Regulation of the near-IR spectral properties of individually dissolved single-walled carbon nanotubes in aqueous solutions of dsDNA

Two different single-walled carbon nanotubes (SWNTs), the so-called HiPco and CoMoCAT, have been individually dissolved in aqueous solutions of double-stranded DNA (dsDNA). Atomic force microscopy (AFM) revealed the fine structures of the dsDNA-wrapped SWNTs. The near-IR absorption and photoluminescence (PL) spectra of aqueous solutions of dsDNA-wrapped SWNTs were recorded and, in pure water, we observed only a single two-dimensional PL spot from (6,5) SWNTs for both HiPco and CoMoCAT. In sharp contrast, when Tris-EDTA (TE) buffer was used in place of pure water, the PL-mapping images of the solutions showed chirality indices of (6,5), (7,5), (7,6), (8,4), (9,4), and (10,2) for HiPco-SWNTs, and (6,5) and (7,5) for CoMoCAT-SWNTs. The first semiconducting bands in the near-IR absorption spectra of solutions of dsDNA-wrapped SWNTs are different. To explain the observed differences in the near-IR absorption and PL behavior we conducted several experiments and found that the near-IR optical properties of the SWNTs can be modulated by changing the pH of the solutions. The pH break-points for near-IR absorption bleaching and PL quenching are different and the phenomena are explained by differences in the numbers of holes generated on the SWNTs. These findings are important from both fundamental and applied viewpoints.     

Changes in the fluorescence spectrum of individual single-wall carbon nanotubes induced by light-assisted oxidation with hydroperoxide

Through fluorescence-spectrum measurements, we investigated the effects of light-assisted oxidation with H2O2 (LAOx) on single-wall carbon nanotubes (SWNTs) that were individually dispersed in an aqueous solution of surfactant. The intensities of the fluorescence spectra were decreased remarkably by the LAOx when the light's wavelength was 400-500 nm and a little when 600-700 nm. The spectrum intensity did not recover even when the pH was restored to an original value of 6.5. The spectra changed little when the LAOx wavelength was 500-600 nm or the light was not irradiated. In addition, the effect of LAOx on SWNTs was related to the diameters of SWNTs. We inferred that these phenomena reflected that H2O2 was dissociated by absorbing the fluorescence light emitted from optically excited SWNTs, which, in turn, accelerated the burning out of SWNTs.     

Water-soluble and optically pH-sensitive single-walled carbon nanotubes from surface modification

There is great interest in using single-walled carbon nanotubes (SWNTs) as nanoscale probes and sensors in biological electronics and optical devices because the electronic and optical properties of SWNTs are extremely sensitive to the surrounding environments. A well-controlled modification of SWNT surfaces may provide unique interfaces that are sensitive to the biological variables such as pH, glucose, various ions and proteins. In this paper, we report a facile chemical routine to prepare water-soluble SWNTs that still retain their van Hove singularities after acid oxidative treatment. The aqueous solutions (0.03-0.15 mg/mL) are stable for more than a month. The solubility in water for as-treated SWNTs with surfaces modified by carboxylate groups provides us with a unique opportunity to reveal the relationship of the SWNT electronic and optical properties with pH. Here we present the first observation that after surface modification with carboxylate groups, the optical absorption of the first interband transition of as-treated water-soluble semiconducting SWNTs reversibly responds to the pH change in aqueous solutions. Our results indicate that surface modification of SWNTs is a promising way for preparing chemically selective SWNT interfaces, which may open new exciting opportunities for various applications.     

