Hyperspectral Detection of the Fluorescence Shift between Chirality-Sorted Empty and Water-Filled Single-Wall Carbon Nanotube Enantiomers.

Single-wall carbon nanotubes (SWCNTs) have extraordinary electronic and optical properties that depend strongly on their exact chiral structure and their interaction with their inner and outer environment. The fluorescence (PL) of semiconducting SWCNTs, for instance, will shift depending on the molecules with which the SWCNT's hollow core is filled. These interaction-induced shifts are challenging to resolve on the ensemble level in samples containing a mixture of different filling contents due to the relatively large inhomogeneous line width of the ensemble SWCNT PL compared to the size of these shifts. To circumvent this inhomogeneous broadening, single-tube spectroscopy and hyperspectral imaging are often applied, which until now required time-consuming statistical studies. Here, we present hyperspectral PL microscopy combined with automated SWCNT segmenting based on either principal component analysis or a convolutional neural network, capable of both spatially and spectrally resolving the PL along the length of many individual SWCNTs at the same time and automatically fitting peak positions and line widths of individual SWCNTs. The methodology is demonstrated by accurately determining the emission shifts and line widths of thousands of left- and right-handed empty and water-filled SWCNTs coated with a chiral surfactant, resulting in four statistical distributions which cannot be resolved in ensemble spectroscopy of unsorted samples. The results demonstrate a robust method to quickly probe ensemble properties with single-enantiomer spectral resolution. Moreover, it promises to be an absolute quantitative method to characterize the relative abundances of SWCNTs with different handedness or filling content in macroscopic samples, simply by counting individual species.

Chirality Dependence of Triplet Excitons in (6,5) and (7,5) Single-Wall Carbon Nanotubes Revealed by Optically Detected Magnetic Resonance.

The excitonic structure of single-wall carbon nanotubes (SWCNTs) is chirality dependent and consists of multiple singlet and triplet excitons (TEs) of which only one singlet exciton (SE) is optically bright. In particular, the dark TEs have a large impact on the integration of SWCNTs in optoelectronic devices, where excitons are created electrically, such as in infrared light-emitting diodes, thereby strongly limiting their quantum efficiency. Here, we report the characterization of TEs in chirality-purified samples of (6,5) and (7,5) SWCNTs, either randomly oriented in a frozen solution or with in-plane preferential orientation in a film, by means of optically detected magnetic resonance (ODMR) spectroscopy. In both chiral structures, the nanotubes are shown to sustain three types of TEs. One TE exhibits axial symmetry with zero-field splitting (ZFS) parameters depending on SWCNT diameter, in good agreement with the tighter confinement expected in narrower-diameter nanotubes. The ZFS of this TE also depends on nanotube environment, pointing to slightly weaker confinement for surfactant-coated than for polymer-wrapped SWCNTs. A second TE type, with much smaller ZFS, does not show the same systematic trends with diameter and environment and has a less well-defined axial symmetry. This most likely corresponds to TEs trapped at defect sites at low temperature, as exemplified by comparing SWCNT samples from different origins and after different treatments. A third triplet has unresolved ZFS, implying it originates from weakly interacting spin pairs. Aside from the diameter dependence, ODMR thus provides insights in both the symmetry, confinement, and nature of TEs on semiconducting SWCNTs.

Troponina I de alta sensibilidad para el descarte temprano del infarto agudo de miocardio / High sensitivity troponin I to early rule out for acute myocardial infarction

Resumen Introducción: La mayor utilidad de las troponinas de alta sensibilidad (Tn-hs) es descartar tempranamente el infarto agudo de miocardio (IAM). El algoritmo recomendado por la guía de práctica clínica (GPC) del Ministerio de Salud de Colombia para descartar el IAM es respaldado por evidencia de baja calidad y no ha sido validado en población colombiana. Objetivo: evaluar la capacidad de este algoritmo empleando troponina I de alta sensibilidad (TnI-hs) para descartar el IAM sin elevación del segmento ST (IAMSEST). Métodos: se analizaron pacientes con sospecha de síndrome coronario agudo (SCA) atendidos en un servicio de urgencias de un centro de alta complejidad. El desenlace primario fue el diagnóstico de IAMSEST tipo 1 y tipo 4b. Se determinaron las características operativas para los puntos de corte del algoritmo para el desenlace primario, reingreso hospitalario y muerte a 30 días. Resultados: se incluyeron 2.282 pacientes en los que el desenlace primario ocurrió en 389. El algoritmo de la GPC colombiana tuvo S del 90,9% (IC 95%: 74-100) y VPN del 99% (IC 95%: 99-100) utilizando el percentil 99 (p99) no discriminado por sexo, pero tanto la S como el VPN mejoraron al 100% cuando se utilizó el p99 por sexo. Conclusión: el algoritmo recomendado por la GPC colombiana utilizando TnI-hs y con el p99 ajustado por sexo tiene excelente capacidad para descartar de manera temprana y segura el diagnóstico de IAMSEST.

