Solvent Isotope Effects on the Creation of Fluorescent Quantum Defects in Carbon Nanotubes by Aryl Diazonium Chemistry.

The integration of aryl diazonium and carbon nanotube chemistries has offered rich and versatile tools for creating nanomaterials of unique optical and electronic properties in a controllable fashion. The diazonium reaction with single-wall carbon nanotubes (SWCNTs) is known to proceed through a radical or carbocation mechanism in aqueous solutions, with deuterated water (D2O) being the frequently used solvent. Here, we show strong water solvent isotope effects on the aryl diazonium reaction with SWCNTs for creating fluorescent quantum defects using water (H2O) and D2O. We found a deduced reaction constant of ∼18.2 times larger value in D2O than in H2O, potentially due to their different chemical properties. We also observed the generation of new defect photoluminescence over a broad concentration range of diazonium reactants in H2O, as opposed to a narrow window of reaction conditions in D2O under UV excitation. Without UV light, the physical adsorption of diazonium on the surface of SWCNTs led to the fluorescence quenching of nanotubes. These findings provide important insights into the aryl diazonium chemistry with carbon nanotubes for creating promising material platforms for optical sensing, imaging, and quantum communication technologies.

Glycopolymer-Wrapped Carbon Nanotubes Show Distinct Interaction of Carbohydrates With Lectins.

Glyconanomaterials with unique nanoscale property and carbohydrate functionality show vast potential in biological and biomedical applications. We investigated the interactions of noncovalent complexes of single-wall carbon nanotubes that are wrapped by disaccharide lactose-containing glycopolymers with the specific carbohydrate-binding proteins. The terminal galactose (Gal) of glycopolymers binds to the specific lectin as expected. Interestingly, an increased aggregation of nanotubes was also observed when interacting with a glucose (Glc) specific lectin, likely due to the removal of Glc groups from the surface of nanotubes resulting from the potential binding of the lectin to the Glc in the glycopolymers. This result indicates that the wrapping conformation of glycopolymers on the surface of nanotubes potentially allows improved accessibility of the Glc for specific lectins. Furthermore, it shows that the interaction between Glc groups in the glycopolymers and nanotubes play a key role in stabilizing the nanocomplexes. Overall, our results demonstrate that nanostructures can enable conformation-dependent interactions of glycopolymers and proteins and can potentially lead to the creation of versatile optical sensors for detecting carbohydrate-protein interactions with enhanced specificity and sensitivity.

Interaction of DNA-Complexed Boron Nitride Nanotubes and Cosolvents Impacts Dispersion and Length Characteristics.

Processing boron nitride nanotubes (BNNTs) for applications ranging from nanomedicine to electronics generally requires dispersions of nanotubes that are stable in various compounds and solvents. We show that alcohol/water cosolvents, particularly isopropyl alcohol (IPA), are essential for the complexation of BNNTs with DNA under mild bath sonication. The resulting DNA-wrapped BNNT complexes are highly stable during purification and solvent exchange from cosolvents to water, providing potential for the versatile liquid-phase processing of BNNTs. Via molecular dynamics simulations, we demonstrate that IPA assists in the solvation of BNNTs due to its pseudosurfactant nature by verifying that water is replaced in the solvation layer as IPA is added. We quantify the solvation free energy of BNNTs in various IPA/water mixtures and observe a nonmonotonic trend, highlighting the importance of utilizing solvent-nanotube interactions in nanomaterial dispersions. Additionally, we show that nanotube lengths can be characterized by rheology measurements via determining the viscosity of dilute dispersions of DNA-BNNTs. This represents the bulk sample property in the liquid state, as compared to conventional imaging techniques that require surface deposition and drying. Our results also demonstrate that BNNT dispersions exhibit the rheological behavior of dilute Brownian rigid rods, which can be further exploited for the controlled processing and property enhancement of BNNT-enabled assemblies such as films and fibers.

Boron nitride nanotubes enhance mechanical properties of fibers from nanotube/polyvinyl alcohol dispersions.

