Carbon Nanotube-Polyurethane Composite Sheets for Flexible Thermoelectric Materials.

Integration of single-wall carbon nanotubes (SWCNTs) in the form of fabriclike sheets or other preformed assemblies (films, fibers, etc.) simplifies their handling and allows for composites with higher nanotube contents, which is needed to better exploit their outstanding properties and achieve multifunctional materials with improved performance. Here, we show the development of p-type SWCNT-thermoplastic polyurethane (TPU) fabric materials with a wide range of SWCNT contents (from 5 to 90 wt %) by employing a one-step filtration method using a suspension of SWCNTs in a TPU solvent/nonsolvent mixture. The mechanical and thermoelectric (TE) properties of these SWCNT-TPU nanocomposites were tailored by varying the SWCNT/TPU wt % ratio, achieving significant advantages relative to the pristine SWCNT buckypaper (BP) sheets in terms of strength and stretchability. In particular, the SWCNT-TPU nanocomposite with a 50/50 wt % ratio composition (equivalent to 15 vol % of SWCNTs) shows a power factor (PF) of 57 µW m-1 K-2, slightly higher compared to the PF of the SWCNT BP prepared under the same conditions (54 µW m-1 K-2), while its mechanical properties significantly increased (e.g., ∼7-, 25-, and 250-fold improvements in stiffness, strength, and tensile toughness, respectively). These results represent a significant step toward the development of easy-to-process self-supporting and stretchable materials with robust mechanical properties for flexible thermoelectric devices.

Elimination of Cancer Cells in Co-Culture: Role of Different Nanocarriers in Regulation of CD47 and Calreticulin-Induced Phagocytosis.

Under healthy conditions, pro- and anti-phagocytic signals are balanced. Cluster of Differentiation 47 (CD47) is believed to act as an anti-phagocytic marker that is highly expressed on multiple types of human cancer cells including acute myeloid leukemia (AML) and lung and liver carcinomas, allowing them to escape phagocytosis by macrophages. Downregulating CD47 on cancer cells discloses calreticulin (CRT) to macrophages and recovers their phagocytic activity. Herein, we postulate that using a modified graphene oxide (GO) carrier to deliver small interfering RNA (siRNA) CD47 (CD47_siRNA) in AML, A549 lung, and HepG2 liver cancer cells in co-culture in vitro will silence CD47 and flag cancer cells for CRT-mediated phagocytosis. Results showed a high knockdown efficiency of CD47 and a significant increase in CRT levels simultaneously by using GO formulation as carriers in all used cancer cell lines. The presence of CRT on cancer cells was significantly higher than levels before knockdown of CD47 and was required to achieve phagocytosis in co-culture with human macrophages. Lipid nanoparticles (LNPs) and modified boron nitride nanotubes (BNPs) were used to carry CD47_siRNA, and the knockdown efficiency values of CD47 were compared in three cancer cells in co-culture, with an achieved knockdown efficiency of >95% using LNPs as carriers. Interestingly, the high efficiency of CD47 knockdown was obtained by using the LNPs and BNP carriers; however, an increase in CRT levels on cancer cells was not required for phagocytosis to happen in co-culture with human macrophages, indicating other pathways' involvement in the phagocytosis process. These findings highlight the roles of 2D (graphene oxide), 1D (boron nitride nanotube), and "0D" (lipid nanoparticle) carriers for the delivery of siRNA to eliminate cancer cells in co-culture, likely through different phagocytosis pathways in multiple types of human cancer cells. Moreover, these results provide an explanation of immune therapies that target CD47 and the potential use of these carriers in screening drugs for such therapies in vitro.

Glass Fiber-Epoxy Composites with Boron Nitride Nanotubes for Enhancing Interlaminar Properties in Structures.

