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Dispersion and exfoliation of carbon nanotubes (CNT) by water soluble dispersants such as surfactant, polymer or protein is a key step toward the application of carbon nanotubes in composite materials, biochemical and biomedical applications. Upon dispersion, the solution phase separates into dispersed nanotubes in the supernatant and a precipitate phase including carbonaceous impurities but also nanotubes and dispersants. Yet, simple but accurate tools for measuring the concentrations of the constituents are not available. In most studies a comparison between CNT suspensions is based on ocular observation or on UV-visible measurement of a featureless spectrum at single wavelength. Such measurements are complex since both nanotubes and most dispersants absorb along the whole UV-visible spectrum and an overlap of their signals occurs. In this paper we employ chemometric techniques to evaluate the pH effect on the concentration of both dispersant (protein-bovine serum albumin, BSA) and single-wall nanotube (SWNT) from a full UV-visible spectrum of aqueous solutions. We find strong correlation between the conformation of the protein and its dispersion efficiency.

In this paper we demonstrate that the sonication-driven exfoliation of aggregates and bundles of single-wall carbon nanotubes (SWNTs) in an aqueous surfactant solution can be easily monitored by UV-vis spectroscopy. The different stages of the exfoliation process were directly visualized by cryogenic temperature transmission electron microscopy, showing an excellent correspondence with the spectroscopic data: the maximum achievable exfoliation (which does not mean that 100% of the NTs are effectively exfoliated) corresponds to the maximum UV-vis absorbance of the NT solution. Moreover, it has been observed that NTs produced by the arc-discharge technology (Carbolex NTs) require less energy to achieve maximum exfoliation than NTs produced by chemical vapor deposition (HiPCO NTs). This difference is attributed to weaker van der Waals attraction between Carbolex NTs in the bundles and aggregates.

Issues concerning the microstructure of C16TABr micelles with solubilized benzene are discussed. It was found that, on benzene addition, the micelles become marginally elongated microemulsion droplets.

Silver metal colloids and ordered lamellar phases of the water/SDS/hexanol/dodecane system can be combined to form hybrid systems. The colloids can be selectively directed to the aqueous region or to the organic region in the lamellar phase, using hydrophilic and hydrophobic particles. Some penetration into the hydrophobic region of the surfactant layer is noted among hydrophobic particles, but hydrophilic particles exist only in the aqueous layers. UV-visible absorption spectroscopic data showed that the phase diagrams of the lamellar phase are only minimally affected by the presence of the colloid, but a systematic shift of the boundary of the L(alpha) region and a change in the interlamellar distances are noted.

An in situ cryogenic-TEM (Cryo-TEM) study was performed on a selected aqueous system, where the lamellar phase dominates, in order to evaluate the possible formation of silicate-surfactant vesicles during the course of the reaction. The employed mixture of an anionic and a cationic surfactant facilitates the formation of vesicles in combination with the decrease in interfacial charge density upon adsorption of negatively charged silicate polyions and toluene is continuously added into the silicate-mixed surfactant assemblies during the formation of the mesophase.

A study was conducted to investigate vesicle formation and general phase behavior in the cationic mixture sodium dodecyl sulfate-didodecyldimethylammonium bromide in water. The samples were left for equilibration for a number of days before phase behavior examination. An Axioplan Universal light microscope was utilized to perform light microscopy studies. In addition, the self-diffusion coefficients of water in the isotropic solutes were obtained at 25 degrees C.

The yet virtually unexplored class of soft colloidal rods with a small aspect ratio is investigated and shown to exhibit a very rich phase and dynamic behavior, spanning from liquid to nearly melt state. Instead of the nematic order, these short and soft nanocylinders alter their organization with increasing concentration from isotropic liquid with random orientation to small domains with preferred local orientation and eventually a multidomain arrangement with a local orientational order. The latter gives rise to a kinetically suppressed state akin to structural glass with detectable terminal relaxation, which, on further increasing concentration, reveals features of hexagonally packed order as in ordered block copolymers. The respective dynamic response comprises four regimes, all above the overlapping concentration of 0.02 g/mL:(I) from 0.03 to 0.1 g/mol, the system undergoes a liquid-to-solidlike transition with a structural relaxation time that grows by 4 orders of magnitude. (II) From 0.1 to 0.2 g/mL, a dramatic slowing-down is observed and is accompanied by an evolution from isotropic to a multidomain structure. (III) Between 0.2 and 0.6 g/mol, the suspensions exhibit signatures of shell interpenetration and jamming, with the colloidal plateau modulus depending linearly on concentration. (IV) At 0.74 g/mL, in the densely jammed state, the viscoelastic signature of hexagonally packed cylinders from microphase-separated block copolymers is detected. These properties set short and soft nanocylinders apart from long colloidal rods (with a large aspect ratio) and provide insights for fundamentally understanding the physics in this intermediate soft colloidal regime and for tailoring the flow properties of nonspherical soft colloids.

