Jason K. Streit

Directly Measured Optical Absorption Cross Sections for Structure-Selected Single-Walled Carbon Nanotubes

We have measured peak and spectrally integrated absolute absorption cross sections for the first (E11) and second (E22) optical transitions of seven semiconducting single-walled carbon nanotube (SWCNT) species in bulk suspensions. Species-specific concentrations were determined using short-wave IR fluorescence microscopy to directly count SWCNTs in a known sample volume. Measured cross sections per atom are inversely related to nanotube diameter. E11 cross sections are larger for mod 1 species than for mod 2; the opposite is found for E22.

Redox Sorting of Carbon Nanotubes

This work expands the redox chemistry of single-wall carbon nanotubes (SWCNTs) by investigating its role in a number of SWCNT sorting processes. Using a polyethylene glycol (PEG)/dextran (DX) aqueous two-phase system, we show that electron-transfer between redox molecules and SWCNTs triggers reorganization of the surfactant coating layer, leading to strong modulation of nanotube partition in the two phases. While the DX phase is thermodynamically more favored by an oxidized SWCNT mixture, the mildly reducing PEG phase is able to recover SWCNTs from oxidation and extract them successively from the DX phase. Remarkably, the extraction order follows SWCNT bandgap: semiconducting nanotubes of larger bandgap first, followed by semiconducting nanotubes of smaller bandgap, then nonarmchair metallic tubes of small but nonvanishing bandgap, and finally armchair metallic nanotubes of zero bandgap. Furthermore, we show that redox-induced surfactant reorganization is a common phenomenon, affecting nanotube buoyancy in a density gradient field, affinity to polymer matrices, and solubility in organic solvents. These findings establish redox modulation of surfactant coating structures as a general mechanism for tuning a diverse range of SWCNT sorting processes and demonstrate for the first time that armchair and nonarmchair metallic SWCNTs can be separated by their differential response to redox.

Differentiating Left- and Right-Handed Carbon Nanotubes by DNA

New structural characteristics emerge when solid-state crystals are constructed in lower dimensions. This is exemplified by single-wall carbon nanotubes, which exhibit a degree of freedom in handedness and a multitude of helicities that give rise to three distinct types of electronic structures: metals, quasi-metals, and semiconductors. Here we report the use of intrinsically chiral single-stranded DNA to achieve simultaneous handedness and helicity control for all three types of nanotubes. We apply polymer aqueous two-phase systems to select special DNA-wrapped carbon nanotubes, each of which we argue must have an ordered DNA structure that binds to a nanotube of defined handedness and helicity and resembles a well-folded biomacromolecule with innate stereoselectivity. We have screened over 300 short single-stranded DNA sequences with palindrome symmetry, leading to the selection of more than 20 distinct carbon nanotube structures that have defined helicity and handedness and cover the entire chiral angle range and all three electronic types. The mechanism of handedness selection is illustrated by a DNA sequence that adopts two distinct folds on a pair of (6,5) nanotube enantiomers, rendering them large differences in fluorescence intensity and chemical reactivity. This result establishes a first example of functionally distinguishable left- and right-handed carbon nanotubes. Taken together, our work demonstrates highly efficient enantiomer differentiation by DNA and offers a first comprehensive solution to achieve simultaneous handedness and helicity control for all three electronic types of carbon nanotubes.

Chromatic aberration short-wave infrared spectroscopy: nanoparticle spectra without a spectrometer.

A new method is described for measuring the short-wave infrared (SWIR) emission wavelengths of numerous individual nanoparticles without using a dedicated spectrometer. Microscope objectives designed for use at visible wavelengths often show severe axial chromatic aberration in the SWIR. This makes coplanar objects emitting at different SWIR wavelengths appear to focus at different depths. After this aberration has been calibrated for a particular objective lens, the depth at which an emissive nanoparticle appears brightest and best focused can be used to deduce its peak emission wavelength. The method is demonstrated using a dilute, structurally polydisperse sample of single-walled carbon nanotubes deposited onto a microscope slide. Discrete emission centers in this sample have different peak wavelengths corresponding to specific nanotube structural species. A set of images was recorded at stepped focus settings and analyzed to find the sharpest focus depth of each nanotube. The chromatic aberration calibration curve converted these depths into peak emission wavelengths with a spectral resolution better than 3 nm, allowing identification of each nanotubes structure. Chromatic aberration spectroscopy is a practical tool for using existing microscopic equipment to extract significant spectral information on coplanar nanoparticle samples that emit or scatter light.

A Low Energy Route to DNA-Wrapped Carbon Nanotubes via Replacement of Bile Salt Surfactants

DNA-wrapped carbon nanotubes are a class of bionano hybrid molecules that have enabled carbon nanotube sorting, controlled assembly, and biosensing and bioimaging applications. The current method of synthesizing these hybrids via direct sonication of DNA/nanotube mixtures is time-consuming and not suitable for high-throughput synthesis and combinatorial sequence screening. Additionally, the direct sonication method does not make use of nanotubes presorted by extensively developed surfactant-based methods, is not effective for large diameter (>1 nm) tubes, and cannot maintain secondary and tertiary structural and functional domains present in certain DNA sequences. Here, we report a simple, quick, and robust process to produce DNA-wrapped carbon nanotube hybrids with nanotubes of broad diameter range and DNA of arbitrary sequence. This is accomplished by exchanging strong binding bile salt surfactant coating with DNA in methanol/water mixed solvent and subsequent precipitation with isopropyl alcohol. The exchange process can be completed within 10 min and converts over 90% nanotubes into the DNA wrapped form. Applying the exchange process to nanotubes presorted by surfactant-based methods, we show that the resulting DNA-wrapped carbon nanotubes can be further sorted to produce nanotubes with defined handedness, helicity, and endohedral filling. The exchange method greatly expands the structural and functional variety of DNA-wrapped carbon nanotubes and opens possibilities for DNA-directed assembly of structurally sorted nanotubes and high-throughput screening of properties that are controlled by the wrapping DNA sequences.