Hybrid composite materials are a class of materials where more than one type of reinforcement is integrated into a matrix to achieve superior properties. This typically involves nanoparticle fillers employed within traditional advanced composites with fiber reinforcements such as carbon or glass. The current study builds on previous investigations of boron nitride nanotube (BNNT) hybrid composites, specifically glass fiber (GF)-epoxy/BNNT composite laminates. GF is an effective and affordable primary reinforcement fiber in many applications, and boron nitride nanotubes (BNNTs) exhibit impressive mechanical properties comparable to carbon nanotubes (CNTs) with distinct functional properties, such as electrical insulation, which is desirable in manufacturing insulating composites when combined with GF. GF-epoxy/BNNT composite laminates, incorporating BNNT materials with different loadings (1 and 2 wt %) and purity, were manufactured using a hand layup technique and prepared for three-point bending, modified Charpy, dynamic mechanical analysis (DMA), and fracture toughness (mode I and mode II) measurements. A comprehensive microscopy study was also performed using scanning electron microscopy (SEM) showing prominent failure mechanism, nanotube dispersion, and their mode of reinforcement in different loading scenarios. Enhanced properties, including a 43% increase in mode II fracture toughness, were observed in hybrid composites with 1 wt % BNNT compared to the GF composites with neat epoxy, and the reinforcement mechanisms were discussed.

Conformational Order in Aggregated rra-P3HT as an Indicator of Quality of Boron Nitride Nanotubes.

We report on investigation, by correlated polarized excitation fluorescence microscopy (PEFM) and atomic force microscopy (AFM) imaging, of the conformational order of regiorandom poly(3-hexyl-thiophene) (rra-P3HT) aggregated on two boron nitride nanotube (BNNT) materials (BNNT-2 and BNNT-3) processed by different purification methods. rra-P3HT photoluminescence excited by linearly polarized light shows polarization direction-dependent intensity with a modulation depth, M, generally >0.5 for rra-P3HT on nanotubes and <0.5 for rra-P3HT on nontubular impurities. PEFM-measured modulation depth value distributions can be decomposed into two components, one corresponding to ordered rra-P3HT on nanotubes and the other to disordered rra-P3HT on impurities. The nanotube component peaks at M = 0.64 and 0.70 and comprises 60% and 78% of the normalized distribution for rra-P3HT on BNNT-2 and BNNT-3, respectively, indicating higher quality and higher fraction of nanotubes in the latter material. The method can be integrated in a material development platform to monitor production and purification progress.

Assessing size-dependent cytotoxicity of boron nitride nanotubes using a novel cardiomyocyte AFM assay.

As boron nitride nanotubes (BNNTs) find increased use in numerous applications, potential adverse health effects of BNNT exposure are a growing concern. Current in vitro cytotoxicity studies on BNNTs are inconsistent and even contradictory, likely due to the lack of reference materials, standardized characterization methods and measurement protocols. New approaches, particularly with the potential to reliably relate in vitro to in vivo studies, are critically needed. This work introduces a novel atomic force microscopy (AFM)-based cardiomyocyte assay that reliably assesses the cytotoxicity of a well-characterized boron nitride nanotube reference material, code named BNNT-1. High energy probe sonication was used to modify and control the length of BNNT-1. The polymer polyethylenimine (PEI) was used concurrently with sonication to produce stable, aqueous dispersions of BNNT-1. These dispersions were used to perform a systematic analysis on both the length and height of BNNT-1 via a correlated characterization approach of dynamic light scattering (DLS) and AFM. Cytotoxicity studies using the novel cardiomyocyte AFM model were in agreement with traditional colorimetric cell metabolic assays, both revealing a correlation between tube length and cytotoxicity with longer tubes having higher cytotoxicity. In addition to the size-dependent cytotoxicity, it was found that BNNT-1 exhibits concentration and cell-line dependent cytotoxic effects.

Fabrication of High Content Carbon Nanotube-Polyurethane Sheets with Tailorable Properties.