When using amphiphilic polymers to exfoliate and disperse carbon nanotubes in water, the balance between the hydrophobic and hydrophilic moieties is critical and nontrivial. Here, we investigate the mode of surface attachment of a triblock copolymer, Pluronics F127, composed of a central hydrophobic polypropylene oxide block flanked by hydrophilic polyethylene oxide blocks, onto single-walled carbon nanotubes (SWNTs). Crucially, we analyze the composition in dispersant of both the as-obtained dispersion (the supernatant) and the precipitate-containing undispersed materials. For this, we combine the carefully obtained data from 1 H NMR peak intensities and self-diffusion and thermogravimetric analysis. The molecular motions behind the observed NMR features are clarified. We find that the hydrophobic blocks attach to the dispersed SWNT surface and remain significantly immobilized leading to 1 H NMR signal loss. On the other hand, the hydrophilic blocks remain highly mobile and thus readily detectable by NMR. The dispersant is shown to possess significant block polydispersity that has a large effect on dispersibility. Polymers with large hydrophobic blocks adsorb on the surface of the carbonaceous particles that precipitate, indicating that although a larger hydrophobic block is good for enhancing adsorption, it may be less effective in dispersing the tubes. A model is also proposed that consistently explains our observations in SWNT dispersions and some contradicting findings obtained previously in carbon nanohorn dispersions. Overall, our findings help elucidating the molecular picture of the dispersion process for SWNTs and are of interest when looking for more effective (i.e., well-balanced) polymeric dispersants.

The uniqueness of Doxil can be attributed, to a large extent, to its intraliposomal doxorubicin-sulfate nanorod crystal. We re-examine these nanocrystal features and their mechanism of the formation by studying pegylated liposomal doxorubicins (PLDs) of the same lipid composition, size distribution, and extraliposome medium that were prepared at different ammonium sulfate (AS) concentrations. This study includes a comparison of the thermotropic behavior, morphology, and in vitro ammonia-induced doxorubicin release (relevant to Doxil's in vivo performance) of these PLDs. In this study, we confirm that a transmembrane ammonium gradient is critical for doxorubicin remote loading, and we demonstrate that the intraliposomal concentration of sulfate counteranions and ammonium ions determine to a large extent the physical state and stability of the PLDs' remote loaded doxorubicin. "Fully-developed" intraliposome doxorubicin-sulfate nanorod crystals (as defined by cryogenic transmission electron microscopy imaging) develop only when the ammonium sulfate (AS) concentration used for PLD preparation is ≥150 mM. Less than 10% of PLDs prepared with 100 mM AS show fully developed nanorod crystals. Intraliposomal AS concentration ≥200 mM is required to support the stable nanocrystallization in PLDs. The presence of nanocrystals and their melting enthalpy and phase transition co-operativity strongly affect the ammonia-induced doxorubicin release of PLDs. A quick, biphasic release occurs for PLDs that lack the nanorod crystals or have crystals of poor crystallinity, whereas PLDs prepared with ≥200 mM AS show a monophasic, zero-order slow release. This study also demonstrates that after remote loading, residual intraliposomal ammonium concentration and the transmembrane pH gradient related to it also play an important role in doxorubicin-sulfate intraliposomal crystallization and ammonia-induced doxorubicin release., Competing Interests: The authors declare the following competing financial interest(s): Yechezkel Barenholz is one of the inventors of two already expired (March 2010) patents relevant to Doxil: (1) Barenholz, Y., and Haran, G. “Method of Amphipathic Drug Loading in Liposomes by pH Gradient”. U.S. Patent 5,192,549, March 9, 1993. U.S. Patent 5,244,574, September 14, 1993; (2) Barenholz Y., and Haran, G. “Liposomes: Efficient Loading and Controlled Release of Amphipathic Molecules”, U.S. Patent 5,316,771, May 31, 1994. The Hebrew University received royalties from Doxil sales until the patents expired. The Barenholz Fund established with a portion of these royalties are used to support research in the Barenholz laboratory, including this study. Dima Shamrakov and Sioma Nudeman are employees of Ayana Ltd., a start-up founded by Yechezkel Barenholz and Yissum Hebrew University TTO. Ayana Ltd. works on the development of liposomal drugs including liposomal doxorubicin.

