Amphiphilic interaction-mediated ordering of nanoparticles in Pickering emulsion droplets.

For various industrial processes, the stabilization of an oil phase is crucial and demands a proper balance of complex interactions in an emulsion system. In Pickering emulsions, this is achieved by introducing nanoparticles, which become organized at the oil-water interface. The influence of interparticle interactions towards the formation of a stable emulsion and the ordering of the stabilizing nanoparticles is intriguing and needs attention. In this work, the role of amphiphilic interactions between hydrophilic silica nanoparticles and the Pluronic F127 tri-block co-polymer towards the spontaneous formation of a fairly stable Pickering emulsion has been studied using small-angle X-ray scattering. Unlike the usual random arrangements of the nanoparticles in a conventional Pickering emulsion, we observed highly organized silica nanoparticles at the oil-water interface. The established standard raspberry structural model of the Pickering emulsion fails to explain such strong ordering as observed in the present case. A plausible formation mechanism of the present Pickering emulsion with a high on-surface silica correlation is elucidated on the basis of the combined interactions of the block co-polymer and silica particles. A computer model is developed to elucidate the effects of size and distribution of the surface-decorating nanoparticles and their positional correlation.

Fluorescence spectroscopic investigation to identify the micelle to gel transition of aqueous triblock copolymer solutions.

Steady-state and time-resolved fluorescence anisotropy measurements using probes coumarin 153 (C153) and 4-heptadecylumbelliferon (HUF) have been carried out to understand the micelle to gel transition of an aqueous triblock copolymer P123 ((EO)(20)-(PO)(70)-(EO)(20)) (EO = ethylene oxide; PO = propylene oxide) solution. Anisotropy results with a normal fluorescent probe, C153, do not show a characteristic change due to the micelle to gel transition. However, the probe HUF having a long hydrocarbon chain that helps its strong association with the micelle shows an increase in anisotropy above the sol-gel transition point. This difference has been explained as invoking a substantial contribution from the micellar structural fluctuations to the depolarization of HUF as its hydrocarbon chain is embedded in the micellar structure, which is not sensed significantly by the normal probe C153. That the extent of change in anisotropy for HUF upon gelation is not that large is possibly caused by the collective motion of the physically interconnected nodes, as observed from the dynamic light scattering studies, which acts in favor of a relatively faster depolarization in the gel phase. Similar studies in other copolymers, such as P85 ((EO)(26)-(PO)(40)-(EO)(26)) and F127 ((EO)(100)-(PO)(65)-(EO)(100)), further demonstrate the potential of probes latched with hydrocarbon chains in displaying a characteristic change for the micelle to gel transition which otherwise remains obscured for normal fluorescent probes.

Water dispersible Fe3O4 nanoparticles carrying doxorubicin for cancer therapy.

Water dispersible Fe3O4 nanoparticles (coated with Poly Vinyl Pyrolidone (PVP) and Poly oxy ethylene 25-propylene glycol stearate (POES)) and complexed with Doxorubicin has been prepared and characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM) and vibrating sample magnetometer (VSM). The antitumor activity of these particles has been studied by targeting the complex to the tumor site, using an externally applied magnetic field, after oral administration of the magnetic nanoparticle-drug complexes. Our results reveal that the chemotherapy effect of Doxorubicin could be considerably enhanced by combination of the application of the drug-conjugated magnetic Fe3O4 nanoparticles, which are biocompatible and stable, and targeted drug delivery with a magnet. The present report provides the first evidence for the promising application of this novel approach with PVP coated Fe3O4 nanoparticles for cancer therapy using an in vivo murine model.

Influence of electrolytes on the microenvironment of F127 triblock copolymer micelles: a solvation and rotational dynamics study of coumarin dyes.