Abstract Introduction: The greatest utility of high-sensitivity troponins (Tn-hs) is to rule out acute myocardial infarction (AMI) early. The algorithm recommended by the Colombian practice guideline clinical (CPG) of Health’s Ministry to rule out AMI is supported by low-quality evidence and has not been validated in the Colombian population. This research aims to evaluate the ability of this algorithm using high sensitivity troponin I (TnI-hs) to rule out AMI without ST segment elevation (STEMI). Methods: Patients with suspected acute coronary syndrome (ACS) treated in an emergency department of a highly complex center were analyzed. The primary outcome was the diagnosis of STEMI type 1 and type 4b. The operativing characteristics for the algorithm cut-off points were determined for the primary outcome, hospital readmission death at and 30 days. Results: 2282 patients were included in whom the primary outcome occurred in 389. The Colombian CPG algorithm had S of 90.9% (95% CI 74-100) and NPV of 99% (95% CI 99-100) using the 99th percentile (p99) not discriminated by sex, but both S and NPV improved 100% when p99 was used by sex. Conclusion: The algorithm recommended by the Colombian CPG using TnI-hs and with the p99 adjusted for sex has an excellent capacity to rule out early and safely the diagnosis of STEMI.

Resonance Raman signature of intertube excitons in compositionally-defined carbon nanotube bundles.

Electronic interactions in low-dimensional nanomaterial heterostructures can lead to novel optical responses arising from exciton delocalization over the constituent materials. Similar phenomena have been suggested to arise between closely interacting semiconducting carbon nanotubes of identical structure. Such behavior in carbon nanotubes has potential to generate new exciton physics, impact exciton transport mechanisms in nanotube networks, and place nanotubes as one-dimensional models for such behaviors in systems of higher dimensionality. Here we use resonance Raman spectroscopy to probe intertube interactions in (6,5) chirality-enriched bundles. Raman excitation profiles for the radial breathing mode and G-mode display a previously unobserved sharp resonance feature. We show the feature is evidence for creation of intertube excitons and is identified as a Fano resonance arising from the interaction between intratube and intertube excitons. The universality of the model suggests that similar Raman excitation profile features may be observed for interlayer exciton resonances in 2D multilayered systems.

Influences of Exciton Diffusion and Exciton-Exciton Annihilation on Photon Emission Statistics of Carbon Nanotubes.

Pump-dependent photoluminescence imaging and second-order photon correlation studies have been performed on individual single-walled carbon nanotubes (SWCNTs) at room temperature. These studies enable the extraction of both the exciton diffusion constant and the Auger recombination coefficient. A linear correlation between these parameters is attributed to the effect of environmental disorder in setting the exciton mean free path and capture-limited Auger recombination at this length scale. A suppression of photon antibunching is attributed to the creation of multiple spatially nonoverlapping excitons in SWCNTs, whose diffusion length is shorter than the laser spot size. We conclude that complete antibunching at room temperature requires an enhancement of the exciton-exciton annihilation rate that may become realizable in SWCNTs allowing for strong exciton localization.

Formation and dynamics of "waterproof" photoluminescent complexes of rare earth ions in crowded environment.

Understanding behavior of rare-earth ions (REI) in crowded environments is crucial for several nano- and bio-technological applications. Evolution of REI photoluminescence (PL) in small compartments inside a silica hydrogel, mimic to a soft matter bio-environment, has been studied and explained within a solvation model. The model uncovered the origin of high PL efficiency to be the formation of REI complexes, surrounded by bile salt (DOC) molecules. Comparative study of these REI-DOC complexes in bulk water solution and those enclosed inside the hydrogel revealed a strong correlation between an up to 5×-longer lifetime of REIs and appearance of the DOC ordered phase, further confirmed by dynamics of REI solvation shells, REI diffusion experiments and morphological characterization of microstructure of the hydrogel.

Influence of exciton dimensionality on spectral diffusion of single-walled carbon nanotubes.