Thermal conductivity (TC) enhancement of an insulating polymer matrix at low filler concentration is possible through the loading of a high aspect ratio, thermally conductive single filler. Unfortunately, the dispersion of high-aspect-ratio particles greatly influences the rheological behavior of the polymer host at relatively low volume fractions, which makes further polymer processing or mixing difficult. A possible remedy is using two (hybrid) fillers, differing in their aspect ratios: (1) a plate-like filler, which sharply increases both viscosity and TC, and (2) an isotropic filler, which gradually increases these properties. We examine this hypothesis in a thermosetting silicone rubber by loading it with different ratios, (1)/(2), of graphene nanoplatelets (GNPs) (1) and graphite powder (2). We constructed a "phase diagram" delineating two composite processability regions: solid-like (moldable) or fluid-like (pourable). This diagram may be employed to tailor the mixture's viscosity to a desired TC value by varying the fillers' volume fraction. The phase diagram highlights the low volume fraction value, above which the composite is solid-like (low processability) for a single high-aspect-ratio nanofiller. By using hybrid filling, one can overcome this limit and prepare a fluid-like composite at a desired TC, not accessible by the single nanofiller. Thus, it provides an indicative tool for polymer processing, especially in applications such as the encapsulation of electronic devices. This approach was demonstrated for a heat source (resistor) potted by silicon rubber graphene-graphite composites, for which a desired TC was obtained in both solid- and liquid-like regions.

Thermal management has become a critical aspect in next-generation miniaturized electronic devices. Efficient heat dissipation reduces their operating temperatures and insures optimal performance, service life, and efficacy. Shielding against shocks, vibrations, and moisture is also imperative when the electronic circuits are located outdoors. Potting (or encapsulating) them in polymer-based composites with enhanced thermal conductivity (TC) may provide a solution for both thermal management and shielding challenges. In the current study, graphene is employed as a filler to fabricate composites with isotropic ultrahigh TC (>12 W m(-1) K(-1)) and good mechanical properties (>30 MPa flexural and compressive strength). To avoid short-circuiting the electronic assemblies, a dispersion of secondary ceramic-based filler reduces the electrical conductivity and synergistically enhances the TC of composites. When utilized as potting materials, these novel hybrid composites effectively dissipate the heat from electronic devices; their operating temperatures decrease from 110 to 37 °C, and their effective thermal resistances are drastically reduced, by up to 90%. The simple filler dispersion method and the precise manipulation of the composite transport properties via hybrid filling offer a universal approach to the large-scale production of novel materials for thermal management and other applications.

A fundamental understanding of the mechanisms involved in the surfactant-assisted exfoliation and dispersion of carbon nanotubes (CNTs) in water calls for well-controlled experimental methodologies and reliable comparative metrics. We have assessed the ability of several ionic surfactants to disperse single and multiwalled carbon nanotubes, resorting to a stringently controlled sonication-centrifugation method for the preparation of the dispersions. The CNT concentration was accurately measured for a wide range of surfactant concentration, using combined thermogravimetric analysis and UV-vis spectroscopy. The obtained dispersibility curves yield several quantitative parameters, which in turn allow for the effects of nanotube morphology and surfactant properties (aromatic rings, chain length, headgroup charge, and cmc) to be assessed and rationalized, both in terms of dispersed nanotube mass and surface area. The data also indicate that the CNT-surfactant association follows patterns that are markedly different from other equilibrium processes governed by hydrophobicity (such as micellization); in particular, the surfactant concentration needed for maximum dispersibility, c(s,max), and the number of surfactant molecules per unit CNT area at c(s,max) are shown to depend linearly on chain length. The results further suggest that the presence of micelles in the exfoliation process is not a key factor either for starting CNT dispersibility or attaining its saturation value.

In an effort to reduce the flammability of polyurethane foam, a thin film of renewable inorganic nanoparticles (i.e., anionic vermiculite [VMT] and cationic boehmite [BMT]) was deposited on polyurethane foam via layer-by-layer (LbL) assembly. One, two, and three bilayers (BL) of BMT-VMT resulted in foam with retained shape after being exposed to a butane flame for 10 s, while uncoated foam was completely consumed. Cone calorimetry confirmed that the coated foam exhibited a 55% reduction in peak heat release rate with only a single bilayer deposited. Moreover, this protective nanocoating reduced total smoke release by 50% relative to untreated foam. This study revealed that 1 BL, adding just 4.5 wt % to PU foam, is an effective and conformal flame retardant coating. These results demonstrate one of the most efficient and renewable nanocoatings prepared using LbL assembly, taking this technology another step closer to commercial viability.