Characteristics of the Raman spectra of single-walled carbon nanotube bundles under electrochemical potential control

Resonant Raman scattering spectra of single-walled carbon nanotube–sodium dodecyl sulfate (SWNT–SDS) bundles adsorbed on Au electrodes have been investigated in aqueous electrolytes. Raman intensities of the radial breathing mode (RBM) with 785-nm laser excitation were monitored at different electrode potentials between −0.5 and +0.8 V relative to the SCE. Six resolved RBM peaks assignable to different diameter tubes all decreased in intensity when the electrode was positively biased, because of depletion of valence-band electrons associated with resonant excitation. The attenuation occurred at more positive potentials for narrower-diameter tubes with higher RBM frequencies consistent with their larger bandgaps. The results suggest the Fermi level is equilibrated in bundled SWNTs in contrast with the large Fermi-level shifts reported for isolated SWNTs.     

Singling out the electrochemistry of individual single-walled carbon nanotubes in solution

Bandgap fluorescence spectroscopy of aqueous, micelle-like suspensions of SWNTs has given access to the electronic energies of individual semiconducting SWNTs, while substantially lower is the success achieved in the determination of the redox properties of SWNTs as individual entities. Here we report an extensive voltammetric and vis-NIR spectroelectrochemical investigation of true solutions of unfunctionalized SWNTs and determine the standard electrochemical potentials of reduction and oxidation as a function of the tube diameter of a large number of semiconducting SWNTs. We also establish the Fermi energy and the exciton binding energy for individual tubes in solution. The linear correlation found between the potentials and the optical transition energies is quantified in two simple equations that allow one to calculate the redox potentials of SWNTs that are insufficiently abundant or absent in the samples.     

Electron and hole transport to trap groups at the ends of conjugated polyfluorenes

Polyfluorenes (pF) were synthesized having anthraquinone (AQ) or naphtylimide (NI) end caps that trap electrons or di- p-tolylaminophenyl (APT2) caps that trap holes. The average lengths of the pF chains in these molecules varied from 7 to 30 nm. End capping was found not to be complete in these molecules so that some were without caps. Electrons or holes were injected into these polymers in solution by pulse radiolysis. Following attachment, the charges migrated to the end cap traps in times near 2 ns in pF12AQ or 5 ns in pF35NI. From these observations, electron mobilities for transport along single chains to the end caps in THF solution were determined to be smaller by a factor of 100 than those observed by microwave conductivity. Despite this, the mobilities were sufficiently large to provide encouragement to the use of such single chains in solar photovoltaics. Most charges were observed to transport over substantial distances in these polymers, but 23, 18, and 37% of the charges attached to pFNI, pFAQ, and pFAPT2, respectively, were trapped in the pF chains and decayed by slower bimolecular reactions. For pFAQ and pFAPT2, all of the trapped charges were accounted for by estimates of the fraction of molecules having no end cap traps. For pF35NI, 23% of the attached electrons were found to be trapped in the chains, but only 4% of chains were expected to have no end caps. This could indicate some trapping by kinks or other defects but may just reflect uncertainties in the capping of this long polymer. When the charges reach the trap groups, their spectra have no features of pF(*-) or pF(*+), nor do the principal bands of the trapped ions resemble spectra of the radical ions of isolated trap molecules. The optical absorption spectra are rather dominated by new bands identified as charge-transfer transitions, which probably reinject electrons or holes into the pF chains. The energies of those bands correlate well with measured redox potentials.     

Effects of surfactant and boron doping on the BWF feature in the Raman spectrum of single-wall carbon nanotube aqueous dispersions

We examine the Breit-Wigner-Fano (BWF) line shape in the Raman spectra of carbon single-wall nanotubes (SWNTs) dispersed in aqueous suspensions. Bundling and electronic effects are studied by comparing undoped SWNTs (C-SWNTs) to boron-doped nanotubes (B-SWNTs) in a variety of different surfactant solutions. For SWNTs dispersed with nonionic surfactants that are less effective in debundling than ionic surfactants, the Raman spectra retain a large BWF feature. However, we demonstrate that even for SWNTs dispersed as isolated nanotubes by ionic surfactants the BWF feature may be present and that the intensity of the BWF is highly sensitive to the specific surfactant. In particular, surfactants with electron-donating groups tend to enhance the BWF feature. Also, modification of the SWNT electronic properties by boron doping leads to enhanced surfactant dispersion relative to undoped C-SWNTs and also to modification of the BWF feature. These observations are in agreement with reports demonstrating an enhancement of the BWF by bundling but also agree with reports that suggest electron donation can enhance the BWF feature even for isolated SWNTs. Importantly, these results serve to caution against using the lack or presence of a BWF feature as an independent measure of SWNT aggregation in surfactant dispersions.     

