An Automated Gradient Titration Fluorescence Methodology for High-Resolution Identification of Aqueous Two-Polymer Phase Extraction Conditions for Single-Wall Carbon Nanotubes.

A significant advance in rate and precision of identifying the co-surfactant concentrations leading to differential extraction of specific single-wall carbon nanotube (SWCNT) species in aqueous two-polymer phase extraction experiments is reported. These gains are achieved through continuous titration of co-surfactant and other solution components during automated fluorescence measurements on SWCNT dispersions. The resulting fluorescence versus concentration curves display intensity and wavelength shift transitions traceable to the nature of the adsorbed surfactant layer on specific SWCNT structures at the (n,m) species and enantiomer level at high resolution. The increased precision and speed of the titration method resolve previously invisible complexity in the SWCNT fluorescence during the transition from one surfactant dominating the SWCNT interface to the other, offering insight into the fine details of the competitive exchange process. For the first time, we additionally demonstrate that the competitive process of the surfactant switch is direction independent (reversible) and hysteresis-free; the latter data effectively specifies an upper bound for the time scale of the exchange process. Titration curves are compared to literature results and initial advanced parameter variation is conducted for previously unreasonable to investigate solution conditions.

Molecular transport enhancement in pure metallic carbon nanotube porins.

Nanofluidic channels impose extreme confinement on water and ions, giving rise to unusual transport phenomena strongly dependent on the interactions at the channel-wall interface. Yet how the electronic properties of the nanofluidic channels influence transport efficiency remains largely unexplored. Here we measure transport through the inner pores of sub-1 nm metallic and semiconducting carbon nanotube porins. We find that water and proton transport are enhanced in metallic nanotubes over semiconducting nanotubes, whereas ion transport is largely insensitive to the nanotube bandgap value. Molecular simulations using polarizable force fields highlight the contributions of the anisotropic polarizability tensor of the carbon nanotubes to the ion-nanotube interactions and the water friction coefficient. We also describe the origin of the proton transport enhancement in metallic nanotubes using deep neural network molecular dynamics simulations. These results emphasize the complex role of the electronic properties of nanofluidic channels in modulating transport under extreme nanoscale confinement.

Broadband Full-Spectrum Raman Excitation Mapping Reveals Intricate Optoelectronic-Vibrational Resonance Structure of Chirality-Pure Single-Walled Carbon Nanotubes.

The Raman excitation spectra of chirality-pure (6,5), (7,5), and (8,3) single-walled carbon nanotubes (SWCNTs) are explored for homogeneous solid film samples over broad excitation energy and scattering energy ranges using a rapid and relatively simple full spectrum Raman excitation mapping technique. Identification of variation in scattering intensity with sample type and phonon energy related to different vibrational bands is clearly realized. Excitation profiles are found to vary strongly for different phonon modes. Some modes' Raman excitation profiles are extracted, with the G band profile compared to earlier work. Other modes, such as the M and iTOLA modes, have quite sharp resonance profiles and strong resonances. Conventional fixed wavelength Raman spectroscopy can miss these effects on the scattering intensities entirely due to the significant intensity changes observed for small variations in excitation wavelength. Peak intensities for phonon modes traceable to a pristine carbon lattice forming a SWCNT sidewall were greater for high-crystallinity materials. In the case of highly defective SWCNTs, the scattering intensities of the G band and the defect-related D band are demonstrated to be affected both in absolute intensities and in relative ratio, with the ratio that would be measured by single wavelength Raman scattering dependent on the excitation wavelength due to differences in the resonance energy profiles of the two bands. Lastly it is shown that the approach of this contribution yields a clear path toward increasing the rigor and quantification of resonance Raman scattering intensity measurements through tractable corrections of excitation and emission side variations in efficiency with excitation wavelength.

The Impact of Carbon Nanotube Length and Diameter on their Global Alignment by Dead-End Filtration.

Dead-end filtration has proven to effectively prepare macroscopically (3.8 cm2 ) aligned thin films from solutionbased single-wall carbon nanotubes (SWCNTs). However, to make this technique broadly applicable, the role of SWCNT length and diameter must be understood. To date, most groups report the alignment of unsorted, large diameter (≈1.4 nm) SWCNTs, but systematic studies on their small diameter are rare (≈0.78 nm). In this work, films with an area of A = 3.81 cm2 and a thickness of ≈40 nm are prepared from length-sorted fractions comprising of small and large diameter SWCNTs, respectively. The alignment is characterized by cross-polarized microscopy, scanning electron microscopy, absorption and Raman spectroscopy. For the longest fractions (Lavg = 952 nm ± 431 nm, Δ = 1.58 and Lavg = 667 nm ± 246 nm, Δ = 1.55), the 2D order parameter, S2D, values of ≈0.6 and ≈0.76 are reported for the small and large diameter SWCNTs over an area of A = 625 µm2 , respectively. A comparison of Derjaguin, Landau, Verwey, and Overbeek (DLVO) theory calculations with the aligned domain size is then used to propose a law identifying the required length of a carbon nanotube with a given diameter and zeta potential.

