R-3 Repository :: Browsing by Author "Bachilo, Sergei M."

Browsing by Author "Bachilo, Sergei M."

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Assessing Inhomogeneity in Sorted Samples of Single-Walled Carbon Nanotubes through Fluorescence and Variance Spectroscopy
(The Electrochemical Society, 2017) Kadria-Vili, Yara; Sanchez, Stephen R.; Bachilo, Sergei M.; Weisman, R. Bruce
Detailed spectroscopic analysis has been used to study the homogeneity of single-walled carbon nanotube fractions carefully prepared by nonlinear density gradient ultracentrifugation sorting. Two distinct colored bands containing (6,5) enantiomers were subdivided into several extracted fractions that were separately diluted with sodium cholate surfactant and characterized by fluorescence, absorption, and variance spectroscopy. Values were measured for emission and absorption peak positions, Stokes shifts, emission peak widths, and emissive quantum yields. In addition, variance data were used to find relative emission per nanotube and to plot covariance slices representing homogeneous emission spectra. It was found that emission from SWCNTs within the upper enantiomer band shifts to shorter wavelengths with increasing depth in the centrifuge tube. In the lower enantiomer band such spectral shifts were not observed, but the emissive quantum yields decreased with depth. Variance analysis revealed spectral differences among SWCNTs within the same fraction of the same band. It is concluded that current methods for density gradient ultracentrifugation sorting produce samples that retain measurable structural and spectral inhomogeneities.
Creating fluorescent quantum defects in carbon nanotubes using hypochlorite and light
(Springer Nature, 2019) Lin, Ching-Wei; Bachilo, Sergei M.; Zheng, Yu; Tsedev, Uyanga; Huang, Shengnan; Weisman, R. Bruce; Belcher, Angela M.; Smalley-Curl Institute
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.
Dye Quenching of Carbon Nanotube Fluorescence Reveals Structure-Selective Coating Coverage
(American Chemical Society, 2020) Zheng, Yu; Alizadehmojarad, Ali A.; Bachilo, Sergei M.; Kolomeisky, Anatoly B.; Weisman, R. Bruce; Smalley-Curl Institute
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.
Enabling in vivo measurements of nanoparticle concentrations with three-dimensional optoacoustic tomography
(Wiley, 2014) Tsyboulski, Dmitri A.; Liopo, Anton V.; Su, Richard; Ermilov, Sergey A.; Bachilo, Sergei M.; Weisman, R. Bruce; Oraevsky, Alexander A.
In this report, we demonstrate the feasibility of using optoacoustic tomography (OAT) to evaluate biodistributions of nanoparticles in animal models. The redistribution of single-walled carbon nanotubes (SWCNTs) was visualized in living mice. Nanoparticle concentrations in harvested organs were measured spectroscopically using the intrinsic optical absorption and fluorescence of SWCNTs. Observed increases in optoacoustic signal brightness in tissues were compared with increases in optical absorption coefficients caused by SWCNT accumulation. The methodology presented in this report can further be extended to calibrate the sensitivity of an optoacoustic imaging system for a range of changes in optical absorption coefficient values at specific locations or organs in a mouse body to enable noninvasive measurements of nanoparticle concentrations in vivo. Additionally, qualitative information provided by OAT and quantitative information obtained ex vivo may provide valuable feedback for advancing methods of quantitative analysis with OAT.
Enantiomers of Single-Wall Carbon Nanotubes Show Distinct Coating Displacement Kinetics
(American Chemical Society, 2018) Zheng, Yu; Bachilo, Sergei M.; Weisman, R. Bruce; Smalley-Curl Institute
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)4ﾠssDNA 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.
Fluorescent security ink using carbon nanotubes
(2010-03-23) Weisman, R. Bruce; Bachilo, Sergei M.; Booth, Eric Christopher; Rice University; United States Patent and Trademark Office
The present invention is directed toward fluorescent inks and markers comprising carbon nanotubes. The present invention is also directed toward methods of making such inks and markers and to methods of using such inks and markers, especially for security applications (e.g., anti-counterfeiting). Such inks and markers rely on the unique fluorescent properties of semiconducting carbon nanotubes.
High Precision Fractionator for use with Density Gradient Ultracentrifugation
(American Chemical Society, 2014) Kadria-Vili, Yara; Canning, Griffin; Bachilo, Sergei M.; Weisman, R. Bruce; Richard E. Smalley Institute for Nanoscale Science and Technology
The recent application of density gradient ultracentrifugation (DGU) for structural sorting of single-walled carbon nanotube samples has created a need for highly selective extraction of closely spaced layers formed in the centrifuged tube. We describe a novel computer-controlled device designed for this purpose. Through the use of fine needles, systematic needle motions, and slow flow rates, multiple sample layers can be aspirated under program control with minimal cross contamination between layers. The fractionator’s performance is illustrated with DGU-sorted samples of single-walled carbon nanotubes.