Recoverable solution reaction of HiPco carbon nanotubes with hydrogen peroxide

There is increasing interest in developing single-walled carbon nanotubes (SWNTs)-based optical biosensors for remote or in vitro and in vivo sensing because the near-IR optical properties of SWNTs are very sensitive to surrounding environmental changes. Many enzyme-catalyzed reactions yield hydrogen peroxide (H(2)O(2)) as a product. To our knowledge, there is no report on the interaction of H(2)O(2) with SWNTs from the optical sensing point of view. Here, we study the reaction of H(2)O(2) with an aqueous suspension of water-soluble (ws) HiPco SWNTs encased in the surfactant sodium dodecyl sulfate (SDS). The SWNTs are optically sensitive to hydrogen peroxide in pH 6.0 buffer solutions through suppression of the near-IR absorption band intensity. Interestingly, the suppressed spectral intensity of the nanotubes recovers by increasing the pH, by decomposing the H(2)O(2) into H(2)O and O(2) with the enzyme catalase, and by dialytically removing H(2)O(2). Preliminary studies on the mechanisms suggest that H(2)O(2) withdraws electrons from the SWNT valence band by charge transfer, which suppresses the nanotube spectral intensity. The findings suggest possible enzyme-assisted molecular recognition applications by selective optical detection of biological species whose enzyme-catalyzed products include hydrogen peroxide.     

Synthesis of block polyethers with various structures and their application in dispersing single-walled carbon nanotubes

The block polyethers with different structure and composition were synthesized by anionic polymerization and used to disperse single-walled carbon nanotubes (SWNTs). The block polyethers with the structure of branch or benzene ring had better dispersion ability than the commercial Pluronic block polyethers (L64 and F127). In order to compare the parameters, dispersion limit and efficiency of polyethers for SWNTs were defined. UV?Cvis?Cnear infrared absorbance spectra showed that eight-branch polyether AE82 had much larger dispersion limit and efficiency than five-branch AE52. BPE containing benzene rings in the molecule had a slightly lower dispersion limit but larger dispersion efficiency than AE82. The defect density of SWNTs dispersed in polyether aqueous solutions was investigated by Raman spectroscopy. The polyethers AE83 and BEP with the structure of poly(ethylene oxide)?Cpoly(propylene oxide) dispersed less defective SWNTs than AE82 and BPE, indicating that the variation of polyether structure and composition could influence the defect density of SWNTs besides dispersion limit and efficiency.     

Control of hole opening in single-wall carbon nanotubes and single-wall carbon nanohorns using oxygen

Due to the simplicity of the process, holes in the graphene walls of single-wall carbon nanotubes (SWNTs) and single-wall carbon nanohorns (SWNHs) have often been opened using O2 gas at high temperatures, even though this contaminates the nanotubes with carbonaceous dust (C-dust). To open holes with less C-dust contamination, we found that a slow temperature increase of 1 degrees C/min or less, in air, was effective. We also found that SWNHs having little C-dust could store a large quantity of materials inside the tubes. We infer that the local temperature increase due to the exothermic reaction of combustion may have been suppressed in the slow combustion process, which was effective in reducing the C-dust.     

