ABSTRACT: Control of single-walled carbon nanotube dispersion properties is of substantial interest to the scientific community. In this work, we sought to investigate the effect of a macrocycle, pillararene, on the dispersion properties of a polymer-nanotube complex. Pillararenes are a class of electron-rich macrocyclic hosts capable of forming inclusion complexes with electron-poor guests, such as alkyl nitriles. A hydroxyl-functionalized pillararene derivative was coupled to the alkyl bromide side chains of a polyfluorene, which was then used to coat the surface of single-walled carbon nanotubes. Noncovalent functionalization of carbon nanotubes with the macrocycle-containing conjugated polymer significantly enhanced nanotube solubility, resulting in dark and concentrated nanotube dispersions (600 ?g mL-1), as evidenced by UV-vis-NIR spectroscopy and thermogravimetric analysis. Differentiation of semiconducting and metallic single-walled carbon nanotube species was analyzed by a combination of UV-vis-NIR, Raman, and fluorescence spectroscopy. Raman spectroscopy confirmed that the concentrated nanotube dispersion produced by the macrocycle-containing polymer was due to well-exfoliated nanotubes, rather than bundle formation. The polymer-nanotube dispersion was investigated using 1H NMR spectroscopy, and it was found that host-guest chemistry between pillararene and 1,6-dicyanohexane occurred in the presence of the polymer-nanotube complex. Utilizing the host-guest capability of pillararene, the polymer-nanotube complex was incorporated into a supramolecular organogel.
Project description:Surface oxidation improves the dispersion of carbon nanotubes in aqueous solutions and plays a key role in the development of biosensors, electrochemical detectors and polymer composites. Accurate characterization of the carbon nanotube surface is important because the development of these nano-based applications depends on the degree of functionalization, in particular the amount of carboxylation. Affinity capillary electrophoresis is used to characterize the oxidation of multi-walled carbon nanotubes. A polytryptophan peptide that contains a single arginine residue (WRWWWW) serves as a receptor in affinity capillary electrophoresis to assess the degree of carboxylation. The formation of peptide-nanotube receptor-ligand complex was detected with a UV absorbance detector. Apparent dissociation constants (KD) are obtained by observing the migration shift of the WRWWWW peptide through background electrolyte at increasing concentrations of multi-walled carbon nanotubes. A 20% relative standard deviation in method reproducibility and repeatability is determined with triplicate analysis within a single sample preparation and across multiple sample preparations for a commercially available carbon nanotube. Affinity capillary electrophoresis is applied to assess differences in degree of carboxylation across two manufacturers and to analyze acid treated carbon nanotubes. The results of these studies are compared to X-ray photoelectron spectroscopy and zeta potential. Affinity capillary electrophoresis comparisons of carbon nanotube samples prepared by varying acid treatment time from 30?min to 3?h yielded significant differences in degree of carboxylation. X-ray photoelectron spectroscopy analysis was inconclusive due to potential acid contamination, while zeta potential showed no change based on surface charge. This work is significant to research involving carbon nanotube-based applications because it provides a new metric to rapidly characterize carbon nanotubes obtained from different vendors, or synthesized in laboratories using different procedures.
Project description:Formation of thick, high energy density, flexible solid supercapacitors is challenging because of difficulties infilling gel electrolytes into porous electrodes. Incomplete infilling results in a low capacitance and poor mechanical properties. Here we report a bottom-up infilling method to overcome these challenges. Electrodes up to 500??m thick, formed from multi-walled carbon nanotubes and a composite of poly(3,4-ethylenedioxythiophene), polystyrene sulfonate and multi-walled carbon nanotubes are successfully infilled with a polyvinyl alcohol/phosphoric acid gel electrolyte. The exceptional mechanical properties of the multi-walled carbon nanotube-based electrode enable it to be rolled into a radius of curvature as small as 0.5?mm without cracking and retain 95% of its initial capacitance after 5000 bending cycles. The areal capacitance of our 500??m thick poly(3,4-ethylenedioxythiophene), polystyrene sulfonate, multi-walled carbon nanotube-based flexible solid supercapacitor is 2662?mF?cm<sup>-2</sup> at 2?mV?s<sup>-1</sup>, at least five times greater than current flexible supercapacitors.
