Rekha Goswami Shrestha

Nanoporous Carbon Tubes from Fullerene Crystals as the π‐Electron Carbon Source

Here we report the thermal conversion of one-dimensional (1D) fullerene (C60) single-crystal nanorods and nanotubes to nanoporous carbon materials with retention of the initial 1D morphology. The 1D C60 crystals are heated directly at very high temperature (up to 2000 °C) in vacuum, yielding a new family of nanoporous carbons having π-electron conjugation within the sp(2)-carbon robust frameworks. These new nanoporous carbon materials show excellent electrochemical capacitance and superior sensing properties for aromatic compounds compared to commercial activated carbons.

Wormlike micelles in mixed amino acid-based anionic/nonionic surfactant systems.

We present the formation of viscoelastic wormlike micelles in mixed amino acid-based anionic and nonionic surfactants in aqueous systems in the absence of salt. N-Dodecylglutamic acid (designated as LAD) has a higher Krafft temperature; however, on neutralization with alkaline amino acid l-lysine, it forms micelles and the solution behaves like a Newtonian fluid at 25 degrees C. Addition of tri(oxyethylene) monododecyl ether (C(12)EO(3)) and tri(oxyethylene) monotetradecyl ether (C(14)EO(3)) to the dilute aqueous solution of the LAD-lysine induces one-dimensional micellar growth. With increasing C(12)EO(3) or C(14)EO(3) concentration, the solution viscosity increases gradually, but after a certain concentration, the elongated micelles entangle forming a rigid network of wormlike micelles and the solution viscosity increases tremendously. Thus formed wormlike micelles show a viscoelastic character and follow the Maxwell model. Tri(oxyethylene) monohexadecyl ether (C(16)EO(3)), on the other hand, could not form wormlike micelles, although the solution viscosity increases too. The micelles become elongated; however, they do not appear to form a rigid network of wormlike micelles in the case of C(16)EO(3). Rheological measurements have shown that zero shear viscosity (eta(0)) increases with the C(12)EO(3) concentration gradually at first and then sharply, and finally decreases before phase separation. However, no such maximum in the eta(0) plot is observed with the C(14)EO(3). The eta(0) increases monotonously with the C(14)EO(3) concentration till phase separation. In studies of the effect of temperature on the wormlike micellar behavior it has been found that the eta(0) decays exponentially with temperature, following an Arrehenius behavior and at sufficiently higher temperatures the solutions follow a Newtonian behavior. The flow activation energy calculated from the slope of log eta(0) versus 1/T plot is very close to the value reported for typical wormlike micelles. Finally, we also present the effect of neutralization degree of lysine on the rheology and phase behavior. The formation of wormlike micelles is confirmed by the Maxwell model fit to the experimental rheological data and by Cole-Cole plots.

Viscoelastic wormlike micelles in mixed nonionic fluorocarbon surfactants and structural transition induced by oils.

Formation and rheological behavior of viscoelastic wormlike micelles in an aqueous solution of a mixed system of nonionic fluorocarbon surfactants, perfluoroalkyl sulfonamide ethoxylate, C8F17SO2N(C3H7)(CH2CH2O)nH (abbreviated as C8F17EOn, n=20 and 3), was studied. A partial ternary phase diagram of water/C8F17EO20/C8F17EO3 was constructed at 25 degrees C by visual inspection through crossed polarizers. In the water/surfactant binary system, C8F17EO20 forms an isotropic micellar solution over a wide concentration range (approximately 80 wt %). The micellar solution of the C8F17EO20 can solubilize a significant amount of C8F17EO3, and the solubility increases with increasing C8F17EO20 concentration. With successive addition of C8F17EO3 to the aqueous C8F17EO20 solution, viscosity increases rapidly, and a viscoelastic solution is formed. The viscosity of the viscous sample was approximately 5th order of magnitude of pure water. The viscoelastic solution follows the Maxwell model typical of wormlike micelles at low-frequency region. With further addition of C8F17EO3 the viscosity decreases, and phase separation occurs. Addition of perfluoropolyether oil, (C3F6O)nCOOH, to the viscoelastic solution decreases the viscosity monotonically until phase separation. On the other hand, when perfluorodecalin oil, C10F18, is added, viscosity first decreases and attains a limiting value before excess oil phase separates out. The viscosity decrease in water/surfactant/oil systems is possibly caused by the microstructural transition in the network structure. Small-angle X-ray scattering (SAXS) measurements were performed to complement the rheological data. It has been found that the C8F17EO3 induces one-dimensional growth to the C8F17EO20 micelles. On the other hand, when (C3F6O)nCOOH is added, wormlike-sphere type transition is more likely to occur.