Swelling the micelle core surrounding single-walled carbon nanotubes with water-immiscible organic solvents

Solvatochromic shifts in the absorbance and fluorescence spectra are observed when surfactant-stabilized aqueous single-walled carbon nanotube (SWNT) suspensions are mixed with immiscible organic solvents. When aqueous surfactant-suspended SWNTs are mixed with o-dichlorobenzene, the spectra closely match the peaks for SWNTs dispersed in only pure o-dichlorobenzene. These spectral changes suggest that the hydrophobic region of the micelle surrounding SWNTs swells with the organic solvent when mixed. The solvatochromic shifts of the aqueous SWNT suspensions are reversible once the solvent evaporates. However, some surfactant-solvent systems show permanent changes to the fluorescence emission intensity after exposure to the organic solvent. The intensity of some large diameter SWNT (n, m) types increase by more than 175%. These differences are attributed to surfactant reorganization, which can improve nanotube coverage, resulting in decreased exposure to quenching mechanisms from the aqueous phase.     

Solubilization of single-walled carbon nanotubes by using polycyclic aromatic ammonium amphiphiles in water--strategy for the design of high-performance solubilizers

We describe the design of polycyclic aromatic compounds with high performance that dissolve single-walled carbon nanotubes (SWNTs). Synthetic amphiphiles trimethyl-(2-oxo-2-phenylethyl)-ammonium bromide (1) and trimethyl-(2-naphthalen-2-yl-2-oxo-ethyl)-ammonium bromide (2) carrying a phenyl or a naphtyl moiety were not able to dissolve/disperse SWNTs in water. By contrast, trimethyl-(2-oxo-2-phenanthren-9-yl-ethyl)-ammonium bromide (3) solubilized SWNTs, although the solubilization ability was lower than that of trimethyl-(2-oxo-2-pyrene-1-yl-ethyl)-ammonium bromide (4) (solubilization behavior observed by using 4 was described briefly in reference 4a). Transmission electron microscopy (TEM), as well as visible/near-IR, fluorescence, and near-IR photoluminescence spectroscopies were employed to reveal the solubilization properties of 4 in water, and to compare these results with those obtained by using sodium dodecyl sulfate (SDS) and hexadecyltrimethylammonium bromide (HTAB) as solubilizers. Compound 4 solubilized both the as-produced SWNTs (raw-SWNTs) and purified SWNTs under mild experimental conditions, and the solubilization ability was better than that of SDS and HTAB. Near-IR photoluminescence measurements revealed that the chiral indices of the SWNTs dissolved in an aqueous solution of 4 were quite different from those obtained by using micelles of SDS and HTAB; for a SWNTs/4 solution, the intensity of the (7,6), (9,5), and (12,1) indices were strong and the chirality distribution was narrower than those of the micellar solutions. This indicates that the aqueous solution of 4 has a tendency to dissolve semiconducting SWNTs with diameters in the range of 0.89-1.0 nm, which are larger than those SWNTs (0.76-0.97 nm) dissolved in the aqueous micelles of SDS and HTAB.     

Light-controlled single-walled carbon nanotube dispersions in aqueous solution

We have succeeded in dispersing single-walled carbon nanotubes (SWNTs) into an aqueous solution of poly(ethylene glycol)-terminated malachite green derivative (PEG-MG) through simple sonication. It was found that UV exposure caused reaggregation of these predispersed SWNTs in the same aqueous medium, as adsorbed PEG-MG photochromic chains could be effectively photocleavaged from the nanotube surface. The observed light-controlled dispersion and reaggragation of SWNTs in the aqueous solution should facilitate the development of SWNT dispersions with a controllable dispersity for potential applications.     

A transmission dielectric time domain spectroscopy method for aqueous systems

A transmission method in dielectric time domain spectroscopy, suitable for aqueous systems, is described. It is demonstrated that the method can be applied to aqueous electrolytes. The dielectric spectra of solutions of the non-electrolyte glucose and the electrolytes CuSO₄ and sodium carboxymethyl cellulose are given as illustrative applications.     

