Scalable Method for the Reductive Dissolution, Purification, and Separation of Single-Walled Carbon Nanotubes

As synthesized, bulk single-walled carbon nanotube (SWNT) samples are typically highly agglomerated and heterogeneous. However, their most promising applications require the isolation of individualized, purified nanotubes, often with specific optoelectronic characteristics. A wide range of dispersion and separation techniques have been developed, but the use of sonication or ultracentrifugation imposes severe limits on scalability and may introduce damage. Here, we demonstrate a new, intrinsically scalable method for SWNT dispersion and separation, using reductive treatment in sodium metal-ammonia solutions, optionally followed by selective dissolution in a polar aprotic organic solvent. <i>In situ</i> small-angle neutron scattering demonstrates the presence of dissolved, unbundled SWNTs in solution, at concentrations reaching at least 2 mg/mL; the ability to isolate individual nanotubes is confirmed by atomic force microscopy. Spectroscopy data suggest that the soluble fraction contains predominately large metallic nanotubes; a potential new mechanism for nanotube separation is proposed. In addition, the G/D ratios observed during the dissolution sequence, as a function of metal:carbon ratio, demonstrate a new purification method for removing carbonaceous impurities from pristine SWNTs, which avoids traditional, damaging, competitive oxidation reactions

Eumelanin Buildup on the Nanoscale: Aggregate Growth/Assembly and Visible Absorption Development in Biomimetic 5,6-Dihydroxyindole Polymerization.

Establishing structure–property relationships in the black insoluble eumelanins, the key determinants of human pigmentation and skin photoprotective system, is a considerable conceptual and experimental challenge in the current drive for elucidation of the biological roles of these biopolymers and their application as advanced materials for organoelectronics. Herein, we report a new breakthrough toward this goal by the first detailed investigation on the nanoscale level of the oxidative polymerization of 5,6-dihydroxyindole (DHI), a model process of eumelanin synthesis. On the basis of a combined use of spectrophotometry, dynamic light scattering (DLS), and small-angle neutron scattering (SANS) investigations, it was possible to unveil the dynamics of the aggregation process before precipitation, the key relationships with visible light absorption and the shape of fundamental aggregates. The results indicated a polymerization mechanism of the type: Polymer_<i>n</i> + DHI_<i>x</i> = Polymer_{<i>n</i>+<i>x</i>}, where DHI_<i>x</i> indicates monomer, dimer, or low oligomers (<i>x</i> ≤ 5). During polymerization, visible absorption increases rapidly, reaching a plateau. Particle growth proceeds slowly, with formation of 2-D structures ∼55 nm thick, until precipitation occurs, that is, when large aggregates with a maximum hydrodynamic radius (<i>R</i>_h) of ∼1200 nm are formed. Notably, markedly smaller <i>R</i>_h values, up to ∼110 nm, were determined in the presence of poly­(vinyl alcohol) (PVA) that was shown to be an efficient aggregation-preventing agent for polymerizing DHI ensuring water solubilization. Finally, it is shown that DHI monomer can be efficiently and partially irreversibly depleted from aqueous solutions by the addition of eumelanin suspensions. This behavior is suggested to reflect oxidant-independent competing pathways of polymer synthesis and buildup <i>via</i> monomer conversion on the active aggregate surface contributing to particle growth. Besides filling crucial gaps in DHI polymerization, these results support the attractive hypothesis that eumelanins may behave as a peculiar example of living biopolymers. The potential of PVA as a powerful tool for solution chemistry-based investigations of eumelanin supramolecular organization and for technological manipulation purposes is underscored

Hybrid CO₂-philic Surfactants with Low Fluorine Content

The relationships between molecular architecture, aggregation, and interfacial activity of a new class of CO₂-philic hybrid surfactants are investigated. The new hybrid surfactant CF2/AOT4 [sodium (4<i>H</i>,4<i>H</i>,5<i>H</i>,5<i>H</i>,5<i>H</i>-pentafluoropentyl-3,5,5-trimethyl-1-hexyl)-2-sulfosuccinate] was synthesized, having one hydrocarbon chain and one separate fluorocarbon chain. This hybrid H–F chain structure strikes a fine balance of properties, on one hand minimizing the fluorine content, while on the other maintaining a sufficient level of CO₂-philicity. The surfactant has been investigated by a range of techniques including high-pressure phase behavior, UV–visible spectroscopy, small-angle neutron scattering (SANS), and air–water (a/w) surface tension measurements. The results advance the understanding of structure–function relationships for generating CO₂-philic surfactants and are therefore beneficial for expanding applications of CO₂ to realize its potential using the most economic and efficient surfactants