Effectively translating the promising properties of boron nitride nanotubes (BNNTs) into macroscopic assemblies has vast potential for applications, such as thermal management materials and protective fabrics against hazardous environment. We spun fibers from aqueous dispersions of BNNTs in polyvinyl alcohol (PVA) solutions by a wet spinning method. Our results demonstrate that BNNTs/PVA fibers exhibit enhanced mechanical properties, which are affected by the nanotube and PVA concentrations, and the coagulation solvent utilized. Compared to the neat PVA fibers, we obtained roughly 4.3-, 12.7-, and 1.5-fold increases in the tensile strength, Young's modulus, and toughness, respectively, for the highest performing BNNTs/PVA fibers produced from dispersions containing as low as 0.1 mass% of nanotube concentration. Among the coagulation solvents tested, we found that solvents with higher polarity such as methanol and ethanol generally produced fibers with improved mechanical properties, where the fiber toughness shows a strong correlation with solvent polarity. These findings provide insights into assembling BNNTs-based fibers with improved mechanical properties for developing unique applications.

Carbohydrate- and Chain Length-Controlled Complexation of Carbon Nanotubes by Glycopolymers.

Stable dispersions of single-wall carbon nanotubes (SWCNTs) by biopolymers in an aqueous environment facilitate their potential biological and biomedical applications. In this report, we investigated a small library of precision synthesized glycopolymers with monosaccharide and disaccharide groups for stabilizing SWCNTs via noncovalent complexation in aqueous conditions. Among the glycopolymers tested, disaccharide lactose-containing glycopolymers demonstrate effective stabilization of SWCNTs in water, which strongly depends on carbohydrate density and polymer chain length as well. The introduction of disaccharide lactose potentially makes glycopolymers less flexible as compared to those containing monosaccharide and facilitates the wrapping conformation of polymers on the surface of SWCNTs while preserving intrinsic photoluminescence of nanotubes in the near-infrared region. This work demonstrates the synergistic effects of the identity of carbohydrate pendant groups and polymer chain length of glycopolymers on stabilizing SWCNTs in water, which has not been achieved previously.

Targeting of CD38 by the Tumor Suppressor miR-26a Serves as a Novel Potential Therapeutic Agent in Multiple Myeloma.

Multiple myeloma is an incurable refractory hematologic malignancy arising from plasma cells in the bone marrow. Here we investigated miR-26a function in multiple myeloma and tested single-wall carbon nanotube delivery of miR-26a in vitro and in vivo. miR-26a was downregulated in patients with multiple myeloma cells compared with plasma cells from healthy donors. miR-26a overexpression inhibited proliferation and migration and induced apoptosis in multiple myeloma cell lines. To identify the targets of miR-26a, RPMI8226-V-miR-26-GFP and RPMI8226-V-GFP cells were cultured using stable isotope labeling by amino acids in cell culture (SILAC) medium, followed by mass spectrometry analysis. In multiple myeloma cells overexpressing miR-26a, CD38 protein was downregulated and subsequently confirmed to be a direct target of miR-26a. Depletion of CD38 in multiple myeloma cells duplicated the multiple myeloma inhibition observed with exogenous expression of miR-26a, whereas restoration of CD38 overcame the inhibition of miR-26a in multiple myeloma cells. In a human multiple myeloma xenograft mouse model, overexpression of miR-26a inhibited CD38 expression, provoked cell apoptosis, and inhibited cell proliferation. Daratumumab is the first CD38 antibody drug for monotherapy and combination therapy for patients with multiple myeloma, but eventually resistance develops. In multiple myeloma cells, CD38 remained at low level during daratumumab treatment, but a high-quality response is sustained. In daratumumab-resistant multiple myeloma cells, CD38 expression was completely restored but failed to correlate with daratumumab-induced cell death. Therefore, a therapeutic strategy to confer selection pressure to maintain low CD38 expression in multiple myeloma cells may have clinical benefit. SIGNIFICANCE: These results highlight the tumor suppressor function of miR-26a via its targeting of CD38 and suggest the therapeutic potential of miR-26a in patients with multiple myeloma.

