Influence of molecular interactions on structure, controlled release and cytotoxicity of curcumin encapsulated chitosan - Silica nanostructured microspheres.

Curcumin possesses numerous medicinal benefits including anti-cancer and anti-viral properties. However, its wide scale use as a drug is often hindered owing to the dearth of suitable drug-delivery systems which can solubilise it for long-term sustained-release and safeguard its beneficial properties. In this work, a fast, one-step method, employing evaporation induced assembly of colloids, has been employed for the synthesis of curcumin encapsulated organic-inorganic hybrid micron-sized spheres. Detailed physical properties of the microspheres, with scaffolds of silica nanoparticles (∼8.5 nm) cross linked by chitosan, are studied to trace the underlying mechanism of structural assembly in such systems, by tuning the polymer matrix with solubilizing agents, DMSO and Tween 20. A systematic modification in the hydrogen bonding network, conformations and interactions between macromolecules is revealed upon tuning the organic matrix. This in turn is found to control the assembly vis-à-vis the granular morphology, drug entrapment and packing fraction of nanoparticles in the microspheres, which have direct influence on the biological properties. Consequently, the microspheres are found to follow a first order drug release kinetics with a tunable rate constant which follows the ordering of packing fraction of silica nanoparticles in the micro-granules. A sustained curcumin release for a period extending up to 24 h has been achieved. Further studies using human lung and cervical cancer cell lines assert good anti-cancer properties of these nanostructured microspheres in cancer cells, while showing no toxicity towards normal cells. Thus, such hybrid organic-inorganic formulations achieved using multi-component colloidal assembly approach, with enhanced stability against degradation, are promising candidates for future clinical applications of water-insoluble drugs.

Role of free volumes and segmental dynamics on ion conductivity of PEO/LiTFSI solid polymer electrolytes filled with SiO2 nanoparticles: a positron annihilation and broadband dielectric spectroscopy study.

The limited ionic conductivity of polymer electrolytes is a major issue for their industrial application. Enhancement of ionic conductivity in the poly(ethylene oxide), PEO, based electrolyte has been achieved by loading passive nanofillers such as SiO2 nanoparticles (NPs). To investigate the role of modifications in free volume characteristics and the polymer chain dynamics induced by the loading of passive fillers on the ionic conductivity of the PEO based ternary electrolyte, a systematic investigation has been carried out using positron annihilation and broadband dielectric spectroscopy. As a result of interfacial interactions, the loading of SiO2 NPs alters the semi-crystalline morphology of PEO resulting in a higher crystallinity at lower loadings due to the surface confinement of PEO chains, and the formation of smaller PEO crystallites at higher loadings due to interparticle nanoconfinement. These modifications are accompanied by a decrease in free volume fraction at the lowest loading (0.5 wt%) followed by an increase at higher loadings (≥2.0 wt%). The Almond-West formalism considering two different universalities in different temperature and frequency ranges has been used to explain the ion-conduction process at different NP loadings. The Li ion conductivity is observed to be maximum for a 5.0 wt% loading of SiO2 NPs. The enhancement in ionic conductivity is observed to be directly correlated with the free volume characteristics and segmental dynamics of the PEO matrix, confirming their role in ion transport in polymer electrolytes.

Colloidal Nanoparticle Interaction Transition during Solvent Evaporation Investigated by in-Situ Small-Angle X-ray Scattering.

In-situ scanning small-angle X-ray scattering (SAXS) experiments have been performed to probe the drying of a single suspended droplet of silica colloids. It has been demonstrated that the formation of a nanoparticle shell during drying can be confirmed just by measuring the temporal evolution of the spatial transmission profile across the drying droplet. The shrinkage of the droplet stops once the shell is formed. The temporal dependence of the shell thickness and droplet radius has been estimated by quantitative analysis of the functionality of the transmission profiles. It is revealed that the position of the correlation peak originating from interactions between silica nanoparticles evolves linearly during the initial stage of drying and exhibits sigmoidal growth behavior in later stages. The interaction between colloidal particles in different drying stages has been investigated. We provide experimental confirmation of the transition from repulsive interaction to a capillary-driven short-range attraction during shell formation. The present work demonstrates that in-situ scanning SAXS on a suspended droplet is an invaluable technique for monitoring the dynamic self-organization of colloids as it probes the drying of complex fluids without the interference of a substrate.

E. coli imprinted nano-structured silica micro-granules by spray drying: optimization of calcination temperature.

We have synthesized nano-structured silica-Escherichia coli composite micro-granules by spray drying of mixed suspension of silica and E. coli through evaporation-induced assembly. Synthesized micro-granules were subjected to calcination in order to form shape-matched macro-pores by removing the bacterial cells. The optimization of calcination temperature is crucial because calcination process leads to two contrasting effects, namely, (i) removal of E. coli from the granules and (ii) alteration of mesoscopic structure in the silica network. We have used small-angle neutron scattering and thermo-gravimetric analysis to determine the optimum temperature for calcination of these granules. It was found that calcination in the temperature range of 200°C to 400°C removes the cells without significant alteration of the nano-structured silica network. However, beyond 500°C, calcination results significant coalescence between the silica particles. Calcination at 600°C eventually collapses the meso-pore network of silica interstices.