Method for separating single-wall carbon nanotubes and compositions thereof
(2006-07-11) Smalley, Richard E.; Hauge, Robert H.; Kittrell, Carter W.; Sivarajan, Ramesh; Strano, Michael S.; Bachilo, Sergei M.; Weisman, R. Bruce; Rice University; United States Patent and Trademark Office
The invention relates to a process for sorting and separating a mixture of (n, m) type single-wall carbon nanotubes according to (n, m) type. A mixture of (n, m) type single-wall carbon nanotubes is suspended such that the single-wall carbon nanotubes are individually dispersed. The nanotube suspension can be done in a surfactant-water solution and the surfactant surrounding the nanotubes keeps the nanotube isolated and from aggregating with other nanotubes. The nanotube suspension is acidified to protonate a fraction of the nanotubes. An electric field is applied and the protonated nanotubes migrate in the electric fields at different rates dependent on their (n, m) type. Fractions of nanotubes are collected at different fractionation times. The process of protonation, applying an electric field, and fractionation is repeated at increasingly higher pH to separated the (n, m) nanotube mixture into individual (n, m) nanotube fractions. The separation enables new electronic devices requiring selected (n, m) nanotube types.
(n,m)-Specific Absorption Cross Sections of Single-Walled Carbon Nanotubes Measured by Variance Spectroscopy
(American Chemical Society, 2016) Sanchez, Stephen R.; Bachilo, Sergei M.; Kadria-Vili, Yara; Lin, Ching-Wei; Weisman, R. Bruce; Smalley-Curl Institute
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 0.69 to 1.03 nm. The measured cross sections per atom tend to vary inversely with nanotube diameter and are slightly greater for structures ofﾠmod 1ﾠtype than forﾠmod 2. Directly measured and extrapolated values are now available to support quantitative analysis of SWCNT samples through absorption spectroscopy.
Near-infrared photoluminescence of Portland cement
(Springer Nature, 2022) Meng, Wei; Bachilo, Sergei M.; Parol, Jafarali; Nagarajaiah, Satish; Weisman, R. Bruce
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.
Next-generation 2D optical strain mapping with strain-sensing smart skin compared to digital image correlation
(Springer Nature, 2022) Meng, Wei; Pal, Ashish; Bachilo, Sergei M.; Weisman, R. Bruce; Nagarajaiah, Satish
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.
Non-contact strain sensing of objects by use of single-walled carbon nanotubes
(2016-02-09) Weisman, R. Bruce; Withey, Paul A.; Bachilo, Sergei M.; Nagarajaiah, Satish; Vemuru, Venkata Srivishnu M.; Rice University; United States Patent and Trademark Office
In some embodiments, the present invention provides methods of detecting strain associated with an object by: (1) irradiating a composition that has been applied to the object, where the composition comprises semiconducting single-walled carbon nanotubes; (2) measuring an emission from the irradiated composition, where the emission comprises near infrared emission; and (3) correlating the near infrared emission to the presence or absence of strain associated with the object. In some embodiments, the aforementioned steps occur without physically contacting the object or the composition. In some embodiments, the aforementioned steps occur without utilizing Raman spectroscopy. Further embodiments of the present invention also include a step of applying the composition to the object.
Resonant optothermoacoustic detection of optical absorption
(2012-01-24) Kosterev, Anatoliy A.; Bachilo, Sergei M.; Rice University; United States Patent and Trademark Office
A device comprising an acoustic detector, one or more thermal sensing elements coupled to the acoustic detector, and a light source. A method comprising directing a beam of light at a wavelength at or near one or more thermal sensing elements, wherein the thermal sensing elements are coupled to an acoustic detector, determining a resonance frequency of the acoustic detector, wherein the acoustic detector is coupled to one or more of the thermal sensing elements, and measuring the response of the acoustic detector to detect optical radiation absorption proximate to or at the surface of one or more thermal sensing elements.