Rapidly functionalized, water-dispersed carbon nanotubes at high concentration

Microwave-assisted functionalization of single-wall carbon nanotubes (SWNTs) in a mixture of nitric and sulfuric acids was carried out to synthesize highly water-dispersible nanotubes. Stable concentrations as high as 10 mg/mL were obtained in deionized water that are nearly 2 orders of magnitude higher than those previously reported. This was after only 3 min of functionalization reaction. Fourier transform infrared spectra showed the presence of carboxylated (-COOH) and acid sulfonated (-SO(2).OH or -SO(3)(-) H(+)) groups on the SWNTs. On the basis of elemental analysis, it was estimated that one out of three carbon atoms was carboxylated, while one out of 10 carbon atoms was sulfonated. The Raman spectra taken both in aqueous dispersion and in the solid phase indicated charge transfer from the SWNT backbone to the functional groups. Scanning electron microscope images of thin films deposited from an aqueous suspension showed that the SWNTs were aligned parallel to one another on the substrate. The images also indicated some reduction in average length of the nanotubes. Transmission electron microscope images of thin films from a dilute methanol dispersion showed that the SWNTs were extensively debundled. Laser light scattering particle size measurements did not show evidence for the existence of particles in the 3-800 nm size range, indicating that the functionalized SWNTs might have dispersed to have formed a true solution. Moreover, the microwave-processed SWNTs were found to contain significantly smaller amounts of the original iron catalyst relative to that present in the starting nanotubes. The electrical conductivity of a thermally annealed thin membrane obtained from the microwave-functionalized SWNTs was found to be the same as that of a similar membrane obtained from a suspension of the starting nanotubes.     

Interactions of DL-serine and L-serine with NaCl and KCl in aqueous solutions

The activity coefficients at 25‡C of DL-serine and L-serine in aqueous solutions of NaCl and KC1 were measured. This study examines the effect of the nature of the cation of the electrolyte on the activity coefficients of the optical-isomers of serine in aqueous solutions for molality of serine up to 0.4 and molality of electrolyte up to 1. An electrochemical cell with two ion-selective electrodes, a cation, and an anion ion selective electrode,vs. a double-junction reference electrode was used to measure the activity coefficients of the electrolyte and the results were converted to the activity coefficients of serine in the aqueous electrolyte solution. The comparison of the results obtained for DL- and L-serine indicates that the two optical isomers have identical interactions with electrolytes in aqueous solutions and that for this amino acid the effect of the cation of the electrolyte is not significant. Comparison of these results with previous measurements for DL-alanine in aqueous solutions of the same electrolytes show the notable effect of the backbone of the amino acid.     

Separation of single-walled carbon nanotubes on silica gel. Materials morphology and Raman excitation wavelength affect data interpretation

In this report, procedures are discussed for the enrichment of single-walled carbon nanotube (SWNT) types by simple filtration of the functionalized SWNTs through silica gel. This separation uses nanotube sidewall functionalization employing two different strategies. In the first approach, a crude mixture of metallic and semiconducting SWNTs was heavily functionalized with 4-tert-butylphenyl addends to impart solubility to the entire sample of SWNTs. Two major polarity fractions were rapidly filtered through silica gel, with the solvent being removed in vacuo, heated to 700 degrees C to remove the addends, and analyzed spectroscopically. The second approach uses two different aryldiazonium salts (one with a polar grafting group and one nonpolar), appended selectively onto the different SWNTs by means of titration and monitoring by UV analysis throughout the functionalization process. The different addends accentuate the polarity differences between the band-gap-based types permitting their partial separation on silica gel. Thermal treatment regenerated pristine SWNTs in enriched fractions. The processed samples were analyzed and characterized by Raman spectroscopy. A controlled functionalization method using 4-fluorophenyl and 4-iodophenyl addends was performed, and XPS analyses yielded data on the degree of functionalization needed to affect the van Hove singularities in the UV/vis/NIR spectra. Finally, we demonstrate that relative peak intensity changes in Raman spectra can be caused by morphological changes in SWNT bundling based on differing flocculation or deposition methods. Therefore a misleading impression of separations can result, underscoring the care needed in assessing efficacies in SWNT enrichment and the prerequisite use of multiple excitation wavelengths and similar flocculation or deposition methods in comparative analyses.     