Relatively fast exposure times (5 s) to aqueous solutions were found to improve the gas barrier of clay-polymer thin films prepared using layer-by-layer (LbL) assembly. Contrary to the common belief about deposition time (i.e., the longer the better), oxygen transmission rates (OTRs) of these nano-brick-wall assemblies are improved by reducing exposure time (from 1 min to 5 s). Regardless of composition, LbL films fabricated using shorter deposition time are always thicker in the first few layers, which correspond to greater clay spacing and lower OTR. A quadlayer (QL) assembly consisting of three repeat units of branched polyethylenimine (PEI), poly(acrylic acid) (PAA), PEI and montmorillonite (MMT) clay is only 24 nm thick when deposited with 1 min exposure to each ingredient. Reducing the exposure time of polyelectrolytes to 5 s not only increases this film thickness to 55 nm but also reduces the oxygen transmission rate (OTR) to 0.05 cm3/(m2 day atm), which is 2 orders of magnitude lower than the same film made using 1 min exposures. A conceptual model is proposed to explain the differences in growth and barrier, which are linked to polyelectrolyte relaxation, desorption, and interdiffusion. The universality of these findings is further exemplified by depositing clays with varying aspect ratios. This ability to quickly deposit high-barrier nanocomposite thin films opens up a tremendous opportunity in terms of commercial-scale processing of LbL assemblies.

An emerging new direction of research focuses on developing "self-synthesizing materials", those supramolecular structures that can promote their own formation by accelerating the synthesis of building blocks and/or an entire assembly. It was postulated recently that practical design of such systems can benefit from the ability to control the assembly of amphiphilic molecules into nanostructures. We describe here the self-assembly pathway of short amphiphilic peptides into various forms of soluble β-sheet structures--β-plates, fibrils, and hollow nanotubes--and their consequent activity as autocatalysts for the synthesis of monomeric peptides from simpler building blocks. A detailed kinetic analysis of both the self-assembly and self-replication processes allows us to suggest a full model and simulate the replication process, revealing that only specific structures, primarily fibrils that are stable within the solution for a time shorter than a few hours, can be active as catalysts. Interestingly, we have found that such a process also induces fibril reproduction, in a mechanism very similar to the propagation of prion proteins by transmission of misfolded states.

The binding of block copolymer Pluronic F-127 in aqueous dispersions of single- (SWCNT) and multiwalled (MWCNT) carbon nanotubes has been studied by pulsed-field-gradient (PFG) (1)H NMR spectroscopy. We show that a major fraction of polymers exist as a free species while a minor fraction is bound to the carbon nanotubes (CNT). The polymers exchange between these two states with residence times on the nanotube surface of 24 ± 5 ms for SWCNT and of 54 ± 11 ms for MWCNT. The CNT concentration in the solution was determined by improved thermal gravimetric analysis (TGA) indicating that the concentration of SWCNT dispersed by F-127 was significantly higher than that for MWCNT. For SWCNT, the area per adsorbed Pluronic F-127 molecule is estimated to be about 40 nm(2).

Bundles of nanotubes have been exfoliated in solution by handful of dispersants, such as surfactants, polymers, or proteins, for efficient use in various applications. Common procedures in carbon nanotube exfoliation and dispersion are sonication followed by centrifugation. The dispersion dynamics of single-walled carbon nanotubes (SWNT) by protein were studied by UV-vis spectroscopy (enhanced with chemometric analysis) and low-temperature transmission electron microscopy (cryo-TEM). We studied the effect of both pH and BSA-to-SWNT ratio on SWNT exfoliation dynamics and recovery. We found that, indeed, BSA properties (i.e., electric charge and conformation) affect the exfoliation dynamics in a similar manner as it affects the SWNT recoveries: bulkier protein conformation-->faster exfoliation-->higher SWNT recoveries. Higher BSA-to-SWNT ratio results in lower recoveries and slower dynamics, suggesting that entropic consideration may take part in the exfoliation-stabilization process of SWNT.

We present a detailed study on the integration of individual single-walled carbon nanotubes (SWNTs) within a lyotropic hexagonal liquid crystal (LC) for the first time. Two systems are studied in this work; in the first, the same surfactant is used for both the dispersion of the SWNTs and the formation of the LC. In the second system, we use different surfactants for the dispersion of SWNTs and LC formation. Light microscopy imaging combined with small-angle X-ray scattering (SAXS) indicates that the nanotubes (NTs) are well dispersed and aligned along the LC director. The macroscopic property, namely, the viscosity, is strongly enhanced by the presence of the NTs.