Project description:Aligned single-walled carbon nanotube arrays provide a great potential for the carbon-based nanodevices and circuit integration. Aligning single-walled carbon nanotubes with selected helicities and identifying their helical structures remain a daunting issue. The widely used gas-directed and surface-directed growth modes generally suffer the drawbacks of mixed and unknown helicities of the aligned single-walled carbon nanotubes. Here we develop a rational approach to anchor the single-walled carbon nanotubes on graphite surfaces, on which the orientation of each single-walled carbon nanotube sensitively depends on its helical angle and handedness. This approach can be exploited to conveniently measure both the helical angle and handedness of the single-walled carbon nanotube simultaneously at a low cost. In addition, by combining with the resonant Raman spectroscopy, the (n,m) index of anchored single-walled carbon nanotube can be further determined from the (d,?) plot, and the assigned (n,m) values by this approach are validated by both the electronic transition energy Eii measurement and nanodevice application.
Project description:Semiconducting single-walled carbon nanotubes (s-SWCNTs) are considered as a replacement for silicon in field-effect transistors (FETs), solar cells, logic circuits, and so forth, because of their outstanding electronic, optical, and mechanical properties. Herein, we have studied the reaction of pristine SWCNTs dispersed in a pluronic F-68 (PF-68) polymer solution with para-amino diphenylamine diazonium sulfate (PADDS) to separate nanotubes based on their metallicity. The preferential selectivity of the reactions was monitored by changes in the semiconducting (S<sub>22</sub> and S<sub>33</sub>) and metallic (M<sub>11</sub>) bands by ultraviolet-visible-near infrared spectroscopy. Metallic selectivity depended on the concentrations of PADDS, reaction time, and the solution pH. Furthermore, separation of pure s-SWCNTs was confirmed by Raman spectroscopy and Fourier-transform infrared spectroscopy. After the removal of metallic SWCNTs, direct current electric field was applied to the pure s-SWCNT solution, which effectively directed the nanotubes to align in one direction as nanotube arrays with a longer length and high density. After that, electrically aligned s-SWCNT solution was cast on a silicon substrate, and the length of the nanotube arrays was measured as ?2 to ?14 ?m with an areal density of ?2 to ?20 tubes/?m of s-SWCNTs. Next, electrically aligned s-SWCNT arrays were deposited on the channel of the FET device by drop-casting. Field-emission scanning electron microscopy and electrical measurements have been carried out to test the performance of the aligned s-SWCNTs/FETs. The fabricated FETs with a channel length of 10 ?m showed stable electrical properties with a field-effect mobility of 30.4 cm<sup>2</sup>/Vs and a log<sub>10</sub> (<i>I</i> <sub>on</sub>/<i>I</i> <sub>off</sub>) current ratio of 3.96. We envisage that this new chemical-based separation method and electric field-assisted alignment could be useful to obtain a high-purity and aligned s-SWCNT array network for the fabrication of high-performance FETs to use in digital and analog electronics.
Project description:Recently portable Raman probes have emerged along with a variety of applications, including carbon nanotube (CNT) characterization. Aqueous dispersed CNTs have shown promise for biomedical applications such as drug/gene delivery vectors, photo-thermal therapy, and photoacoustic imaging. In this study we report the simultaneous detection and irradiation of carbon nanotubes in 2D monolayers of cancer cells and in 3D spheroids using a portable Raman probe. A portable handheld Raman instrument was utilized for dual purposes: as a CNT detector and as an irradiating laser source. Single-walled carbon nanotubes (SWCNTs) and multi-walled carbon nanotubes (MWCNTs) were dispersed aqueously using a lipid-polymer (LP) coating, which formed highly stable dispersions both in buffer and cell media. The LP coated SWCNT and MWCNT aqueous dispersions were characterized by atomic force microscopy, transmission electron microscopy, dynamic light scattering, Fourier transform infrared spectroscopy and Raman spectroscopy. The cellular uptake of the LP-dispersed SWCNTs and MWCNTs was observed using confocal microscopy, and fluorescein isothiocyanate (FITC)-nanotube conjugates were found to be internalized by ovarian cancer cells by using Z-stack fluorescence confocal imaging. Biocompatibility of SWCNTs and MWCNTs was assessed using a cell viability MTT assay, which showed that the nanotube dispersions did not hinder the proliferation of ovarian cancer cells at the dosage tested. Ovarian cancer cells treated with SWCNTs and MWCNTs were simultaneously detected and irradiated live in 2D layers of cancer cells and in 3D environments using the portable Raman probe. An apoptotic terminal deoxynucleotidyl transferase dUTP nick end labeling (TUNEL) assay carried out after laser irradiation confirmed that cell death occurred only in the presence of nanotube dispersions. We show for the first time that both SWCNTs and MWCNTs can be selectively irradiated and detected in cancer cells using a simple handheld Raman instrument. This approach could potentially be used to treat various diseases, including cancer.