Hidden Fine Structure of Quantum Defects Revealed by Single Carbon Nanotube Magneto-Photoluminescence.

Organic color-center quantum defects in semiconducting carbon nanotube hosts are rapidly emerging as promising candidates for solid-state quantum information technologies. However, it is unclear whether these defect color-centers could support the spin or pseudospin-dependent excitonic fine structure required for spin manipulation and readout. Here we conducted magneto-photoluminescence spectroscopy on individual organic color-centers and observed the emergence of fine structure states under an 8.5 T magnetic field applied parallel to the nanotube axis. One to five fine structure states emerge depending on the chirality of the nanotube host, nature of chemical functional group, and chemical binding configuration, presenting an exciting opportunity toward developing chemical control of magnetic brightening. We attribute these hidden excitonic fine structure states to field-induced mixing of singlet excitons trapped at sp3 defects and delocalized band-edge triplet excitons. These findings provide opportunities for using organic color-centers for spintronics, spin-based quantum computing, and quantum sensing.

Mod(n-m,3) Dependence of Defect-State Emission Bands in Aryl-Functionalized Carbon Nanotubes.

Molecularly functionalized single-walled carbon nanotubes (SWCNTs) are potentially useful for fiber optical applications due to their room temperature single-photon emission capacity at telecommunication wavelengths. Several distinct defect geometries are generated upon covalent functionalization. While it has been shown that the defect geometry controls electron localization around the defect site, thereby changing the electronic structure and generating new optically bright red-shifted emission bands, the reasons for such localization remain unexplained. Our joint experimental and computational studies of functionalized SWCNTs with various chiralities show that the value of mod(n-m,3) in an (n,m) chiral nanotube plays a key role in the relative ordering of defect-dependent emission energies. This dependence is linked to the complex nodal characteristics of electronic wave function extending along specific bonds in the tube, which justifies the defect-geometry dependent exciton localization. This insight helps to uncover the essential structural motifs allowing tuning the redshifts of emission energies in functionalized SWCNTs.

An optical nanoreporter of endolysosomal lipid accumulation reveals enduring effects of diet on hepatic macrophages in vivo.

The abnormal accumulation of lipids within the endolysosomal lumen occurs in many conditions, including lysosomal storage disorders, atherosclerosis, nonalcoholic fatty liver disease (NAFLD), and drug-induced phospholipidosis. Current methods cannot monitor endolysosomal lipid content in vivo, hindering preclinical drug development and research into the mechanisms linking endolysosomal lipid accumulation to disease progression. We developed a single-walled carbon nanotube-based optical reporter that noninvasively measures endolysosomal lipid accumulation via bandgap modulation of its intrinsic near-infrared emission. The reporter detected lipid accumulation in Niemann-Pick disease, atherosclerosis, and NAFLD models in vivo. By applying the reporter to the study of NAFLD, we found that elevated lipid quantities in hepatic macrophages caused by a high-fat diet persist long after reverting to a normal diet. The reporter dynamically monitored endolysosomal lipid accumulation in vivo over time scales ranging from minutes to weeks, indicating its potential to accelerate preclinical research and drug development processes.

Narrow-band single-photon emission through selective aryl functionalization of zigzag carbon nanotubes.

The introduction of sp3 defects into single-walled carbon nanotubes through covalent functionalization can generate new light-emitting states and thus dramatically expand their optical functionality. This may open up routes to enhanced imaging, photon upconversion, and room-temperature single-photon emission at telecom wavelengths. However, a significant challenge in harnessing this potential is that the nominally simple reaction chemistry of nanotube functionalization introduces a broad diversity of emitting states. Precisely defining a narrow band of emission energies necessitates constraining these states, which requires extreme selectivity in molecular binding configuration on the nanotube surface. We show here that such selectivity can be obtained through aryl functionalization of so-called 'zigzag' nanotube structures to achieve a threefold narrowing in emission bandwidth. Accompanying density functional theory modelling reveals that, because of the associated structural symmetry, the defect states become degenerate, thus limiting emission energies to a single narrow band. We show that this behaviour can only result from a predominant selectivity for ortho binding configurations of the aryl groups on the nanotube lattice.