We have fabricated carbon nanotube (CNT)-polyurethane (TPU) sheets via a one-step filtration method that uses a TPU solvent/nonsolvent combination. This solution method allows for control of the composition and processing conditions, significantly reducing both the filtration time and the need for large volumes of solvent to debundle the CNTs. Through an appropriate selection of the solvents and tuning the solvent/nonsolvent ratio, it is possible to enhance the interaction between the CNTs and the polymer chains in solution and improve the CNT exfoliation in the nanocomposites. The composition of the nanocomposites, which defines the characteristics of the material and its mechanical properties, can be precisely controlled. The highest improvements in tensile properties were achieved at a CNT:TPU weight ratio around 35:65 with a Young's modulus of 1270 MPa, stress at 50% strain of 35 MPa, and strength of 41 MPa, corresponding to ∼10-fold improvement in modulus and ∼7-fold improvement in stress at 50% strain, while maintaining a high failure strain. At the same composition, CNTs with higher aspect ratio produce nanocomposites with greater improvements (e.g., strength of 99 MPa). Electrical conductivity also shows a maximum near the same composition, where it can exceed the values achieved for the pristine nanotube buckypaper. The trend in mechanical and electrical properties was understood in terms of the CNT-TPU interfacial interactions and morphological changes occurring in the nanocomposite sheets as a function of increasing the TPU content. The availability of such a simple method and the understanding of the structure-property relationships are expected to be broadly applicable in the nanocomposites field.

Mechanistic insights into the effect of nanoparticles on zebrafish hatch.

Aquatic organisms are susceptible to waterborne nanoparticles (NP) and there is only limited understanding of the mechanisms by which these emerging contaminants may affect biological processes. This study used silicon (nSi), cadmium selenide (nCdSe), silver (nAg) and zinc NPs (nZnO) as well as single-walled carbon nanotubes (SWCNT) to assess NP effects on zebrafish (Danio rerio) hatch. Exposure of 10 mg/L nAg and nCdSe delayed zebrafish hatch and 100 mg/L of nCdSe as well as 10 and 100 mg/L of uncoated nZnO completely inhibited hatch and the embryos died within the chorion. Both the morphology and the movement of the embryos were not affected, and it was determined that the main mechanism of hatch inhibition by NPs is likely through the interaction of NPs with the zebrafish hatching enzyme. Furthermore, it was concluded that the observed effects arose from the NPs themselves and not their dissolved metal components.

Influence of the reaction stoichiometry on the mechanical and thermal properties of SWCNT-modified epoxy composites.

Previous studies suggest that carbon nanotubes (CNTs) have a considerable influence on the curing behavior and crosslink density of epoxy resins. This invariably has an important effect on different thermal and mechanical properties of the epoxy network. This work focuses on the important role of the epoxy/hardener mixing ratio on the mechanical and thermal properties of a high temperature aerospace-grade epoxy (MY0510 Araldite as an epoxy and 4,4'-diaminodiphenylsulfone as an aromatic hardener) modified with single-walled carbon nanotubes (SWCNTs). The effects of three different stoichiometries (stoichiometric and off-stoichiometric) on various mechanical and thermal properties (fracture toughness, tensile properties, glass transition temperature) of the epoxy resin and its SWCNT-modified composites were obtained. The results were also supported by Raman spectroscopy and scanning electron microscopy (SEM). For the neat resin, it was found that an epoxy/hardener molar ratio of 1:0.8 provides the best overall properties. In contrast, the pattern in property changes with the reaction stoichiometry was considerably different for composites reinforced with unfunctionalized SWCNTs and reduced SWCNTs. A comparison among composites suggests that a 1:1 molar ratio considerably outperforms the other two ratios examined in this work (1:0.8 and 1:1.1). This composition at 0.2 wt% SWCNT loading provides the highest overall mechanical properties by improving fracture toughness, ultimate tensile strength and ultimate tensile strain of the epoxy resin by 40%, 34%, 54%, respectively.

Reactive fillers based on SWCNTs functionalized with matrix-based moieties for the production of epoxy composites with superior and tunable properties.