We study temporal evolution of photoluminescence (PL) spectra from individual single-walled carbon nanotubes (SWCNTs) at cryogenic and room temperatures. Sublinear and superlinear correlations between fluctuating PL spectral positions and line widths are observed at cryogenic and room temperatures, respectively. We develop a simple model to explain these two different spectral diffusion behaviors in the framework of quantum-confined Stark effect (QCSE) caused by surface charges trapped in the vicinity of SWCNTs. We show that the wave function properties of excitons, namely, localization at cryogenic temperature and delocalization at room temperature, play a critical role in defining sub- and superlinear correlations. Room temperature PL spectral positions and line widths of SWCNTs coupled to gold dimer nanoantennas on the other hand exhibit sublinear correlations, indicating that excitonic emission mainly originates from nanometer range regions and excitons appear to be localized. Our numerical simulations show that such apparent localization of excitons results from plasmonic confinement of excitation and an enhancement of decay rates in the gap of the dimer nanoantennas.

Role of surfactants and salt in aqueous two-phase separation of carbon nanotubes toward simple chirality isolation.

Aqueous two-phase extraction has recently been demonstrated as a new method to separate single-wall carbon nanotubes (SWCNTs). In this work, we determined that the mechanism of separation is driven by the hydrophobicity of the surfactant, or combination of surfactants, at the SWCNT surface. This knowledge allowed us to develop a simple approach for obtaining highly enriched single-chirality suspensions in only 1 or 2 steps. These results were obtained by strategically combining multiple surfactants with different diameter-dependent binding affinities for SWCNTs and salts that readjust the surfactant structure within the mixed micelle surrounding the SWCNTs. The procedure is successfully applied to SWCNTs from different sources (CoMoCAT and HiPco) with various diameter distributions (from 0.53 to 1.2 nm). Each separation step is characterized by optical absorption, resonant Raman, and photoluminescence excitation spectroscopies. By determining the SWCNT sorting mechanism, we were able to develop a new set of parameters that separated another chirality.

Developing Monolithic Nanoporous Gold with Hierarchical Bicontinuity Using Colloidal Bijels.

We report a universal platform for the synthesis of monolithic porous gold materials with hierarchical bicontinuous morphology and combined macro- and mesoporosity using a synergistic combination of nanocasting and chemical dealloying. This robust and accessible approach offers a new design paradigm for the parallel optimization of active surface area and mass transport in porous metal electrodes.

Recent developments in the photophysics of single-walled carbon nanotubes for their use as active and passive material elements in thin film photovoltaics.

The search for environmentally clean energy sources has spawned a wave of research into the use of carbon nanomaterials for photovoltaic applications. In particular, research using semiconducting single-walled carbon nanotubes has undergone dramatic transformations due to the availability of high quality samples through colloidal separation techniques. This has led to breakthrough discoveries on how energy and charge transport occurs in these materials and points to applications in energy harvesting. We present a review of the relevant photophysics of carbon nanotubes that dictate processes important for integration as active and passive material elements in thin film photovoltaics. Fundamental processes ranging from light absorption and internal conversion to exciton transport and dissociation are discussed in detail from both a spectroscopic and a device perspective. We also give a perspective on the future of these fascinating materials to be used as active and passive material elements in photovoltaics.

Mechanism of electrolyte-induced brightening in single-wall carbon nanotubes.

While addition of electrolyte to sodium dodecyl sulfate suspensions of single-wall carbon nanotubes has been demonstrated to result in significant brightening of the nanotube photoluminescence (PL), the brightening mechanism has remained unresolved. Here, we probe this mechanism using time-resolved PL decay measurements. We find that PL decay times increase by a factor of 2 on addition of CsCl as the electrolyte. Such an increase directly parallels an observed near-doubling of PL intensity, indicating the brightening results primarily from changes in nonradiative decay rates associated with exciton diffusion to quenching sites. Our findings indicate that a reduced number of these sites results from electrolyte-induced reorientation of the surfactant surface structure that partially removes pockets of water from the tube surface where excitons can dissociate, and thus underscores the contribution of interfacial water in exciton recombination processes.

Fundamental optical processes in armchair carbon nanotubes.

