Sequence-Dependent Surface Coverage of ssDNA Coatings on Single-Wall Carbon Nanotubes.

A combination of experimental measurements and molecular dynamics (MD) simulations was used to investigate how the surfaces of single-wall carbon nanotubes (SWCNTs) are covered by adsorbed ssDNA oligos with different base compositions and lengths. By analyzing the UV absorption spectra of ssDNA-coated SWCNTs before and after coating displacement by a transparent surfactant, the mass ratios of adsorbed ssDNA to SWCNTs were determined for poly-T, poly-C, GT-containing, and AT-containing ssDNA oligos. Based on the measured mass ratios, it is estimated that an average of 20, 22, 26, or 32 carbon atoms are covered by one adsorbed thymine, cytosine, adenine, or guanine nucleotide, respectively. In addition, the UV spectra revealed electronic interactions of varying strengths between the nucleobase aromatic rings and the nanotube π-systems. Short poly-T DNA oligos show stronger π-π stacking interactions with SWCNT surfaces than do short poly-C DNA oligos, whereas both long poly-C and poly-T DNA oligos show strong interactions. These experiments were complemented by MD computations on simulated systems that were constrained to match the measured ssDNA/SWCNT mass ratios. The surface coverages computed from the MD results varied with oligo composition in a pattern that correlates higher measured yields of nanotube fluorescence with greater surface coverage.

Diameter-Dependent Competitive Adsorption of Sodium Dodecyl Sulfate and Single-Stranded DNA on Carbon Nanotubes.

The equilibrium compositions of coatings on single-wall carbon nanotubes were spectroscopically deduced for samples dispersed in dilute sodium dodecyl sulfate (SDS) and then exposed to low concentrations of ssDNA oligomers. With all studied oligomers, displacement of the SDS tended to occur at lower ssDNA concentrations for smaller diameter nanotubes than for larger diameter ones. However, the behavior varied significantly with oligomer. For example, the diameter dependence was steeper for (TAT)4 than for (ATT)4, suggesting that interstrand head-to-tail hydrogen bonding interactions play a role in SWCNT wrapping. Concentrations of ssDNA in the range of several µg/mL displace SDS from nanotubes dispersed in 1500 µg/mL SDS solutions. This effect allows the use of coating exchange to prepare ssDNA dispersions with minimal oligomer costs. Another demonstrated use exploits the structure-dependent relative coating affinities in a simple filtration method for the diameter enrichment of SWCNT mixtures.

Kinetics of Single-Wall Carbon Nanotube Coating Displacement by Single-Stranded DNA Depends on Nanotube Structure.

Time-resolved fluorescence spectroscopy has been used to study the displacement of adsorbed sodium dodecyl sulfate (SDS) from the surface of single-wall carbon nanotubes (SWCNTs) by short strands of single-stranded DNA. Intensity changes in near-infrared emission peaks of various SWCNT structures were analyzed following the addition of six different (GT)n oligomers (n from 3 to 20) to SDS-coated nanotube samples. There is a strong kinetic dependence on the oligomer length, with (GT)3 giving an initial rate more than 300 times greater than that of (GT)20. For shorter oligos in the (GT)n series, we observe an inverse dependence of the displacement rate on the SWCNT diameter, with SDS displaced from (6,5) more than twice as fast as from (8,7). However, this diameter dependence is reversed for oligos with more than six (GT) units. There is also a systematic dependence of the displacement rate on the nanotube chiral angle that is strongest for (GT)5, leading to a factor of ∼3 initial rate difference between (9,1) and (6,5) despite their identical diameters. To account for these findings, we propose a simple two-step kinetic model in which disruption of the original SDS coating is followed by conformational relaxation of ssDNA on the nanotube surface. The relaxation is relatively fast for ssDNA oligos shorter than 12 bp, making the first step rate-determining. Conversely, relaxation of the longer oligomers is slow enough that the second step becomes rate-determining.

Structure-Resolved Monitoring of Single-Wall Carbon Nanotube Functionalization from Raman Intermediate Frequency Modes.