Demonstration of Ultrarapid Interfacial Formation of 1D Fullerene Nanorods with Photovoltaic Properties

We demonstrate ultrarapid interfacial formation of one-dimensional (1D) single-crystalline fullerene C60 nanorods at room temperature in 5 s. The nanorods of ∼ 11 μm in length and ∼ 215 nm in diameter are developed in a hexagonal close-pack crystal structure, contrary to the cubic crystal structure of pristine C60. Vibrational and electronic spectroscopy provide strong evidence that the nanorods are a van der Waals solid, as evidenced from the preservation of the electronic structure of the C60 molecules within the rods. Steady state optical spectroscopy reveals a dominance of charge transfer excitonic transitions in the nanorods. A significant enhancement of photogenerated charge carriers is observed in the nanorods in comparison to pristine C60, revealing the effect of shape on the photovoltaic properties. Due to their ultrarapid, large-scale, room-temperature synthesis with single-crystalline structure and excellent optoelectronic properties, the nanorods are expected to be promising for photosensitive devices applications.

Wormlike Micelle Formation by Acylglutamic Acid with Alkylamines

Rheological properties of alkyl dicarboxylic acid-alkylamine complex systems have been characterized. The complex materials employed in this study consist of an amino acid-based surfactant (dodecanoylglutamic acid, C12Glu) and a tertiary alkylamine (dodecyldimethylamine, C12DMA) or a secondary alkylamine (dodecylmethylamine, C12MA). (1)H NMR and mass spectroscopic data have suggested that C12Glu forms a stoichiometric 1:1 complex with C12DMA and C12MA. Rheological measurements have suggested that the complex systems yield viscoelastic wormlike micellar solutions and the rheological behavior is strongly dependent on the aqueous solution pH. This pH-dependent behavior results from the structural transformation of the wormlike micelles to occur in the narrow pH range 5.5-6.2 (in the case of C12Glu-C12DMA system); i.e., positive curved aggregates such as spherical or rodlike micelles tend to be formed at high pH values. Our current study offers a unique way to obtain viscoelastic wormlike micellar solutions by means of alkyl dicarboxylic acid-alkylamine complex as gemini-like amphiphiles.

Tunable parameters for the structural control of reverse micelles in glycerol monoisostearate/oil systems: a SAXS study.

Formation of reverse micelles in surfactant/oil binary systems without water addition and the tunable parameters for the structure control of such micelles are presented. The small-angle X-ray scattering (SAXS) technique has been used for the structural characterization of micelles. It has been found that the nonionic surfactant glycerol monoisostearate (abbreviated as iso-C18G1) forms reverse micelles in different organic solvents such as cyclohexane, n-decane, and n-hexadecane without the addition of water. The structure (shape and size) of the reverse micelles has been found to depend on the solvent nature (alkyl chain length of oil), composition, temperature, and added water. Phase behavior study has shown that iso-C18G1 forms isotropic single-phase solutions in the aforementioned oils at 25 degrees C. At lower temperatures (<20 degrees C) II phases (dispersion of solid or liquid crystal phase) has been observed. SAXS data were evaluated by the generalized indirect Fourier transformation (GIFT) method, which has drawn a clear picture on the structural variations of the reverse micellar aggregates. Small globular types of micelles are found in the iso-C18G1/cyclohexane system. On the other hand, elongated ellipsoidal prolatelike or rodlike micelles are found in iso-C18G1/decane or iso-C18G1/hexadecane systems. The underlying mechanism of this structural evolution may be explained in terms of the transfer free energy of hydrophilic glycerol moiety from hydrophilic to hydrophobic environment of oils with different chain lengths. Besides, the penetration of oils to the lipophilic chain of the surfactant in reverse micellar systems differs depending on the chain length of oils. Lowering temperature and increasing surfactant concentration similarly lead to micellar growth while the cross-section structure remains essentially unchanged. Addition of trace water induced micellar growth, which is accompanied by the rapid swelling of the micellar core. The results obtained by this study demonstrate that the solvent nature, temperature, composition, and water addition can be the tunable parameters for the size, shape, and internal structure control of the iso-C18G1-based reverse micelles.