Spectral triangulation: a 3D method for locating single-walled carbon nanotubes in vivo
(Royal Society of Chemistry, 2016) Lin, Ching-Wei; Bachilo, Sergei M.; Vu, Michael; Beckingham, Kathleen M.; Weisman, R.Bruce; Smalley-Curl Institute
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. A new method, called spectral triangulation, is presented for three dimensional (3D) localization using sparse optical measurements made at the specimen surface. Structurally unsorted SWCNT samples emitting over a range of wavelengths are excited inside tissue phantoms by an LED matrix. The resulting SWIR emission is sampled at points on the surface by a scanning fibre optic probe leading to an InGaAs spectrometer or a spectrally filtered InGaAs avalanche photodiode detector. Because of water absorption, attenuation of the SWCNT fluorescence in tissues is strongly wavelength-dependent. We therefore gauge the SWCNT–probe distance by analysing differential changes in the measured SWCNT emission spectra. SWCNT fluorescence can be clearly detected through at least 20 mm of tissue phantom, and the 3D locations of embedded SWCNT test samples are found with sub-millimeter accuracy at depths up to 10 mm. Our method can also distinguish and locate two embedded SWCNT sources at distinct positions.
Structure-Dependent Thermal Defunctionalization of Single-Walled Carbon Nanotubes
(American Chemical Society, 2015) Ghosh, Saunab; Wei, Fang; Bachilo, Sergei M.; Hauge, Robert H.; Billups, W.E.; Weisman, R. Bruce; Smalley Institute for Nanoscale Science and Technology
Covalent sidewall functionalization of single-walled carbon nanotubes (SWCNTs) is an important tool for tailoring their properties for research purposes and applications. In this study, SWCNT samples were first functionalized by reductive alkylation using metallic lithium and 1-iodododecane in liquid ammonia. Samples of the alkyl-functionalized SWCNTs were then pyrolyzed under an inert atmosphere at selected temperatures between 100 and 500 °C to remove the addends. The extent of defunctionalization was assessed using a combination of thermogravimetric analysis, Raman measurements of the D, G, and radial breathing bands, absorption spectroscopy of the first- and second-order van Hove peaks, and near-IR fluorescence spectroscopy of (n,m)-specific emission bands. These measurements all indicate a substantial dependence of defunctionalization rate on nanotube diameter, with larger diameter nanotubes showing more facile loss of addends. The effective activation energy for defunctionalization is estimated to be a factor of ∼1.44 greater for 0.76 nm diameter nanotubes as compared to those with 1.24 nm diameter. The experimental findings also reveal the quantitative variation with functionalization density of the Raman D/G intensity ratio and the relative near-IR fluorescence intensity. Pyrolyzed samples show spectroscopic properties that are equivalent to those of SWCNTs prior to functionalization. The strong structure dependence of the defunctionalization rate suggests an approach for scalable diameter sorting of mixed SWCNT samples.
Toward Practical Non-Contact Optical Strain Sensing Using Single-Walled Carbon Nanotubes
(The Electrochemical Society, 2016) Sun, Peng; Bachilo, Sergei M.; Nagarajaiah, Satish; Weisman, R. Bruce
Progress is reported in an emerging non-contact strain sensing technology based on optical properties of single-walled carbon nanotubes (SWCNTs). In this strain-sensing smart skin (“S4”) method, nanotubes are dilutely embedded in a thin polymer film applied to a substrate of interest. Subsequent strain in the substrate is transferred to the nanotubes, causing systematic spectral shifts in their characteristic short-wave infrared fluorescence peaks. A small diode laser excites a spot on the coated surface, and the resulting emission is captured and spectrally analyzed to deduce local strain. To advance performance of the method, we prepare S4 films with structurally selected SWCNTs. These give less congested emission spectra that can be analyzed precisely. However, quenching interactions with the polymer host reduce SWCNT emission intensity by an order of magnitude. The instrumentation that captures SWCNT fluorescence has been made lighter and smaller for hand-held use or mounting onto a positioning mechanism that makes efficient automated strain scans of laboratory test specimens. Statistical analysis of large S4 data sets exposes uncertainties in measurements at single positions plus spatial variations in deduced baseline strain levels. Future refinements to S4 film formulation and processing should provide improved strain sensing performance suitable for industrial application.
Variance Spectroscopy
(American Chemical Society, 2015) Streit, Jason K.; Bachilo, Sergei M.; Sanchez, Stephen R.; Lin, Ching-Wei; Weisman, R. Bruce; Smalley-Curl Institute
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. Furthermore, correlations between intensity variations at different wavelengths provide two-dimensional covariance maps that isolate the spectra of homogeneous subpopulations. Covariance analysis is also a sensitive probe of particle aggregation. It shows that well-dispersed nanotube samples can spontaneously form loose aggregates of a type not previously recognized. Variance spectroscopy is a simple and practical technique that should find application in many nanoparticle studies.

Browsing by Author "Bachilo, Sergei M."

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