Aqueous dispersion, surface thiolation, and direct self-assembly of carbon nanotubes on gold

We report the efficient aqueous dispersion of pristine HiPco single-walled carbon nanotubes (SWNTs) with ionic liquid (IL)-based surfactants 1-dodecyl-3-methylimidazolium bromide (1) and 1-(12-mercaptododecyl)-3-methylimidazolium bromide (2), the thiolation of nanotube sidewalls with 2, and the controlled self-assembly of positively charged SWNT-1,2 composites on gold. Optical absorption spectra and resonance Raman (RR) data of obtained aqueous SWNT-1,2 dispersions are consistent with debundled and noncovalently functionalized nanotubes whose electronic properties have not been disturbed. Additionally, the dispersion of pristine nanotube material with surfactants 1 and 2 leads to a high degree of purification from carbonaceous particles. The chiralities of the 14 smallest semiconducting HiPco SWNTs in resonance with Raman excitation at 1064 nm (1.165 eV) were determined in SWNT-2 aqueous dispersion using UV-vis-NIR and RR spectra. X-ray photoelectron spectroscopy (XPS) and surface-enhanced resonance Raman scattering (SERRS) spectroscopy of SWNT-2 submonolayers on gold verified the encapsulation of individualized SWNTs with IL surfactants, the cleavage of S-S disulfide bonds formed in aqueous SWNT-2 suspensions, and the direct chemisorption of the SWNT-2 composite on bare gold via the Au-S bond. Aqueous dispersions of SWNTs with IL-based surfactants add biofunctionality to carbon nanotubes by imparting the positive surface charge necessary for interactions with cell membranes. Our technique, which purifies pristine nanotube material and produces water-soluble, positively charged nanotubes with pendent surface-active thiol groups, may also be translated to other carbon nanotubes and carbon nanostructures. Self-assembled, positively charged submonolayers of SWNTs can be further used for applications in cell biology and sensor technology.     

Effects of ionic surfactant adsorption on single-walled carbon nanotube thin film devices in aqueous solutions

Field-effect transistors were fabricated using high-density single-walled carbon nanotube (SWNT) thin films directly grown on suitable substrates. Such approach eliminated the variations of device behaviors in individual SWNT devices by utilizing a large number of SWNTs in each device. We have found that the behaviors of such devices are closely related to the surface charge densities around SWNTs in aqueous solutions. Adsorption of ionic surfactants on the surface could significantly modulate the device characteristics, which could be detected by measuring the conductance of the devices. The devices could be tuned to be sensitive to either anionic or cationic surfactants by tailoring the surface properties of SiO(2) substrates around SWNTs. This effect could be potentially used to design chemical and biological sensors.     

Optically sensing additional sonication effects on dispersed HiPco nanotubes in aerated water

Ultrasonication is a necessary process to make single-walled carbon nanotubes (SWNTs) soluble in aqueous solution with surfactants such as sodium dodecyl sulfate (SDS). However, an understanding of the sonication effects on the electronic and optical properties of SWNTs in aqueous solution is still lacking. Here, we have observed that sonication-induced pH changes suppress the optical transitions of the first interband transition pair (S11) in the density of states of semiconducting SWNTs while other possible intermediates induced by sonication contribute less significantly to the observed spectral changes without the involvement of sonication-induced pH decrease. The suppressed S11 peaks can be restored by adding basic solution, suggesting that the lattice structure of SWNTs is undisrupted by the sonication used here. The absorbance of S11 peaks shows a nearly linear relationship with sonication-induced pH changes in the narrow pH range of 5.2 and 6.1. The results indicate that SDS-encased SWNTs may be used as an indicator for sonolysis-related applications.