Single-wall carbon nanotubes (SWCNTs) can be covalently modified to generate useful changes in their spectroscopic and photophysical properties. We report here a new method to monitor the extent of such functionalization reactions for different nanotube structures. Raman spectra are analyzed to find the intensities of structure-specific intermediate frequency mode (IFM) features in the range of ca. 350 to 650 cm-1, which are induced by introduction of sp3 defects. The IFM frequencies are found to depend on both the nanotube diameter and Raman excitation wavelength. The growth of IFM features is accompanied by a decrease in RBM intensities, so the IFM to RBM intensity ratio can provide a sensitive, structure-specific measure of nanotube functionalization.

Photostable Small-Molecule NIR-II Fluorescent Scaffolds that Cross the Blood-Brain Barrier for Noninvasive Brain Imaging.

The second near-infrared (NIR-II, 1000-1700 nm) fluorescent probes have significant advantages over visible or NIR-I (600-900 nm) imaging for both depth of penetration and level of resolution. Since the blood-brain barrier (BBB) prevents most molecules from entering the central nervous system, NIR-II dyes with large molecular frameworks have limited applications for brain imaging. In this work, we developed a series of boron difluoride (BF2) formazanate NIR-II dyes, which had tunable photophysical properties, ultrahigh photostability, excellent biological stability, and strong brightness. Modulation of the aniline moiety of BF2 formazanate dyes significantly enhances their abilities to cross the BBB for noninvasive brain imaging. Furthermore, the intact mouse brain imaging and dynamic dye diffusion across the BBB were monitored using these BF2 formazanate dyes in the NIR-II region. In murine glioblastoma models, these dyes can differentiate tumors from normal brain tissues. We anticipate that this new type of small molecule will find potential applications in creating probes and drugs relevant to theranostic for brain pathologies.

Compositional Analysis of ssDNA-Coated Single-Wall Carbon Nanotubes through UV Absorption Spectroscopy.

Aqueous suspensions of single-wall carbon nanotubes (SWCNTs) coated by ssDNA are analyzed using UV absorption and total carbon measurements. The results give absolute average concentrations of both components in samples without free ssDNA. From those values, the average mid-UV SWCNT absorptivity is deduced for three different batches of relatively small diameter nanotubes: two HiPco and one CoMoCAT. The absorptivity values enable the use of simple spectrophotometry to measure absolute concentrations of similar SWCNT samples in aqueous SDS. The results also quantify the mass ratio of ssDNA to SWCNT, defining the average number of nanotube carbon atoms suspended by one ssDNA strand of T15GT15 or T30G. Comparing this experimental parameter with results from replica exchange molecular dynamics simulations of one ssDNA strand freely adsorbed on a (6,5) segment shows close agreement between the computed number of SWCNT atoms covered per strand and the measured number of SWCNT atoms suspended per strand.

Next-generation 2D optical strain mapping with strain-sensing smart skin compared to digital image correlation.

This study reports next generation optical strain measurement with "strain-sensing smart skin" (S4) and a comparison of its performance against the established digital image correlation (DIC) method. S4 measures strain-induced shifts in the emission wavelengths of single-wall carbon nanotubes embedded in a thin film on the specimen. The new S4 film improves spectral uniformity of the nanotube sensors, avoids the need for annealing at elevated temperatures, and allows for parallel DIC measurements. Noncontact strain maps measured with the S4 films and point-wise scanning were directly compared to those from DIC on acrylic, concrete, and aluminum test specimens, including one with subsurface damage. Strain features were more clearly revealed with S4 than with DIC. Finite element method simulations also showed closer agreement with S4 than with DIC results. These findings highlight the potential of S4 strain measurement technology as a promising alternative or complement to existing technologies, especially when accumulated strains must be detected in structures that are not under constant observation.

Guanine-Specific Chemical Reaction Reveals ssDNA Interactions on Carbon Nanotube Surfaces.