Mapping Structure-Property Relationships of Organic Color Centers.

Organic color centers are an emergent class of quantum emitters that hold vast potential for applications in bioimaging, chemical sensing, and quantum information processing. Here, we show that these synthetic color centers follow interesting structure-property relationships through comparative spectral studies of 14 purified single-walled carbon nanotube chiralities and 30 different functional groups that vary in electron-withdrawing capability and bonding configurations. The defect emission is tunable by as much as 400 meV in the near-infrared as a function of host structure and the chemical nature of the color centers. However, the emission energy is nearly free from chiral angle and family patterns of the nanotube host (although this strongly depends on the nanotube diameter), suggesting that a trapped exciton at the organic color centers to some degree electronically decouples from the one-dimensional semiconductor host. Our findings provide important insights for designing and controlling this new family of synthetic color centers.

Differentiating Left- and Right-Handed Carbon Nanotubes by DNA.

New structural characteristics emerge when solid-state crystals are constructed in lower dimensions. This is exemplified by single-wall carbon nanotubes, which exhibit a degree of freedom in handedness and a multitude of helicities that give rise to three distinct types of electronic structures: metals, quasi-metals, and semiconductors. Here we report the use of intrinsically chiral single-stranded DNA to achieve simultaneous handedness and helicity control for all three types of nanotubes. We apply polymer aqueous two-phase systems to select special DNA-wrapped carbon nanotubes, each of which we argue must have an ordered DNA structure that binds to a nanotube of defined handedness and helicity and resembles a well-folded biomacromolecule with innate stereoselectivity. We have screened over 300 short single-stranded DNA sequences with palindrome symmetry, leading to the selection of more than 20 distinct carbon nanotube structures that have defined helicity and handedness and cover the entire chiral angle range and all three electronic types. The mechanism of handedness selection is illustrated by a DNA sequence that adopts two distinct folds on a pair of (6,5) nanotube enantiomers, rendering them large differences in fluorescence intensity and chemical reactivity. This result establishes a first example of functionally distinguishable left- and right-handed carbon nanotubes. Taken together, our work demonstrates highly efficient enantiomer differentiation by DNA and offers a first comprehensive solution to achieve simultaneous handedness and helicity control for all three electronic types of carbon nanotubes.

Intensity Ratio of Resonant Raman Modes for (n,m) Enriched Semiconducting Carbon Nanotubes.

Relative intensities of resonant Raman spectral features, specifically the radial breathing mode (RBM) and G modes, of 11, chirality-enriched, single-wall carbon nanotube (SWCNT) species were established under second-order optical transition excitation. The results demonstrate an under-recognized complexity in the evaluation of Raman spectra for the assignment of (n,m) population distributions. Strong chiral angle and mod dependencies affect the intensity ratio of the RBM to G modes and can result in misleading interpretations. Furthermore, we report five additional (n,m) values for the chirality-dependent G(+) and G(-) Raman peak positions and intensity ratios; thereby extending the available data to cover more of the smaller diameter regime by including the (5,4) second-order, resonance Raman spectra. Together, the Raman spectral library is demonstrated to be sufficient for decoupling G peaks from multiple species via a spectral fitting process, and enables fundamental characterization even in mixed chiral population samples.

Solution-Processable Carbon Nanoelectrodes for Single-Molecule Investigations.

Here we present a solution-based assembly method for producing molecular transport junctions employing metallic single-walled carbon nanotubes as nanoelectrodes. The molecular junction conductance of a series of oligophenyls was successfully measured, highlighting the potential of an all-carbon based approach for the fabrication of solution-processable single-molecule junctions for molecular electronics.

Directed Assembly of Single Wall Carbon Nanotube Field Effect Transistors.