Surfactant Chemistry and Polymer Choice Affect Single-Wall Carbon Nanotube Extraction Conditions in Aqueous Two-Polymer Phase Extraction.

Quantitative determination of the effects of surfactant chemistry and polymer chain length on the concentration conditions necessary to yield extraction of specific single-wall carbon nanotube (SWNCT) species in an aqueous two-polymer phase extraction (ATPE) separation are reported. In particular, the effects of polyethylene glycol (PEG) chain length, surfactant ratios, and systematic structural variations of alkyl surfactants and bile salts on the surfactant ratios necessary for extraction were investigated using a recently reported fluorescence-based method. Alkyl surfactant tail length was observed to strongly affect the amount of surfactant necessary to cause PEG-phase extraction of nanotube species in ATPE, while variation in the anionic sulfate/sulfonate head group chemistry has less impact on the concentration necessary for extraction. Substitution of different bile salts results in different surfactant packings on the SWCNTs, with substitution greatly affecting the alkyl surfactant concentrations required for (n,m) extraction. Finally, distinct alkyl-to-bile surfactant ratios were found to extract specific (n,m) SWCNTs across the whole effective window of absolute concentrations, supporting the hypothesized competitive adsorption mechanism model of SWCNT sorting. Altogether, these results provide valuable insights into the underlying mechanisms behind ATPE-based SWCNT separations, towards further development and optimization of the ATPE method for SWCNT chirality and handedness sorting.

van der Waals SWCNT@BN Heterostructures Synthesized from Solution-Processed Chirality-Pure Single-Wall Carbon Nanotubes.

Single-wall carbon nanotubes in boron nitride (SWCNT@BN) are one-dimensional van der Waals heterostructures that exhibit intriguing physical and chemical properties. As with their carbon nanotube counterparts, these heterostructures can form from different combinations of chiralities, providing rich structures but also posing a significant synthetic challenge to controlling their structure. Enabled by advances in nanotube chirality sorting, clean removal of the surfactant used for solution processing, and a simple method to fabricate free-standing submonolayer films of chirality pure SWCNTs as templates for the BN growth, we show it is possible to directly grow BN on chirality enriched SWCNTs from solution processing to form van der Waals heterostructures. We further report factors affecting the heterostructure formation, including an accelerated growth rate in the presence of H2, and significantly improved crystallization of the grown BN, with the BN thickness controlled down to one single BN layer, through the presence of a Cu foil in the reactor. Transmission electron microscopy and electron energy-loss spectroscopic mapping confirm the synthesis of SWCNT@BN from the solution purified nanotubes. The photoluminescence peaks of both (7,5)- and (8,4)-SWCNT@BN heterostructures are found to redshift (by ∼10 nm) relative to the bare SWCNTs. Raman scattering suggests that the grown BN shells pose a confinement effect on the SWCNT core.

Efficient Inner-to-Outer Wall Energy Transfer in Highly Pure Double-Wall Carbon Nanotubes Revealed by Detailed Spectroscopy.

The coaxial stacking of two single-wall carbon nanotubes (SWCNTs) into a double-wall carbon nanotube (DWCNT), forming a so-called one-dimensional van der Waals structure, leads to synergetic effects that dramatically affect the optical and electronic properties of both layers. In this work, we explore these effects in purified DWCNT samples by combining absorption, wavelength-dependent infrared fluorescence-excitation (PLE), and wavelength-dependent resonant Raman scattering (RRS) spectroscopy. Purified DWCNTs are obtained by careful solubilization that strictly avoids ultrasonication or by electronic-type sorting, both followed by a density gradient ultracentrifugation to remove unwanted SWCNTs that could obscure the DWCNT characterization. Chirality-dependent shifts of the radial breathing mode vibrational frequencies and transition energies of the inner and outer DWCNT walls with respect to their SWCNT analogues are determined by advanced two-dimensional fitting of RRS and PLE data of DWCNT and their reference SWCNT samples. This exhaustive data set verifies that fluorescence from the inner DWCNT walls of well-purified samples is severely quenched through efficient energy transfer from the inner to the outer DWCNT walls. Combined analysis of the PLE and RRS results further reveals that this transfer is dependent on the inner and outer wall chirality, and we identify the specific combinations dominant in our DWCNT samples. These obtained results demonstrate the necessity and value of a combined structural characterization approach including PLE and RRS spectroscopy for bulk DWCNT samples.