Membrane Charging and Swelling upon Calcium Adsorption as Revealed by Phospholipid Nanodiscs

Direct binding of calcium ions (Ca²⁺) to phospholipid membranes is an unclarified yet critical signaling pathway in diverse Ca²⁺-regulated cellular phenomena. Here, high-pressure-liquid-chromatography, small-angle X-ray scattering (SAXS), UV–vis absorption, and differential refractive index detections are integrated to probe Ca²⁺-binding to the zwitterionic lipid membranes in nanodiscs. The responses of the membranes upon Ca²⁺-binding, in composition and conformation, are quantified through integrated data analysis. The results indicate that Ca²⁺ binds specifically into the phospholipid headgroup zone, resulting in membrane charging and membrane swelling, with a saturated Ca²⁺-lipid binding ratio of 1:8. A Ca²⁺-binding isotherm to the nanodisc is further established and yields an unexpectedly high binding constant <i>K</i> = 4260 M^–1 and a leaflet potential of ca. 100 mV based on a modified Gouy–Chapman model. The calcium-lipid binding ratio, however, drops to 40% when the nanodisc undergoes a gel-to-fluid phase transition, leading to an effective charge capacity of a few μF/cm²

Nanostructures in Water-in-CO₂ Microemulsions Stabilized by Double-Chain Fluorocarbon Solubilizers

High-pressure small-angle neutron scattering (HP-SANS) studies were conducted to investigate nanostructures and interfacial properties of water-in-supercritical CO₂ (W/CO₂) microemulsions with double-fluorocarbon-tail anionic surfactants, having different fluorocarbon chain lengths and linking groups (glutarate or succinate). At constant pressure and temperature, the microemulsion aqueous cores were found to swell with an increase in water-to-surfactant ratio, <i>W</i>₀, until their solubilizing capacities were reached. Surfactants with fluorocarbon chain lengths of <i>n</i> = 4, 6, and 8 formed spherical reversed micelles in supercritical CO₂ even at <i>W</i>₀ over the solubilizing powers as determined by phase behavior studies, suggesting formation of Winsor-IV W/CO₂ microemulsions and then Winsor-II W/CO₂ microemulsions. On the other hand, a short C2 chain fluorocarbon surfactant analogue displayed a transition from Winsor-IV microemulsions to lamellar liquid crystals at <i>W</i>₀ = 25. Critical packing parameters and aggregation numbers were calculated by using area per headgroup, shell thickness, the core/shell radii determined from SANS data analysis: these parameters were used to help understand differences in aggregation behavior and solubilizing power in CO₂. Increasing the microemulsion water loading led the critical packing parameter to decrease to ∼1.3 and the aggregation number to increase to >90. Although these parameters were comparable between glutarate and succinate surfactants with the same fluorocarbon chain, decreasing the fluorocarbon chain length <i>n</i> reduced the critical packing parameter. At the same time, reducing chain length to 2 reduced negative interfacial curvature, favoring planar structures, as demonstrated by generation of lamellar liquid crystal phases

Structure and Morphology of Charged Graphene Platelets in Solution by Small-Angle Neutron Scattering

Solutions of negatively charged graphene (graphenide) platelets were produced by intercalation of nanographite with liquid potassium–ammonia followed by dissolution in tetrahydrofuran. The structure and morphology of these solutions were then investigated by small-angle neutron scattering. We found that >95 vol % of the solute is present as single-layer graphene sheets. These charged sheets are flat over a length scale of >150 Å in solution and are strongly solvated by a shell of solvent molecules. Atomic force microscopy on drop-coated thin films corroborated the presence of monolayer graphene sheets. Our dissolution method thus offers a significant increase in the monodispersity achievable in graphene solutions