Cavitation on deterministically nanostructured surfaces in contact with an aqueous phase: a small-angle neutron scattering study.

The structure of deterministically nanopatterned surfaces created using a combination of electron beam lithography and reactive ion etching was evaluated using small-angle neutron scattering (SANS). Samples exhibit 2D neutron scattering patterns that confirm the presence of ordered nanoscale cavities consistent with the targeted morphologies as well as with SEM data analysis. Comparison of SANS intensities obtained from samples in air and in contact with an aqueous phase (pure deuterium oxide, D2O, or a contrast matched mixture of D2O + H2O) reveals formation of stable gaseous nanobubbles trapped inside the cavities. The relative volume of nanobubbles depends strongly on the hydrophobicity of the cavity walls. In the case of hydrophobic surfaces, nanobubbles occupy up to 87% of the total cavity volume. The results demonstrate the high degree of sensitivity of SANS measurements for detecting and characterizing nano- and mesoscale bubbles with the volume fraction as low as ∼10(-6).

Probing evaporation induced assembly across a drying colloidal droplet using in situ small-angle X-ray scattering at the synchrotron source.

Colloidal particles in a tiny drying droplet are forced to assemble due to attractive capillary forces. Jamming of the particles throughout the droplet remains either isotropic or anisotropic depending upon the drying kinetics and the physicochemical environment. In this work, we explore the dynamical evolution of such an assembly process across a single evaporative droplet by in situ scanning small-angle scattering using a micro-focused X-ray beam at the synchrotron source. A methodology has been elucidated to differentiate quantitatively between the isotropic and the anisotropic jamming process. Switching of jamming behaviour depending on the initial particle volume fraction in the droplet has been demonstrated. Three distinct stages of assembly, associated with droplet shrinkage, have been revealed even during isotropic jamming. This is in contrast to the drying of a pure liquid droplet under diffusion limited evaporation. It has been established that such in situ scattering measurements can also be used to estimate the temporal evolutions of the viscosity of a drying suspension as well as the diffusivity of nanoparticles in a droplet.

Investigation of nanolevel molecular packing and its role in thermo-mechanical properties of PVA-fMWCNT composites: positron annihilation and small angle X-ray scattering studies.

Carbon based nanofillers have shown phenomenal improvements in thermo-mechanical properties of poly vinyl alcohol (PVA) based nanocomposites depending on their interaction with PVA molecules and dispersion in the polymer matrix. In the present study, PVA based nanocomposites with amino-functionalized multi-wall carbon nanotubes (fMWCNTs, 0.2, 0.4, 0.8 and 1.0 wt%) were prepared by a simple casting method from aqueous solution. The relative increase in Young's modulus with 0.4% fMWCNTs was observed to be comparable with that for PVA-nanodiamond composite films which have been shown to have higher strength compared to nanotube and graphene oxide based nanocomposites. In order to investigate the nanolevel molecular packing (sub-nano level free volumes and nano level lamellar structure) and its role in thermal and mechanical properties, positron annihilation spectroscopy and small angle scattering have been used. The crystallinity and morphology of the samples were characterized using X-ray diffraction and scanning electron microscopy. The studies showed that interfacial interaction between PVA molecules and functionalities on the surface of fMWCNTs results in the formation of an ordered structure of PVA molecules which enhances load transfer between the PVA matrix and fMWCNTs leading to improved mechanical properties. The thermal properties of the composites were observed to be unaffected at the studied filler concentration.

One-step fabrication of thermally stable TiO2/SiO2 nanocomposite microspheres by evaporation-induced self-assembly.

The evaporation-induced self-assembly of mixed colloids has been employed to synthesize microspheres of TiO(2)/SiO(2) nanocomposites. Small-angle neutron/X-ray scattering and scanning electron microscopy experiments reveal the hierarchical morphology of the microspheres. Although the internal structure of the microspheres, consisting of solely silica nanoparticles, gets significantly modified with time because of the reduction in the high specific surface area by internal coalescence, the same for the composite microspheres remains stable over an aging time of 1 year. Such temporal stability of the composite microspheres is attributed to the inhibition of coalescence of the silica nanoparticles in the presence of titania nanoparticles. X-ray diffraction and thermogravimetric results show the improved thermal stability of the composite grains against the anatase-to-rutile phase transition. Such thermal stability is attributed to the suppression of the growth of titania nanoparticles in the presence of silica nanoparticles. The UV-vis results indicate the confinement effect of the TiO(2) nanoparticles in the silica matrix. A plausible mechanism has been elucidated for the formation of microspheres with different morphology during self-assembly.

Control of buckling in colloidal droplets during evaporation-induced assembly of nanoparticles.