DNA-guided lattice remodeling of carbon nanotubes.

Covalent modification of carbon nanotubes is a promising strategy for engineering their electronic structures. However, keeping modification sites in registration with a nanotube lattice is challenging. We report a solution using DNA-directed, guanine (G)-specific cross-linking chemistry. Through DNA screening we identify a sequence, C3GC7GC3, whose reaction with an (8,3) enantiomer yields minimum disorder-induced Raman mode intensities and photoluminescence Stokes shift, suggesting ordered defect array formation. Single-particle cryo-electron microscopy shows that the C3GC7GC3 functionalized (8,3) has an ordered helical structure with a 6.5 angstroms periodicity. Reaction mechanism analysis suggests that the helical periodicity arises from an array of G-modified carbon-carbon bonds separated by a fixed distance along an armchair helical line. Our findings may be used to remodel nanotube lattices for novel electronic properties.

Computational Design of Homotetrameric Peptide Bundle Variants Spanning a Wide Range of Charge States.

With the ability to design their sequences and structures, peptides can be engineered to realize a wide variety of functionalities and structures. Herein, computational design was used to identify a set of 17 peptides having a wide range of putative charge states but the same tetrameric coiled-coil bundle structure. Calculations were performed to identify suitable locations for ionizable residues (D, E, K, and R) at the bundle's exterior sites, while interior hydrophobic interactions were retained. The designed bundle structures spanned putative charge states of -32 to +32 in units of electron charge. The peptides were experimentally investigated using spectroscopic and scattering techniques. Thermal stabilities of the bundles were investigated using circular dichroism. Molecular dynamics simulations assessed structural fluctuations within the bundles. The cylindrical peptide bundles, 4 nm long by 2 nm in diameter, were covalently linked to form rigid, micron-scale polymers and characterized using transmission electron microscopy. The designed suite of sequences provides a set of readily realized nanometer-scale structures of tunable charge that can also be polymerized to yield rigid-rod polyelectrolytes.

Dependence of Single-Wall Carbon Nanotube Alignment on the Filter Membrane Interface in Slow Vacuum Filtration.

The recent introduction of slow vacuum filtration (SVF) technology has shown great promise for reproducibly creating high-quality, large-area aligned films of single-wall carbon nanotubes (SWCNTs) from solution-based dispersions. Despite clear advantages over other SWCNT alignment techniques, SVF remains in the developmental stages due to a lack of an agreed-upon alignment mechanism, a hurdle which hinders SVF optimization. In this work, the filter membrane surface is modified to show how the resulting SWCNT nematic order can be significantly enhanced. It is observed that directional mechanical grooving on filter membranes does not play a significant role in SWCNT alignment, despite the tendency for nanotubes to follow the groove direction. Chemical treatments to the filter membrane are shown to increase SWCNT alignment by nearly 1/3. These findings suggest that membrane surface structure acts to create a directional flow along the filter membrane surface that can produce global SWCNT alignment during SVF, rather serving as an alignment template.

Colloid-like solution behavior of computationally designed coiled coil bundlemers.

The use of isotropic potential models of simple colloids for describing complex protein-protein interactions is a topic of ongoing debate in the biophysical community. This contention stems from the unavailability of synthetic protein-like model particles that are amenable to systematic experimental characterization. In this article, we test the utility of colloidal theory to capture the solution structure, interactions and dynamics of novel globular protein-mimicking, computationally designed peptide assemblies called bundlemers that are programmable model systems at the intersection of colloids and proteins. Small-angle neutron scattering (SANS) measurements of semi-dilute bundlemer solutions in low and high ionic strength solution indicate that bundlemers interact locally via repulsive interactions that can be described by a screened repulsive potential. We also present neutron spin echo (NSE) spectroscopy results that show high-Q freely-diffusive dynamics of bundlemers. Importantly, formation of clusters due to short-range attractive, inter-bundlemer interactions is observed in SANS even at dilute bundlemer concentrations, which is indicative of the complexity of the bundlemer charged surface. The similarities and differences between bundlemers and simple colloidal as well as complex protein-protein interactions is discussed in detail.

Tuning Net Charge in Aliphatic Polycarbonates Alters Solubility and Protein Complexation Behavior.