Project description:For the first time, stable pillararene/Ag<sup>+</sup> nanoparticles, consisting of water-soluble pillararene containing ?-sulfobetaine fragments and Ag<sup>+</sup> ions without Ag-Ag bonds, were synthesized and characterized. The pillararene/Ag<sup>+</sup> (ratio 1:10) nanoparticles obtained were cubic with a rib length of 100 nm and are less cytotoxic than Ag<sup>+</sup> ions. The survival of the A549 model cells in the presence of pillararene/Ag<sup>+</sup> (1:10) nanoparticles at a concentration of 30 and 40 ?M was 76% and 55%, while in the absence of pillararene, the cell survival for free Ag<sup>+</sup> ions at the same concentration was 30% and 10%, respectively. The results can be used to create new antibacterial materials and 2D biomedical coatings.
Project description:The use of single-walled carbon nanotubes (SWCNTs) as near-infrared optical probes and sensors require the ability to simultaneously modulate nanotube fluorescence and functionally derivatize the nanotube surface using noncovalent methods. We synthesized a small library of polycarbodiimides to noncovalently encapsulate SWCNTs with a diverse set of functional coatings, enabling their suspension in aqueous solution. These polymers, known to adopt helical conformations, exhibited ordered surface coverage on the nanotubes and allowed systematic modulation of nanotube optical properties, producing up to 12-fold differences in photoluminescence efficiency. Polymer cloaking of the fluorescent nanotubes facilitated the first instance of controllable and reversible internanotube exciton energy transfer, allowing kinetic measurements of dynamic self-assembly and disassembly.
Project description:Electronic and biological applications of carbon nanotubes can be highly dependent on the species (chirality) of nanotube, purity, and concentration. Existing bulk methods, such as absorbance spectroscopy, can quantify sp2 carbon based on spectral bands, but nanotube length distribution, defects, and carbonaceous impurities can complicate quantification of individual particles. We present a general method to relate the optical density of a photoluminescent nanotube sample to the number of individual nanotubes. By acquiring 3-dimensional images of nanotubes embedded in a gel matrix with a reducing environment, we quantified all emissive nanotubes in a volume. Via spectral imaging, we assessed structural impurities and precisely determined molar concentrations of the (8,6) and (9,4) nanotube species. We developed an approach to obtain the molarity of any structurally enriched semiconducting single-walled carbon nanotube preparation on a per-nanotube basis.
Project description:Efficient selection of semiconducting single-walled carbon nanotubes (SWNTs) from as-grown nanotube samples is crucial for their application as printable and flexible semiconductors in field-effect transistors (FETs). In this study, we use atactic poly(9-dodecyl-9-methyl-fluorene) (a-PF-1-12), a polyfluorene derivative with asymmetric side-chains, for the selective dispersion of semiconducting SWNTs with large diameters (>1 nm) from plasma torch-grown SWNTs. Lowering the molecular weight of the dispersing polymer leads to a significant improvement of selectivity. Combining dense semiconducting SWNT networks deposited from an enriched SWNT dispersion with a polymer/metal-oxide hybrid dielectric enables transistors with balanced ambipolar, contact resistance-corrected mobilities of up to 50 cm(2)·V(-1)·s(-1), low ohmic contact resistance, steep subthreshold swings (0.12-0.14 V/dec) and high on/off ratios (10(6)) even for short channel lengths (<10 ?m). These FETs operate at low voltages (<3 V) and show almost no current hysteresis. The resulting ambipolar complementary-like inverters exhibit gains up to 61.
Project description:Suspensions of single-walled, double-walled and multi-walled carbon nanotubes (CNTs) were generated in the same solvent at similar concentrations. Films were fabricated from these suspensions and used in carbon nanotube/silicon heterojunction solar cells and their properties were compared with reference to the number of walls in the nanotube samples. It was found that single-walled nanotubes generally produced more favorable results; however, the double and multi-walled nanotube films used in this study yielded cells with higher open circuit voltages. It was also determined that post fabrication treatments applied to the nanotube films have a lesser effect on multi-walled nanotubes than on the other two types.