Complexity in the Photofunctionalization of Single-Wall Carbon Nanotubes with Hypochlorite.

The reaction of aqueous suspensions of single-wall carbon nanotubes (SWCNTs) with UV-excited sodium hypochlorite has previously been reported to be an efficient route for doping nanotubes with oxygen atoms. We have investigated how this reaction system is affected by pH level, dissolved O content, and radical scavengers and traps. Products were characterized with near-IR fluorescence, Raman, and XPS spectroscopy.

A Review: Non-Contact and Full-Field Strain Mapping Methods for Experimental Mechanics and Structural Health Monitoring.

Non-contact and full-field strain mapping captures strain across an entire surface, providing a complete two-dimensional (2D) strain distribution without attachment to sensors. It is an essential technique with wide-ranging applications across various industries, significantly contributing to experimental mechanics and structural health monitoring. Although there have been reviews that focus on specific methods, such as interferometric techniques or carbon nanotube-based strain sensors, a comprehensive comparison that evaluates these diverse methods together is lacking.

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.

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.

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.

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) oligomers ( from 3 to 20) to SDS-coated nanotube samples. There is a strong kinetic dependence on the oligomer length, with (GT) giving an initial rate more than 300 times greater than that of (GT).

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.

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" (S) and a comparison of its performance against the established digital image correlation (DIC) method. S measures strain-induced shifts in the emission wavelengths of single-wall carbon nanotubes embedded in a thin film on the specimen. The new S film improves spectral uniformity of the nanotube sensors, avoids the need for annealing at elevated temperatures, and allows for parallel DIC measurements.

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.

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.

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.

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 (O). 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.

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.

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.

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.

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.

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.

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.

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) 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.

Skewness Analysis in Variance Spectroscopy Measures Nanoparticle Individualization.

An important enabling step in nanoparticle studies is the sorting of heterogeneous mixtures to prepare structurally homogeneous samples. It is also necessary to detect and monitor aggregation of the individual nanoparticles. Although variance spectroscopy provides a simple optical method for finding low concentrations of heteroaggregates in samples such as single-walled carbon nanotube dispersions, it cannot detect the homoaggregates that are relevant for well-sorted samples.

Quenching of Single-Walled Carbon Nanotube Fluorescence by Dissolved Oxygen Reveals Selective Single-Stranded DNA Affinities.

The selective interactions between short oligomers of single-stranded DNA (ssDNA) and specific structures of single-walled carbon nanotubes have been exploited in powerful methods for nanotube sorting. We report here that nanotubes coated with ssDNA also display selective interactions through the selective quenching of nanotube fluorescence by dissolved oxygen. In aqueous solutions equilibrated under 1 atm of O, emission intensity from semiconducting nanotubes is reduced by between 9 and 40%, varying with the combination of ssDNA sequence and nanotube structure.

(n,m)-Specific Absorption Cross Sections of Single-Walled Carbon Nanotubes Measured by Variance Spectroscopy.

A new method based on variance spectroscopy has enabled the determination of absolute absorption cross sections for the first electronic transition of 12 (n,m) structural species of semiconducting single-walled carbon nanotubes (SWCNTs). Spectrally resolved measurements of fluorescence variance in dilute bulk samples provided particle number concentrations of specific SWCNT species. These values were converted to carbon concentrations and correlated with resonant components in the absorbance spectrum to deduce (n,m)-specific absorption cross sections (absorptivities) for nanotubes ranging in diameter from 0.

Spectral triangulation: a 3D method for locating single-walled carbon nanotubes in vivo.

Nanomaterials with luminescence in the short-wave infrared (SWIR) region are of special interest for biological research and medical diagnostics because of favorable tissue transparency and low autofluorescence backgrounds in that region. Single-walled carbon nanotubes (SWCNTs) show well-known sharp SWIR spectral signatures and therefore have potential for noninvasive detection and imaging of cancer tumours, when linked to selective targeting agents such as antibodies. However, such applications face the challenge of sensitively detecting and localizing the source of SWIR emission from inside tissues.

Variance Spectroscopy.

Spectroscopic analysis and study of nanoparticle samples is often hampered by structural diversity that presents a complex superposition of spectral signatures. By probing the spectra of small volumes within dilute samples, we can expose statistical variations in composition to obtain information unavailable from bulk spectroscopy. This new approach is demonstrated using fluorescence spectra of unsorted single-walled carbon nanotube samples to deduce structure-specific abundances and emissive efficiencies.