Understanding the conformations of physisorbed single-stranded DNA (ssDNA) oligos on single-wall carbon nanotube (SWCNT) surfaces is important for advancing basic nanoscience and for developing applications in biomedicine and quantum information processing. Here we report evidence that the ssDNA strands are partly desorbed from the nanotube surface under common conditions. SWCNT suspensions were prepared in eight ssDNA oligos, each containing 1 guanine and 30 thymine bases but differing in the position of the guanine within the strand. Singlet oxygen exposure then covalently functionalized the guanine to the SWCNT surface, red-shifting the nanotube fluorescence by an amount reflecting the guanine spatial density at the surface. Spectral shifts were greatest for central guanine positions and smallest for end positions. In conjunction with steered molecular dynamics simulations, the results suggest that steric interference between neighboring ssDNA strands on an individual nanotube causes significant dislocation or desorption of the strand ends while central regions remain better wrapped around the nanotube. This effect decreases with decreasing concentrations of free ssDNA.

Near-infrared photoluminescence of Portland cement.

Portland cement emits bright near-infrared photoluminescence that can be excited by light wavelengths ranging from at least 500-1000 nm. The emission has a peak wavelength near 1140 nm and a width of approximately 30 nm. Its source is suggested to be small particles of silicon associated with calcium silicate phases. The luminescence peak wavelength appears independent of the cement hydration state, aggregates, and mechanical strain but increases weakly with increasing temperature. It varies slightly with the type of cement, suggesting a new non-contact method for identifying cement formulations. After a thin opaque coating is applied to a cement or concrete surface, subsequent formation of microcracks exposes the substrate's near-infrared emission, revealing the fracture locations, pattern, and progression. This damage would escape detection in normal imaging inspections. Near-infrared luminescence imaging may therefore provide a new tool for non-destructive testing of cement-based structures.

Quantum Light Emission from Coupled Defect States in DNA-Functionalized Carbon Nanotubes.

Solid-state single-photon sources are essential building blocks for quantum photonics and quantum information technologies. This study demonstrates promising single-photon emission from quantum defects generated in single-wall carbon nanotubes (SWCNTs) by covalent reaction with guanine nucleotides in their single-stranded DNA coatings. Low-temperature photoluminescence spectroscopy and photon-correlation measurements on individual guanine-functionalized SWCNTs (GF-SWCNTs) indicate that multiple, closely spaced guanine defect sites within a single ssDNA strand collectively form an exciton trapping potential that supports a localized quantum state capable of room-temperature single-photon emission. In addition, exciton traps from adjacent ssDNA strands are weakly coupled to give cross-correlations between their separate photon emissions. Theoretical modeling identifies coupling mechanism as a capture of band-edge excitons. Because the spatial pattern of nanotube functionalization sites can be readily controlled by selecting ssDNA base sequences, GF-SWCNTs should become a versatile family of quantum light emitters with engineered properties.

Oxime as a general photocage for the design of visible light photo-activatable fluorophores.

Photoactivatable fluorophores have been widely used for tracking molecular and cellular dynamics with subdiffraction resolution. In this work, we have prepared a series of photoactivatable probes using the oxime moiety as a new class of photolabile caging group in which the photoactivation process is mediated by a highly efficient photodeoximation reaction. Incorporation of the oxime caging group into fluorophores results in loss of fluorescence. Upon light irradiation in the presence of air, the oxime-caged fluorophores are oxidized to their carbonyl derivatives, restoring strong fluorophore fluorescence. To demonstrate the utility of these oxime-caged fluorophores, we have created probes that target different organelles for live-cell confocal imaging. We also carried out photoactivated localization microscopy (PALM) imaging under physiological conditions using low-power light activation in the absence of cytotoxic additives. Our studies show that oximes represent a new class of visible-light photocages that can be widely used for cellular imaging, sensing, and photo-controlled molecular release.

Delayed Fluorescence from Carbon Nanotubes through Singlet Oxygen-Sensitized Triplet Excitons.

Single-wall carbon nanotubes (SWCNTs) in liquid suspension have been observed to emit delayed, microsecond-scale fluorescence arising from upconverted triplet excitons that are directly created through energy transfer from singlet oxygen molecules (1O2). The singlet oxygen is produced through quenching of an optically excited organic sensitizer. The mechanism of this delayed fluorescence has been deduced from measurements of time-resolved emission kinetics, delayed emission spectra, and polarization-resolved excitation-emission spectra. The observed strong dependence of 1O2 sensitization efficiency on SWCNT structure suggests that (7,6) triplet excitons have an energy near 970 meV. The yields for E11T → E11S upconversion are found to be in the range of several percent. These yields increase with increasing temperature and decrease with increasing excitation intensities, reflecting thermal activation and triplet-triplet exciton annihilation processes.