Dynamic Stokes' shift and fluorescence anisotropy measurements of coumarin 153 (C153) and coumarin 151 (C151) as fluorescence probes have been carried out to understand the influence of electrolytes (NaCl and LiCl) on the hydration behavior of aqueous (ethylene oxide)100-(propylene oxide)70-(ethylene oxide)100 (EO100-PO70-EO100, F127) block copolymer micelles. A small blue shift in the fluorescence spectra of C153 has been observed in presence of electrolytes due to the dehydration of the oxyethylene chains in the PEO-PPO region, although fluorescence spectra of C151 remain unaltered. The close vicinity of bulk water for C151 probably negates the effect of dehydration in the PEO region. Fluorescence anisotropy measurements indicate a gradual increase in microviscosity with electrolyte concentrations. The partial collapse of copolymer blocks in the presence of electrolytes has been suggested as a reason for the increase in microviscosity along with the strong hydration of ions in the corona region. The interplay between the ion hydration and the mechanically trapped water content, and specific interaction of ions, such as complexation of Li+ ions with the copolymer block, is found to control solvation dynamics in the corona region. In addition to that, it has been established that Na+ ions reside deep into the corona region whereas Li+ ions prefer to reside closer to the surface. Owing to its higher lyotropicity, LiCl influences the corona hydration to a greater extent than NaCl and sets in micelle-micelle interaction above the 2 M LiCl concentration, as reflected in the saturation of solvation time constants. The formation of larger clusters of F127 micelles above 2 M LiCl has been confirmed by dynamic light scattering measurements; however, such cluster formation is not evident with NaCl.

TODGA based w/o microemulsion in dodecane: an insight into the micellar aggregation characteristics by dynamic light scattering and viscometry.

N,N,N',N'-tetraoctyl diglycolamide abbreviated as TODGA, is one of the most promising extractant for actinide partitioning from high level nuclear waste. It forms reverse micelles in non polar solvents on equilibration with aqueous HNO(3) solutions. This reverse micellar system undergoes phase separation into dilute and concentrated reverse micellar solutions at high aqueous acid concentration. Small angle neutron scattering (SANS) studies reported in the literature explained this phenomenon based on gas-liquid type phase transition in the framework of Baxter adhesive hard sphere theory in the presence of a strong inter-micellar attractive interaction. The present investigation attempts to throw further light on this system by carrying out systematic dynamic light scattering (DLS) and viscometry studies, and their modeling on the TODGA reverse micellar solutions in the dodecane medium. The variation of the diffusion coefficient with the micellar volume fraction observed from the DLS studies is suggestive of the presence of an attractive interaction between the TODGA reverse micelles, which weakens at the high micellar volume fraction due to the increased dominance of the excluded volume effect. It is suggested that this weakened interaction is responsible for the absence of phase separation in this system at high TODGA concentration. The results thus highlight the importance of the presence of an attractive interaction between the TODGA micelles in determining the observed phase separation in the TODGA reverse micellar systems. The modeling of the DLS and viscosity data, however, suggest that the characteristic stickiness parameter of this system could be smaller than the critical value required for inducing a gas-liquid type phase transition.

Time-resolved fluorescence and small angle neutron scattering study in pluronics-surfactant supramolecular assemblies.

Interaction of cationic surfactant, cetyl trimethyl ammonium bromide (CTAB), with pluronics F88 (EO(103)-PO(39)-EO(103)) and P105 (EO(37)-PO(56)-EO(37)) micelles and its effect on modulating the location of an anionic solute in the mixed micelles have been investigated using time-resolved fluorescence and small angle neutron scattering (SANS) studies. SANS results indicate the formation of pluronic-CTAB supramolecular assemblies, in which the hydrophobic chains of CTAB occupy the hydrophobic core of the pluronic micelle while the positively charged head groups reside at the micellar core-corona interface. Rotational correlation time of the anionic probe in these supramolecular assemblies increases with an increase in the CTAB concentration, and the observed results are explained on the basis of the probe movement from the surface to the interior of the micelle due to the increased electrostatic attraction. Dynamic Stokes' shift measurements also support the movement of the probe due to the addition of the surfactant to the supramolecular assemblies. From the studies with different pluronics, it is indicated that the concentration of CTAB required to drag the probe molecule into the interior of the micelles is linearly correlated to the thickness of the corona region of the respective micelles.