The outstanding electronic properties of single wall carbon nanotubes (SWCNTs) have made them prime candidates for future nanoelectronics technologies. One of the main obstacles to the implementation of advanced SWCNT electronics to date is the inability to arrange them in a manner suitable for complex circuits. Directed assembly of SWCNT segments onto lithographically patterned and chemically functionalized substrates is a promising way to organize SWCNTs in topologies that are amenable to integration for advanced applications, but the placement and orientational control required have not yet been demonstrated. We have developed a technique for assembling length sorted and chirality monodisperse DNA-wrapped SWCNT segments on hydrophilic lines patterned on a passivated oxidized silicon substrate. Placement of individual SWCNT segments at predetermined locations was achieved with nanometer accuracy. Three terminal electronic devices, consisting of a single SWCNT segment placed either beneath or on top of metallic source/drain electrodes were fabricated. Devices made with semiconducting nanotubes behaved as typical p-type field effect transistors (FETs), whereas devices made with metallic nanotubes had a finite resistance with little or no gate modulation. This scalable, high resolution approach represents an important step forward toward the potential implementation of complex SWCNT devices and circuits.

Preparation and separation of DNA-wrapped carbon nanotubes.

Purification of single-chirality single-wall carbon nanotubes (SWCNTs) from their synthetic mixture is a prerequisite for many applications. DNA-controlled carbon nanotube (CNT) purification has evolved over a decade along with other separation techniques utilizing different types of dispersing agents such as surfactants and polymers. The size of single-stranded DNA (ssDNA) libraries affords practically unlimited ways of coating SWCNTs. Recent developments in separating surfactant-dispersed SWCNTs by polymer aqueous two-phase (ATP) extraction has enabled rapid and efficient SWCNT separation on a larger volume scale. Applying the ATP separation method to DNA-SWCNT hybrids opens a new route for effective sorting of nanotubes into each and every single-chirality species. Here, we report protocols for purifying as many as 15 single-chirality nanotube species from a synthetic mixture based on the separation of DNA-SWCNTs by the aqueous two-phase (ATP) method.

DNA-controlled partition of carbon nanotubes in polymer aqueous two-phase systems.

Sorting single-wall carbon nanotubes (SWCNTs) of different chiralities is both scientifically interesting and technologically important. Recent studies have shown that polymer aqueous two-phase extraction is a very effective way to achieve nanotube sorting. However, works published to date have demonstrated only separation of surfactant-dispersed SWCNTs, and the mechanism of chirality-dependent SWCNT partition is not well understood. Here we report a systematic study of spontaneous partition of DNA-wrapped SWCNTs in several polymer aqueous two-phase systems. We show that partition of DNA-SWCNT hybrids in a given polymer two-phase system is strongly sequence-dependent and can be further modulated by salt and polymer additives. With the proper combination of DNA sequence, polymer two-phase system, and partition modulators, as many as 15 single-chirality nanotube species have been effectively purified from a synthetic mixture. As an attempt to provide a unified partition mechanism of SWCNTs dispersed by surfactants and by DNA, we present a qualitative analysis of solvation energy for SWCNT colloids in a polymer-modified aqueous phase. Our observation and analysis highlight the sensitive dependence of the hydration energy on the spatial distribution of hydrophilic functionalities.

Cholesteric and nematic liquid crystalline phase behavior of double-stranded DNA stabilized single-walled carbon nanotube dispersions.

The first lyotropic cholesteric single-walled carbon nanotube (SWNT) liquid crystal phase was obtained by dispersing SWNTs in an aqueous solution of double-stranded DNA (dsDNA). Depending on the dispersion methodology, the polydomain nematic phase previously reported for other lyotropic carbon nanotube dispersions could also be obtained. The phase behavior and dispersion microstructure were affected by the relative concentrations of dsDNA and SWNT and whether small bundles were removed prior to concentrating the dispersions. This readily controlled phase behavior opens new routes for producing SWNT films with controlled morphology.