Dye Quenching of Carbon Nanotube Fluorescence Reveals Structure-Selective Coating Coverage.

Many properties and applications of single-wall carbon nanotubes (SWCNTs) depend strongly on the coatings that allow their suspension in aqueous media. We report that SWCNT fluorescence is quenched by reversible physisorption of dye molecules such as methylene blue, and that measurements of that quenching can be used to infer structure-specific exposures of the nanotube surface to the surrounding solution. SWCNTs suspended in single-stranded DNA oligomers show quenching dependent on the combination of nanotube structure and ssDNA base sequence. Several sequences are found to give notably high or low surface coverages for specific SWCNT species. These effects seem correlated with the selective recognitions used for DNA-based structural sorting of nanotubes. One notable example is that dye quenching of fluorescence from SWCNTs coated with the (ATT)4 base sequence is far stronger for one (7,5) enantiomer than for the other, showing that coating coverage is associated with the coating affinity difference reported previously for this system. Equilibrium modeling of quenching data has been used to extract parameters for comparative complexation constants and accessible surface areas. Further insights are obtained from molecular dynamics simulations, which give estimated contact areas between ssDNA and SWCNTs that correlate with experimentally inferred surface exposures and account for the enantiomeric discrimination of (ATT)4.

Tailoring the Properties of Single-Wall Carbon Nanotube Samples through Structure-Selective Near-Infrared Photochemistry.

As-produced samples of single-wall carbon nanotubes (SWCNTs) contain many structural forms with characteristic properties. In particular, semiconducting SWCNTs display distinct near-IR optical absorption and emission peaks. We show that the selective irradiation of these absorption features can induce structure-specific functionalization in unsorted SWCNT samples. This approach is demonstrated with an ambient temperature photoreaction involving dissolved O2 and irradiation at 955, 985, and 1130 nm, causing preferential covalent reactions of (8,3), (6,5), and (7,6) SWCNTs, respectively. Treated samples showed permanent fluorescence quenching and absorption bleaching near the irradiation wavelength and an increase in the Raman D/G intensity ratio, indicating the formation of covalent defects. The reaction has a very low photochemical quantum yield and was observed for samples suspended in single-stranded DNA and in conventional surfactants that gave incomplete coverage of the nanotube surface. The approach of exploiting sharp nanotube near-IR transitions for structure-selective photochemistry provides a path to tailor SWCNT optical properties for several potential applications without the need for physical sorting.

Photoexcited Aromatic Reactants Give Multicolor Carbon Nanotube Fluorescence from Quantum Defects.

Covalent functionalization of single-wall carbon nanotubes (SWCNTs) can be valuable for modifying their electronic properties and creating fluorescent quantum defects. We report here a previously unreported category of such reactions involving interactions of photoexcited aromatic compounds with SWCNT sidewalls. When aqueous suspensions of SWCNTs are exposed to organic aromatic compounds and then irradiated by UV light, fluorescent defects are formed in the nanotubes at rates that depend on the aromatic ring substituents. In reactions with aniline or iodoaniline, strong spectral sidebands appear within 1 min. Total SWCNT photoluminescence can be enhanced by a factor as large as ∼5. Notably, emission spectra of reacted SWCNTs depend on the presence or absence of dissolved oxygen during the reaction. For (6,5) SWCNTs, treatment when oxygen is present gives an additional emission band red-shifted by 160 meV from the pristine position, whereas treatment without oxygen leads to two additional emission bands red-shifted by 140 and 270 meV. Variance spectroscopy shows the presence of individual "multicolor" nanotubes with three distinct emission bands (pristine plus two shifted). The facile generation of dual fluorescent quantum defects in SWCNTs provides emission closer to standard telecom wavelengths, advancing the prospects for applications as single-photon sources in quantum information processing.