Composite materials based on epoxy matrix and single-walled carbon nanotubes (SWCNTs) are able to exhibit outstanding improvements in physical properties when using a tailored covalent functionalization with matrix-based moieties containing terminal amines or epoxide rings. The proper choice of grafted moiety and integration protocol makes it feasible to tune the composite physical properties. At 0.5 wt% SWCNT loading, these composites exhibit up to 65% improvement in storage modulus, 91% improvement in tensile strength, and 65% improvement in toughness. A 15 °C increase in the glass transition temperature relative to the parent matrix was also achieved. This suggests that a highly improved interfacial bonding between matrix and filler, coupled to improved dispersion, are achieved. The degradation temperatures show an upshift in the range of 40-60 °C, which indicates superior thermal performance. Electrical conductivity ranges from ~10(-13) to ~10(-3) S cm(-1), which also shows the possibility of tuning the insulating or conductive behaviour of the composites. The chemical affinity of the functionalization moieties with the matrix and the unchanged molecular structure at the SWCNT/matrix interface are responsible for such improvements.

Toughening of epoxy matrices with reduced single-walled carbon nanotubes.

Reduced single-walled carbon nanotubes (r-SWCNT) are shown to react readily at room temperature under inert atmosphere conditions with epoxide moieties, such as those in triglycidyl p-amino phenol (TGAP), to produce a soft covalently bonded interface around the SWCNT. The soft interface is compatible with the SWCNT-free cross-linked cured matrix and acts as a toughener for the composite. Incorporation of 0.2 wt % r-SWCNT enhances the ultimate tensile strength, toughness and fracture toughness by 32, 118, and 40%, respectively, without change in modulus. A toughening rate (dK(IC)/dwt(f)) of 200 MPa m(0.5) is obtained. The toughening mechanism is elucidated through dynamic mechanical analyses, Raman spectroscopy and imaging, and stress-strain curve analyses. The method is scalable and applicable to epoxy resins and systems used commercially.

Coupled thermogravimetry, mass spectrometry, and infrared spectroscopy for quantification of surface functionality on single-walled carbon nanotubes.

We have successfully applied coupled thermogravimetry, mass spectrometry, and infrared spectroscopy to the quantification of surface functional groups on single-walled carbon nanotubes. A high-purity single-walled carbon nanotube sample was subjected to a rapid functionalization reaction that attached butyric acid moieties to the nanotube sidewalls. This sample was then subjected to thermal analysis under inert desorption conditions. Resultant infrared and mass spectrometric data were easily utilized to identify the desorption of the butyric acid groups across a narrow temperature range and we were able to calculate the degree of substitution of the attached acid groups within the nanotube backbone as 1.7 carbon atoms per hundred, in very good agreement with independent analytical measurements made by inductively coupled plasma optical emission spectrometry (ICP-OES). The thermal analysis technique was also able to discern the presence of secondary functional moieties on the nanotube samples that were not accessible by ICP-OES. This work demonstrates the potential of this technique for assessing the presence of multiple and diverse functional addends on the nanotube sidewalls, beyond just the principal groups targeted by the specific functionalization reaction.

About the solubility of reduced SWCNT in DMSO.

Single-walled carbon nanotubes (SWCNT) have been reduced with sodium naphthalide in THF. The reduced SWCNT are not only soluble in dimethylsulfoxide (DMSO) to form a stable solution/suspension, but also react spontaneously at room temperature with DMSO to evolve hydrocarbon gases and are converted into functionalized SWCNT. The degree of functionalization is about 2C% and the addends are mainly methyl and small oxygen-containing hydrocarbons. The functionalized SWCNT are apparently more soluble and stable in DMSO solution. It may open a new era for further processing and applications.

Rapid and controllable covalent functionalization of single-walled carbon nanotubes at room temperature.

We report a rapid and efficient procedure to functionalize SWNT where free radicals generated at room temperature by a redox reaction between reduced SWNT and diacyl peroxide derivatives were covalently attached to the SWNT wall.