Peptide-based gemini amphiphiles: phase behavior and rheology of wormlike micelles.

Aqueous binary phase behavior of a peptide-based gemini amphiphile with glutamic acid and lysine as spacer group, acylglutamyllysilacylglutamate (m-GLG-m where m = 12, 14, and 16), has been reported over a wide range of concentration and temperature. Lauroylglutamyllysillauroylglutamate, 12-GLG-12, self-assembles into spherical micelles above critical micelle concentration (CMC). The micellar region extends up to 32 wt %, and an ordering of spherical micelles into micellar cubic phase, I(1), takes place at 33 wt % at 25 °C. The phase transition, I(1) - hexagonal liquid crystal, (H(1)) - lamellar liquid crystal, (L(α)) has been observed with further increase in concentration; moreover, mixed phases are also observed between the pure liquid crystal domains. Similar phases were observed with 16-GLG-16 above 50 °C (Krafft temperature). The partial ternary phase behavior shows that the micellar solutions of m-GLG-m can solubilize a large amount of cationic amphiphile, alkyltrimethylammonium bromide, C(n)TAB, (where n = 14 (TTAB) and 16 (CTAB)) at 25 °C. An addition of C(n)TAB to the aqueous solutions of 16-GLG-16 in a dilute region forms a transparent solution of viscoelastic wormlike micelles at very low concentration (0.25 wt %) even at ambient condition. A mixture of oppositely charged amphiphiles, m-GLG-m and C(n)TAB, exhibits synergism as a result the amphiphile layer curvature, becomes less positive, and favors the transition from sphere to rod to transient networks (wormlike micelles). The gemini amphiphile, 16-GLG-16, forms wormlike micelles at relatively low concentrations compared to others reported so far. Viscosity increases by six orders of magnitude compared to that of pure solvent. The hydrophobic chain length of m-GLG-m and coamphiphile affects the rheology; the maximum viscosity achieved with 16-GLG-16/H(2)O/CTAB is higher than that of 14-GLG-14/H(2)O/CTAB, 12-GLG-12/H(2)O/CTAB, and 16-GLG-16/H(2)O/TTAB systems. These temperature-sensitive systems exhibited viscoelastic behavior described by the Maxwell mechanical model with a single stress relaxation mode.

Rheological Properties of Polyoxyethylene Cholesteryl Ether Wormlike Micelles in Aqueous System

