine nanotubes coated with SbpA was determined by zeta potential measurements (−24.4 +/− 0.6 mV, pH = 7). Finally, the SbpA-coated MWNTs were silicified with tetramethoxysilane (TMOS) using a mild biogenic approach. As expected, the thickness of the silica layer could be controlled by the reaction time and was 6.3 +/− 1.25 nm after 5 min and 25.0 +/− 5.9 nm after 15 min. Since S-layer proteins have already demonstrated their capability to bind (bio)molecules in dense packing or to act as catalytic sites in biomineralization processes, the successful coating of pristine MWNTs has great potential in the development of new materials, such as biosensor architectures.

The Importance of Evaluating the Lot-to-Lot Batch Consistency of Commercial Multi-Walled Carbon Nanotube Products

The biological response of multi-walled carbon nanotubes (MWNTs) is related to their physicochemical properties and a thorough MWNT characterization should accompany an assessment of their biological activity, including their potential toxicity. Beyond characterizing the physicochemical properties of MWNTs from different sources or manufacturers, it is also important to characterize different production lots of the same MWNT product from the same vendor (i.e., lot-to-lot batch consistency). Herein, we present a comprehensive physicochemical characterization of two lots of commercial pristine MWNTs (pMWNTs) and carboxylated MWNTs (cMWNTs) used to study the response of mammalian macrophages to MWNTs. There were many similarities between the physicochemical properties of the two lots of cMWNTs and neither significantly diminished the 24-h proliferation of RAW 264.7 macrophages up to the highest concentration tested (200 μg cMWNTs/mL). Conversely, several physicochemical properties of the two lots of pMWNTs were different; notably, the newer lot of pMWNTs displayed less oxidative stability, a higher defect density, and a smaller amount of surface oxygen species relative to the original lot. Furthermore, a 72-h half maximal inhibitory concentration (IC-50) of ~90 µg pMWNTs/mL was determined for RAW 264.7 cells with the new lot of pMWNTs. These results demonstrate that subtle physicochemical differences can lead to significantly dissimilar cellular responses, and that production-lot consistency must be considered when assessing the toxicity of MWNTs.

Effect of Sidewall Fluorination on the Mechanical Properties of Catalytically Grown Multi-Wall Carbon Nanotubes

ABSTRACTWe report on the usage of a simple microfabricateddevice, that works in conjunction with a quantitative nanoindenter inside a scanning electron microscope (SEM), for the in situ quantitative tensile testing of individual sidewall fluorinated multi-wall carbon nanotubes (MWNTs). The stress vs. strain curves and the tensile strength values for five fluorinated specimens have been presented and compared to those of pristine MWNT specimens (data reported earlier). The fluorinated specimens were found to deform and fail in a brittle fashion similar to pristine MWNTs. However, sidewall fluorination was found to have considerably degraded the mechanical properties (tensile strength and load bearing capacity) of the MWNTs.

GAMMA-RAY IRRADIATION-INDUCED IMPROVEMENT OF HYDROGEN ADSORPTION IN MULTI-WALLED CARBON NANOTUBES

An improved hydrogen adsorption capacity of 0.5–0.6 wt% was obtained at room temperature and 10.0 MPa pressure for commercial MWNT sample by γ-ray irradiation, compared with 0.33 wt% of pristine MWNTs. The irradiation-induced defects in structure, which is favorable for hydrogen adsorption, were characterized by ESR spectrum, elemental analysis, and Raman spectrum. The results show that γ-ray irradiation increased the hydrogen adsorption capacity due to the increasing number of defects created by γ-photons, but would reach the maximum when defect concentration achieves saturation.

Effect of Functionalization on the Crystallization Behavior of MWNT-PBT Nanocomposites

ABSTRACTThere is tremendous interest in using low loadings of multiwalled carbon nanotubes (MWNTs) to enhance the multifunctional properties of polymers, with functionalization often pursued to increase the dispersion and effective reinforcement of MWNTs within the polymer. In our interest to understand the effect of MWNT functionalization on Poly (butylene terephthalate) (PBT) crystallization kinetics, morphology and mechanical properties, nanocomposites were fabricated with both as-received and carboxyl group (-COOH) functionalized MWNTs. Initial results indicate as-received and functionalized nanotubes alter the crystallization temperature and crystal size for quiescent samples. In addition, isothermal crystallization studies using an Advanced Rheometric Expansion System (ARES) show that the addition of MWNTs increases the rate of PBT crystallization. However, functionalization was found to decrease the rate of nanocomposite crystallization as compared to nanocomposites samples prepared using pristine MWNTs, suggesting that nanotube functionalization weakens the nucleation effect observed in the nanocomposite samples. These results suggest that semicrystalline polymer nanocomposite crystallization kinetics and morphology can be significantly influenced by nanoparticle functionalization and chemistry. Further study of how these changes impact the rheological and multifunctional properties of semicrystalline nanocomposite systems are ongoing.