Fate of Liposomes in the Presence of Phospholipase C and D: From Atomic to Supramolecular Lipid Arrangement

Understanding the origins of lipid membrane bilayer rearrangement in response to external stimuli is an essential component of cell biology and the bottom-up design of liposomes for biomedical applications. The enzymes phospholipase C and D (PLC and PLD) both cleave the phosphorus–oxygen bonds of phosphate esters in phosphatidylcholine (PC) lipids. The atomic position of this hydrolysis reaction has huge implications for the stability of PC-containing self-assembled structures, such as the cell wall and lipid-based vesicle drug delivery vectors. While PLC converts PC to diacylglycerol (DAG), the interaction of PC with PLD produces phosphatidic acid (PA). Here we present a combination of small-angle scattering data and all-atom molecular dynamics simulations, providing insights into the effects of atomic-scale reorganization on the supramolecular assembly of PC membrane bilayers upon enzyme-mediated incorporation of DAG or PA. We observed that PC liposomes completely disintegrate in the presence of PLC, as conversion of PC to DAG progresses. At lower concentrations, DAG molecules within fluid PC bilayers form hydrogen bonds with backbone carbonyl oxygens in neighboring PC molecules and burrow into the hydrophobic region. This leads initially to membrane thinning followed by a swelling of the lamellar phase with increased DAG. At higher DAG concentrations, localized membrane tension causes a change in lipid phase from lamellar to the hexagonal and micellar cubic phases. Molecular dynamics simulations show that this destabilization is also caused in part by the decreased ability of DAG-containing PC membranes to coordinate sodium ions. Conversely, PLD-treated PC liposomes remain stable up to extremely high conversions to PA. Here, the negatively charged PA headgroup attracts significant amounts of sodium ions from the bulk solution to the membrane surface, leading to a swelling of the coordinated water layer. These findings are a vital step toward a fundamental understanding of the degradation behavior of PC lipid membranes in the presence of these clinically relevant enzymes, and toward the rational design of diagnostic and drug delivery technologies for phospholipase-dysregulation-based diseases

Fate of Liposomes in the Presence of Phospholipase C and D: From Atomic to Supramolecular Lipid Arrangement

Understanding the origins of lipid membrane bilayer rearrangement in response to external stimuli is an essential component of cell biology and the bottom-up design of liposomes for biomedical applications. The enzymes phospholipase C and D (PLC and PLD) both cleave the phosphorus–oxygen bonds of phosphate esters in phosphatidylcholine (PC) lipids. The atomic position of this hydrolysis reaction has huge implications for the stability of PC-containing self-assembled structures, such as the cell wall and lipid-based vesicle drug delivery vectors. While PLC converts PC to diacylglycerol (DAG), the interaction of PC with PLD produces phosphatidic acid (PA). Here we present a combination of small-angle scattering data and all-atom molecular dynamics simulations, providing insights into the effects of atomic-scale reorganization on the supramolecular assembly of PC membrane bilayers upon enzyme-mediated incorporation of DAG or PA. We observed that PC liposomes completely disintegrate in the presence of PLC, as conversion of PC to DAG progresses. At lower concentrations, DAG molecules within fluid PC bilayers form hydrogen bonds with backbone carbonyl oxygens in neighboring PC molecules and burrow into the hydrophobic region. This leads initially to membrane thinning followed by a swelling of the lamellar phase with increased DAG. At higher DAG concentrations, localized membrane tension causes a change in lipid phase from lamellar to the hexagonal and micellar cubic phases. Molecular dynamics simulations show that this destabilization is also caused in part by the decreased ability of DAG-containing PC membranes to coordinate sodium ions. Conversely, PLD-treated PC liposomes remain stable up to extremely high conversions to PA. Here, the negatively charged PA headgroup attracts significant amounts of sodium ions from the bulk solution to the membrane surface, leading to a swelling of the coordinated water layer. These findings are a vital step toward a fundamental understanding of the degradation behavior of PC lipid membranes in the presence of these clinically relevant enzymes, and toward the rational design of diagnostic and drug delivery technologies for phospholipase-dysregulation-based diseases