Single-wall carbon nanotubes provide ideal model one-dimensional (1-D) condensed matter systems in which to address fundamental questions in many-body physics, while, at the same time, they are leading candidates for building blocks in nanoscale optoelectronic circuits. Much attention has been recently paid to their optical properties, arising from 1-D excitons and phonons, which have been revealed via photoluminescence, Raman scattering, and ultrafast optical spectroscopy of semiconducting carbon nanotubes. On the other hand, dynamical properties of metallic nanotubes have been poorly explored, although they are expected to provide a novel setting for the study of electron-hole pairs in the presence of degenerate 1-D electrons. In particular, (n,n)-chirality, or armchair, metallic nanotubes are truly gapless with massless carriers, ideally suited for dynamical studies of Tomonaga-Luttinger liquids. Unfortunately, progress towards such studies has been slowed by the inherent problem of nanotube synthesis whereby both semiconducting and metallic nanotubes are produced. Here, we use post-synthesis separation methods based on density gradient ultracentrifugation and DNA-based ion-exchange chromatography to produce aqueous suspensions strongly enriched in armchair nanotubes. Through resonant Raman spectroscopy of the radial breathing mode phonons, we provide macroscopic and unambiguous evidence that density gradient ultracentrifugation can enrich ensemble samples in armchair nanotubes. Furthermore, using conventional, optical absorption spectroscopy in the near-infrared and visible range, we show that interband absorption in armchair nanotubes is strongly excitonic. Lastly, by examining the G-band mode in Raman spectra, we determine that observation of the broad, lower frequency (G(-)) feature is a result of resonance with non-armchair "metallic" nanotubes. These findings regarding the fundamental optical absorption and scattering processes in metallic carbon nanotubes lay the foundation for further spectroscopic studies to probe many-body physical phenomena in one dimension.

Disorder limited exciton transport in colloidal single-wall carbon nanotubes.

We present measurements of S(1) exciton transport in (6,5) carbon nanotubes at room temperature in a colloidal environment. Exciton diffusion lengths associated with end quenching paired with photoluminescence lifetimes provide a direct basis for determining a median diffusion constant of approximately 7.5 cm(2)s(-1). Our experimental results are compared to model diffusion constants calculated using a realistic exciton dispersion accounting for a logarithmic correction due to the exchange self-energy and a nonequilibrium distribution between bright and dark excitons. The intrinsic diffusion constant associated with acoustic phonon scattering is too large to explain the observed diffusion length, and as such, we attribute the observed transport to disorder-limited diffusional transport associated with the dynamics of the colloidal interface. In this model an effective surface potential limits the exciton mean free path to the same size as that of the exciton wave function, defined by the strength of the electron-hole Coulomb interaction.

Quantum interference between the third and fourth exciton states in semiconducting carbon nanotubes using resonance Raman spectroscopy.

We exploit an energy level crossover effect [Haroz et al., Phys. Rev. B 77, 125405 (2008)] to probe quantum interference in the resonance Raman response from carbon nanotube samples highly enriched in the single semiconducting chiralities of (8,6), (9,4), and (10,5). UV Raman excitation profiles of G-band spectra reveal unambiguous signatures of interference between the third and fourth excitonic states (E(33) and E(44)). Both constructive and destructive responses are observed and lead to anomalous intensity ratios in the LO and TO modes. Especially large anomalies for the (10,5) structure result from nearly identical energies found for the two E(ii) transitions. The interference patterns demonstrate that the sign of the exciton-phonon coupling matrix elements changes for the LO mode between the two electronic states, and remains the same for the TO mode. Significant non-Condon contributions to the Raman response are also found.

Photoluminescence imaging of electronic-impurity-induced exciton quenching in single-walled carbon nanotubes.

The electronic properties of single-walled carbon nanotubes can be altered by surface adsorption of electronic impurities or dopants. However, fully understanding the influence of these impurities is difficult because of the inherent complexity of the solution-based colloidal chemistry of nanotubes, and because of a lack of techniques for directly imaging dynamic processes involving these impurities. Here, we show that photoluminescence microscopy can be used to image exciton quenching in semiconducting single-walled carbon nanotubes during the early stages of chemical doping with two different species. The addition of AuCl(3) leads to localized exciton-quenching sites, which are attributed to a mid-gap electronic impurity level, and the adsorbed species are also found sometimes to be mobile on the surface of the nanotubes. The addition of H(2)O(2) leads to delocalized exciton-quenching hole states, which are responsible for long-range photoluminescence blinking, and are also mobile.

Unique origin of colors of armchair carbon nanotubes.