Synchro-Excited Free-Running Single Photon Counting: A Novel Method for Measuring Short-Wave Infrared Emission Kinetics.

Time-resolved measurements of short-wave infrared (SWIR) photoluminescence on the submicrosecond to millisecond scale are needed for physical and chemical studies involving singlet oxygen, single-walled carbon nanotubes, and other samples with weak, slow emission. We present here an alternative to the common method of time-correlated single photon counting (TCSPC) that is well suited to indium gallium arsenide avalanche photodiode (APD) detectors operated in Geiger mode. In the new method, termed synchro-excited free-running single photon counting (SEFR-SPC), excitation pulses from inexpensive laser diodes (providing a variety of wavelengths) are synchronized to detection events from a free-running detector covering the 900 to 1700 nm range. In contrast to traditional TCSPC, data from this method can be rigorously corrected for pile-up distortions, allowing operation with high excitation powers and low repetition rates. A technique is described to extend the system's dynamic range to approximately 108. We also show that SEFR-SPC provides state-of-the-art sensitivity in the SWIR spectral region and that spectrally filtered kinetic data can offer additional insights. A six-step correction protocol has been developed and implemented as a LabVIEW program for very accurate acquisition of kinetic shapes. The SEFR-SPC method will be a valuable tool for studies of weak, long-lived emission sources.

Controlled Patterning of Carbon Nanotube Energy Levels by Covalent DNA Functionalization.

Each structural form of single-wall carbon nanotube (SWCNT) has specific electronic and optical properties, but it has not been possible to achieve spatial or energetic modulation of those properties in controllable ways. We present here a simple method for using chemical reactions with single-stranded DNA (ssDNA) to accomplish such modulation. When aqueous suspensions of SWCNTs coated with ssDNA are exposed to singlet oxygen under ambient conditions, the nanotubes selectively form covalent bonds to the guanine nucleotides. This locally modulates semiconducting SWCNT energy levels and red-shifts their emission wavelengths by up to 10%. Both the magnitude and spatial pattern of these shifts can be controlled by selecting the nucleotide sequence used to coat the nanotubes. Biomedical, optoelectronic, and single-photon emission applications are foreseen.

Creating fluorescent quantum defects in carbon nanotubes using hypochlorite and light.

Covalent doping of single-walled carbon nanotubes (SWCNTs) can modify their optical properties, enabling applications as single-photon emitters and bio-imaging agents. We report here a simple, quick, and controllable method for preparing oxygen-doped SWCNTs with desirable emission spectra. Aqueous nanotube dispersions are treated at room temperature with NaClO (bleach) and then UV-irradiated for less than one minute to achieve optimized O-doping. The doping efficiency is controlled by varying surfactant concentration and type, NaClO concentration, and irradiation dose. Photochemical action spectra indicate that doping involves reaction of SWCNT sidewalls with oxygen atoms formed by photolysis of ClO- ions. Variance spectroscopy of products reveals that most individual nanotubes in optimally treated samples show both pristine and doped emission. A continuous flow reactor is described that allows efficient preparation of milligram quantities of O-doped SWCNTs. Finally, we demonstrate a bio-imaging application that gives high contrast short-wavelength infrared fluorescence images of vasculature and lymphatic structures in mice injected with only ~100 ng of the doped nanotubes.

Enantiomers of Single-Wall Carbon Nanotubes Show Distinct Coating Displacement Kinetics.

It is known that specific oligomers of single-stranded DNA (ssDNA) can show remarkable selectivity when coating different structural species of single-wall carbon nanotubes (SWCNTs). We report that (ATT)4 ssDNA coatings strongly distinguish between the two optical isomers of (7,5) SWCNTs. This causes resolvable shifts in their fluorescence spectra and differences of 2 orders of magnitude in the room temperature rates of coating displacement, as monitored through changes in nanotube fluorescence wavelength and intensity on exposure to sodium deoxycholate. During coating displacement, the enantiomer with high affinity for the ssDNA oligomer is deduced to form an intermediate hybrid that is not observed for the low affinity enantiomer. These results reveal that enantiomeric differences in SWCNTs complexed with ssDNA are more diverse and dramatic than previously recognized.