A synthetic strategy yielded polyelectrolytes and polyampholytes with tunable net charge for complexation and protein binding. Organocatalytic ring-opening polymerizations yielded aliphatic polycarbonates that were functionalized with both carboxylate and ammonium side chains in a post-polymerization, radical-mediated thiol-ene reaction. Incorporating net charge into the polymer architecture altered the chain dimensions in phosphate buffered solution in a manner consistent with self-complexation and complexation behavior with model proteins. A net cationic polyampholyte with 5% of carboxylate side chains formed large clusters rather than small complexes with bovine serum albumin, while 50% carboxylate polyampholyte was insoluble. Overall, the aliphatic polycarbonates with varying net charge exhibited different macrophase solution behaviors when mixed with protein, where self-complexation appears to compete with protein binding and larger-scale complexation.

Selective filling of n-hexane in a tight nanopore.

Molecular sieving may occur when two molecules compete for a nanopore. In nearly all known examples, the nanopore is larger than the molecule that selectively enters the pore. Here, we experimentally demonstrate the ability of single-wall carbon nanotubes with a van der Waals pore size of 0.42 nm to separate n-hexane from cyclohexane-despite the fact that both molecules have kinetic diameters larger than the rigid nanopore. This unexpected finding challenges our current understanding of nanopore selectivity and how molecules may enter a tight channel. Ab initio molecular dynamics simulations reveal that n-hexane molecules stretch by nearly 11.2% inside the nanotube pore. Although at a relatively low probability (28.5% overall), the stretched state of n-hexane does exist in the bulk solution, allowing the molecule to enter the tight pore even at room temperature. These insights open up opportunities to engineer nanopore selectivity based on the molecular degrees of freedom.

Prevalence and hospital charges from firearm injuries treated in US emergency departments from 2006 to 2016.

BACKGROUND: Age- and intent-related differences in the burden and costs of firearm injury treated in emergency departments are not well-documented. METHODS: We performed a serial cross-sectional study of the Healthcare Cost and Utilization Program Nationwide Emergency Department Survey from 2006 to 2016. We used International Classification of Diseases diagnoses codes revisions 9 and 10 to identify firearm injuries. We calculated survey-weighted counts, proportions, means, and rates and confidence intervals of national, age-specific (0-4, 5-9, 10-14, 15-17, 18-44, 45-64, 65-84, >84) and intent-specific (assault, unintentional, suicide, undetermined) emergency department discharges for firearm injuries. We used survey-weighted regression to assess temporal trends. RESULTS: There was a total of 868,483 (25.5 per 100,000) emergency department visits for firearm injuries from 2006 to 2016, and 7.8% died in the emergency department. Overall, firearm injury rates remained steady (P = .78). The largest burden was among those 25 to 44 years of age, but their rates remained stable (10.8 per 100,000). Overall assault injuries declined from 39.7% to 36.4%, and overall unintentional injuries increased from 46.4% to 54.7%. Legal-intervention injuries declined from 0.6 to 0.3 per 100,000. The charges (total $4,059,070,364, $369,006,396/year) increased across time in age and intent groups. The mean predicted charges increased from $1,922 to $3,348 in those alive versus $3,741 to $6,515 among those who died. CONCLUSION: Interventions and programs to manage the consequences of firearm injury in persons who live with ongoing morbidity and economic burden are warranted.

Optical Property Tuning of Single-Wall Carbon Nanotubes by Endohedral Encapsulation of a Wide Variety of Dielectric Molecules.

Specific and tunable modification to the optical properties of single-wall carbon nanotubes (SWCNTs) is demonstrated through direct encapsulation into the nanotube interior of guest molecules with widely varying static dielectric constants. Filled through simple ingestion of the guest molecule, each SWCNT population is demonstrated to display a robust modification to absorbance, fluorescence, and Raman spectra. Over 30 distinct compounds, covering static dielectric constants from 1.8 to 109, are inserted in large diameter SWCNTs (d = 1.104-1.524 nm) and more than 10 compounds in small diameter SWCNTs (d = 0.747-1.153 nm), demonstrating that the general effect of filler dielectric on the nanotube optical properties is a monotonic energy reduction (red-shifting) of the optical transitions with increased magnitude of the dielectric constant. Systematic fitting of the two-dimensional fluorescence-excitation and Raman spectra additionally enables determination of the critical filling diameter for each molecule and distinguishing of overall trends from specific guest-host interactions. Comparisons to predictions from existing theory are presented, and specific guest molecule/SWCNT chirality combinations that disobey the general trend and theory are identified. A general increase of the fluorescence intensity and line narrowing is observed for low dielectric constants, with long linear alkane filled SWCNTs exhibiting emission intensities approaching those of empty SWCNTs. These results demonstrate an exploitable modulation in the optical properties of SWCNTs and provide a foundation for examining higher-order effects, such as due to nonbulk-like molecule stacking, in host-guest interactions in well-controlled nanopore size materials.