Polyoxyethylene cholesteryl ether (ChEO(20)) nonionic surfactant self-assembles into spherical micelles above the critical micelle concentration in water. An ordering of micelles takes place with an increase in surfactant concentration and forms a micellar cubic phase with the space group Pm3n at ∼30%. Cocamid methyl MEA (designated as C-11S) cosurfactant is soluble at the palisade layer of the ChEO(20) micelle as a result; the curvature of the aggregates tends to decrease and favors sphere-to-rod transition. The axial length of the rod increases with C-11S concentration, and after a certain concentration, elongated micelles entangle with each other, forming a transient network of wormlike micelles. Viscosity increases by 5 orders of magnitude. The zero-shear viscosity (η(0)) versus C-11S concentration curve shows a peak, and the position of the peak shifts toward the right (at higher concentration of C-11S) when the concentration of ChEO(20) in water is increased from 10 to 15%. On the other hand, the peak position shifts toward the left with a decrease in the ethylene oxide (EO) chain of the surfactant, i.e., in the ChEO(15) system. Viscosity increases only slightly with a longer EO chain ChEO(30) system, and it does not show any viscoelastic properties. These wormlike micelles exhibited viscoelastic behavior and could be described by the Maxwell mechanical model with a single stress relaxation mode that is sensitive to temperature. Viscosity and relaxation time were first increased and then decreased, but the plateau modulus increased continuously upon heating. These observations revealed that micelles first grew with temperature and then branched. Dynamic rheology and small-angle X-ray scattering (SAXS) further support the rheology data.

Intrinsic Parameters for the Structure Control of Nonionic Reverse Micelles in Styrene: SAXS and Rheometry Studies

Shape, size, and internal structure of nonionic reverse micelle in styrene depending on surfactant chain length, concentration, temperature, and water addition have been investigated using a small-angle X-ray scattering (SAXS) technique. The generalized indirect Fourier transformation (GIFT) method has been employed to deduce real-space structural information. The consistency of the GIFT method has been tested by the geometrical model fittings, and the micellar aggregation number (N(agg)) has been determined. It was found that diglycerol monocaprate (C(10)G(2)), diglycerol monolaurate (C(12)G(2)), and diglycerol monomyristate (C(14)G(2)), spontaneously self-assemble into reverse micelles in organic solvent styrene under ambient conditions. The micellar size and the N(agg) decrease with an increase in surfactant chain length, a scenario that could be understood from the modification of the critical packing parameter (cpp). A clear picture of one-dimensional (1-D) micellar growth was observed with an increase in surfactant weight fraction (W(s)) in the C(10)G(2) system, which eventually formed rodlike micelles at W(s) ≥ 15%. On the other hand, micelles shrunk favoring a rod-to-sphere type transition upon heating. Reverse micelles swelled with water, forming a water pool at the micellar core; the size of water-incorporated reverse micelles was much bigger than that of the empty micelles. Model fittings showed that water addition not only increase the micellar size but also increase the N(agg). Zero-shear viscosity was found to decrease with surfactant chain but increase with W(s), supporting the results derived from SAXS.

Stabilization of nonaqueous foam with lamellar liquid crystal particles in diglycerol monolaurate/olive oil system

Nonaqueous foams stabilized by lamellar liquid crystal (L alpha) dispersion in diglycerol monolaurate (designated as C12G2)/olive oil systems are presented. Foamability and foam stability depending on composition and the effects of added water on the nonaqueous foaming behavior were systematically studied. It was found that the foamability increases with increasing C12G2 concentration from 1 to 3 wt% and then decreases with further increasing concentration, but the foam stability increases continuously with concentration. Depending on compositions, foams are stable for a few minutes to several hours. Foams produced by 10 wt% C12G2/olive oil system are stable for more than 6 h. In the study of effects of added water on the foaming properties of 5 wt% C12G2/olive oil system, it was found that the foamability and foam stability of 5 wt% C12G2/olive oil decreases upon addition of 1 wt% water, but with further increasing water, both the foamability and foam stability increase. Foams with 10% water added system are stable for approximately 4 h. Phase behavior study of the C12G2 in olive oil has shown the dispersion of L alpha particles in the dilute regions at 25 degrees C. Thus, stable foams in the C12G2/olive oil system can be attributed to L alpha particle, which adsorb at the gas-liquid interface as confirmed by surface tension measurements and optical microscopy. Laser diffraction particle size analyzer has shown that the average particle diameter decreases with increasing the C12G2 concentration and, hence, the foams are more stable at higher surfactant concentration. Judging from foaming test, optical micrographs, and particle size, it can be concluded that stable nonaqueous foams in the studied systems are mainly caused by the dispersion of L alpha particles and depending on the particle size the foam stability largely differs.