The colors of suspended metallic colloidal particles are determined by their size-dependent plasma resonance, while those of semiconducting colloidal particles are determined by their size-dependent band gap. Here, we present a novel case for armchair carbon nanotubes, suspended in aqueous medium, for which the color depends on their size-dependent excitonic resonance, even though the individual particles are metallic. We observe distinct colors of a series of armchair-enriched nanotube suspensions, highlighting the unique coloration mechanism of these one-dimensional metals.

Chiral index dependence of the G+ and G- Raman modes in semiconducting carbon nanotubes.

Raman spectroscopy on the radial breathing mode is a common tool to determine the diameter d or chiral indices (n,m) of single-wall carbon nanotubes. In this work we present an alternative technique to determine d and (n,m) based on the high-energy G(-) mode. From resonant Raman scattering experiments on 14 highly purified single chirality (n,m) samples we obtain the diameter, chiral angle, and family dependence of the G(-) and G(+) peak position. Considering theoretical predictions we discuss the origin of these dependences with respect to rehybridization of the carbon orbitals, confinement, and electron-electron interactions. The relative Raman intensities of the two peaks have a systematic chiral angle dependence in agreement with theories considering the symmetry of nanotubes and the associated phonons.

Fluorescent single-walled carbon nanotube aerogels in surfactant-free environments.

A general challenge in generating functional materials from nanoscale components is integrating them into useful composites that retain or enhance their properties of interest. Development of single walled carbon nanotube (SWNT) materials for optoelectronics and sensing has been especially challenging in that SWNT optical and electronic properties are highly sensitive to environmental interactions, which can be particularly severe in composite matrices. Percolation of SWNTs into aqueous silica gels shows promise as an important route for exploiting their properties, but retention of the aqueous and surfactant environment still impacts and limits optical response, while also limiting the range of conditions in which these materials may be applied. Here, we present for the first time an innovative approach to obtain highly fluorescent solution-free SWNT-silica aerogels, which provides access to novel photophysical properties. Strongly blue-shifted spectral features, revelation of new diameter-dependent gas-phase adsorption phenomena, and significant increase (approximately three times that at room temperature) in photoluminescence intensities at cryogenic temperatures all indicate greatly reduced SWNT-matrix interactions consistent with the SWNTs experiencing a surfactant-free environment. The results demonstrate that this solid-state nanomaterial will play an important role in further revealing the true intrinsic SWNT chemical and photophysical behaviors and represent for the first time a promising new solution- and surfactant-free material for advancing SWNT applications in sensing, photonics, and optoelectronics.

Violation of the condon approximation in semiconducting carbon nanotubes.

The Condon approximation is widely applied in molecular and condensed matter spectroscopy and states that electronic transition dipoles are independent of nuclear positions. This approximation is related to the Franck-Condon principle, which in its simplest form holds that electronic transitions are instantaneous on the time scale of nuclear motion. The Condon approximation leads to a long-held assumption in Raman spectroscopy of carbon nanotubes: intensities arising from resonance with incident and scattered photons are equal. Direct testing of this assumption has not been possible due to the lack of homogeneous populations of specific carbon nanotube chiralities. Here, we present the first complete Raman excitation profiles (REPs) for the nanotube G band for 10 pure semiconducting chiralities. In contrast to expectations, a strong asymmetry is observed in the REPs for all chiralities, with the scattered resonance always appearing weaker than the incident resonance. The observed behavior results from violation of the Condon approximation and originates in changes in the electronic transition dipole due to nuclear motion (non-Condon effect), as confirmed by our quantum chemical calculations. The agreement of our calculations with the experimental REP asymmetries and observed trends in family dependence indicates the behavior is intrinsic.

Electrodynamic and excitonic intertube interactions in semiconducting carbon nanotube aggregates.

The optical properties of selectively aggregated, nearly single chirality single-wall carbon nanotubes were investigated by both continuous-wave and time-resolved spectroscopies. With reduced sample heterogeneities, we have resolved aggregation-dependent reductions of the excitation energy of the S(1) exciton and enhanced electron-hole pair absorption. Photoluminescence spectra revealed a spectral splitting of S(1) and simultaneous reductions of the emission efficiencies and nonradiative decay rates. The observed strong deviations from isolated tube behavior are accounted for by enhanced screening of the intratube Coulomb interactions, intertube exciton tunneling, and diffusion-driven exciton quenching. We also provide evidence that density gradient ultracentrifugation can be used to structurally sort single-wall carbon nanotubes by aggregate size as evident by a monotonic dependence of the aforementioned optical properties on buoyant density.