Brightly Luminescent CsPbBr3 Nanocrystals through Ultracentrifugation.

Using a combination of density-gradient and analytical ultracentrifugation, we studied the photophysical profile of CsPbBr3 nanocrystal (NC) suspensions by separating them into size-resolved fractions. Ultracentrifugation drastically alters the ligand profile of the NCs, which necessitates postprocessing to restore colloidal stability and enhance quantum yield (QY). Rejuvenated fractions show a 50% increase in QY compared to no treatment and a 30% increase with respect to the parent. Our results demonstrate how the NC environment can be manipulated to improve photophysical performance, even after there has been a measurable decline in the response. Size separation reveals blue-emitting fractions, a narrowing of photoluminescence spectra in comparison to the parent, and a crossover from single- to stretched-exponential relaxation dynamics with decreasing NC size. As a function of edge length, L, our results confirm that the photoluminescence peak energy scales a L-2, in agreement with the simplest picture of quantum confinement.

Precise pitch-scaling of carbon nanotube arrays within three-dimensional DNA nanotrenches.

Precise fabrication of semiconducting carbon nanotubes (CNTs) into densely aligned evenly spaced arrays is required for ultrascaled technology nodes. We report the precise scaling of inter-CNT pitch using a supramolecular assembly method called spatially hindered integration of nanotube electronics. Specifically, by using DNA brick crystal-based nanotrenches to align DNA-wrapped CNTs through DNA hybridization, we constructed parallel CNT arrays with a uniform pitch as small as 10.4 nanometers, at an angular deviation <2° and an assembly yield >95%.

DNA-directed nanofabrication of high-performance carbon nanotube field-effect transistors.

Biofabricated semiconductor arrays exhibit smaller channel pitches than those created using existing lithographic methods. However, the metal ions within biolattices and the submicrometer dimensions of typical biotemplates result in both poor transport performance and a lack of large-area array uniformity. Using DNA-templated parallel carbon nanotube (CNT) arrays as model systems, we developed a rinsing-after-fixing approach to improve the key transport performance metrics by more than a factor of 10 compared with those of previous biotemplated field-effect transistors. We also used spatially confined placement of assembled CNT arrays within polymethyl methacrylate cavities to demonstrate centimeter-scale alignment. At the interface of high-performance electronics and biomolecular self-assembly, such approaches may enable the production of scalable biotemplated electronics that are sensitive to local biological environments.

Improved Electrophoretic Deposition of Vertical Single Wall Carbon Nanotubes with Nanoscopic Electrostatic Lenses.

Under certain conditions, electrophoretic deposition (EPD) of single-wall carbon nanotubes (SWCNTs) onto metal at the base of nanoscale insulating windows can result in a single SWCNT per window, bonded at one end to the metal. During EPD charge, buildup on the insulator creates electrostatic lenses at the windows that control the trajectory of the SWCNTs. The aim is to develop a reproducible process for deposition of individual vertically oriented SWCNTs into each window to enable novel devices. The length of the SWCNTs is shown to be the most critical parameter in achieving results that could be used for devices. In particular, single nanotube deposition in windows by EPD was achieved with SWCNTs with lengths on the order of the window depth. By performing current vs voltage (IV) measurements against a platinum wire in a phosphate buffer and by modeling the data, the presence of the nanotube can be detected, the contact interface can be studied, and the nanotube's viability for device applications can be determined. These results provide a basis for process integration of vertical SWCNTs using EPD.

Bright Silicon Nanocrystals from a Liquid Precursor: Quasi-Direct Recombination with High Quantum Yield.

Silicon nanocrystals (SiNCs) with bright bandgap photoluminescence (PL) are of current interest for a range of potential applications, from solar windows to biomedical contrast agents. Here, we use the liquid precursor cyclohexasilane (Si6H12) for the plasma synthesis of colloidal SiNCs with exemplary core emission. Through size separation executed in an oxygen-shielded environment, we achieve PL quantum yields (QYs) approaching 70% while exposing intrinsic constraints on efficient core emission from smaller SiNCs. Time-resolved PL spectra of these fractions in response to femtosecond pulsed excitation reveal a zero-phonon radiative channel that anticorrelates with QY, which we model using advanced computational methods applied to a 2 nm SiNC. Our results offer additional insight into the photophysical interplay of the nanocrystal surface, quasi-direct recombination, and efficient SiNC core PL.