Micrometric grains of anisotropic morphology have been achieved by evaporation-induced self-assembly of silica nanoparticles. The roles of polymer concentration and its molecular weight in controlling the buckling behavior of drying droplets during assembly have been investigated. Buckled doughnut grains have been observed in the case of only silica colloid. Such buckling of the drying droplet could be arrested by attaching poly(ethylene glycol) on the silica surface. The nature of buckling in the case of only silica as well as modified silica colloids has been explained in terms of theory of homogeneous elastic shell under capillary pressure. However, it has been observed that colloids, modified by polymer with relatively large molecular weight, gives rise to buckyball-type grains at higher concentration and could not be explained by the above theory. It has been demonstrated that the shell formed during drying of colloidal droplet in the presence of polymer becomes inhomogeneous due to the presence of soft polymer rich zones on the shell that act as buckling centers, resulting in buckyball-type grains.

Origin of buckling phenomenon during drying of micrometer-sized colloidal droplets.

The origin of the buckling of micrometer-sized colloidal droplets during evaporation-induced self-assembly (EISA) has been elucidated using electron microscopy and small-angle neutron scattering. Doughnut-like assembled grains with varying aspect ratios are formed during EISA at different physicochemical conditions. It has been revealed that this phenomenon is better explained by an existing hypothesis based on the formation of a viscoelastic shell of nanoparticles during drying than by other existing hypotheses based on the inertial instability of the initial droplets and hydrodynamic instability due to thermocapillary forces. This conclusion was further supported by the arrest of buckling through modification of the colloidal interaction in the initial dispersion.

Evaporation-induced self assembly of nanoparticles in non-buckling regime: volume fraction dependent packing.

Hierarchically structured micrometric spheres are synthesized by evaporation-induced self assembly of silica colloids using spray drying technique. Packing of nanoparticles during drying of droplets is an important issue. The motivation of the present work is to investigate the effects of concentration of initial colloidal dispersion on the packing of the nanoparticles in assembled grains in non-buckling regime of drying. It has been observed that the packing of nanoparticles inside the dried grains, even in the non-buckling regime, varies significantly with concentration. Although, the packing of nanoparticles remains uniform in an assembled grain at smaller concentration, the same becomes non-uniform at higher concentration. Further, the average packing fraction of the nanoparticles within the assembled grains, decreases with increasing colloidal concentration. These observations have been attributed to the modification in viscosity of the initial dispersion. Electron microscopy, light scattering measurements have been performed to probe overall morphology of the dried grains, while inter-particle correlation inside the grains has been investigated by small angle neutron scattering.

Buckling-driven morphological transformation of droplets of a mixed colloidal suspension during evaporation-induced self-assembly by spray drying.

Morphological transformation during evaporation-induced self-assembly of a mixed colloidal suspension in micrometric droplets has been investigated. It has been demonstrated that a buckling-driven shape transition of drying droplets of mixed colloidal suspension takes place during evaporation-induced self-assembly. Further, it is also shown that the distortion modulations get significantly amplified with enhancement in volume fraction of anisotropic soft colloidal component of the mixed colloids. It has been argued that the reduction in elastic modulus of formed shell, at the boundary of a drying droplet, and the anisotropic nature of one of the colloidal components facilitate the deformation process. Hierarchical structures of these assembled colloidal grains have been probed using electron microscopy and scattering techniques.

Use of small-angle neutron scattering to investigate modifications of internal structure in self-assembled grains of nanoparticles synthesized by spray drying.

Micrometric spherical grains consisting of self-assembled silica nanoparticles have been synthesized by spray drying of colloidal suspension. Inter-particle correlation and available specific surface area of silica and void interfaces, in the assembled grains, were modified by addition of electrolyte in initial colloidal dispersion prior to self-assembly process but keeping the overall spherical shape of the assembled grains un-altered. While the external morphology of the assembled grains was probed by scanning electron microscopy, small-angle neutron scattering technique has been employed to investigate the modifications in the internal structure and the inter-particle correlation inside the assembled grains. It is revealed that a sticky hard sphere type of inter-particle correlation between the constituent particles gets altered to a fractal type of correlation with addition of electrolyte. Further, the specific surface area of the silica-void interface gets somewhat enhanced by addition of electrolyte and particularly at higher electrolyte concentration due to formation of some hollow and buckled assembled grains.

Decoration of carbon nanotubes with metal nanoparticles by wet chemical method: a small-angle neutron scattering study.

Multi-wall carbon nanotubes have been synthesized by catalytic chemical vapour deposition method. Attempts have been made to decorate the walls of these nanotubes with various metal nanoparticles (Ni, Cu and Fe) after functionalizing the nanotubes walls by wet chemical method. Small-Angle Neutron Scattering data reveals chain cluster type morphology of the carbon nanotubes. Transmission electron microscopy, Energy dispersive analysis of X-rays and Small-Angle Neutron Scattering measurements show that decoration of nanotube walls by metallic nano-particles could be realized for Ni and Cu nano-particles. Further, wall decoration by nano-particles of Fe could not be achieved by wet chemical method due to strong agglomeration behavior of Fe nano-particles.

Evolution of a fractal system with conserved order parameter under thermal annealing.

Mesoscopic structural evolution under thermal annealing of yttrium aluminium garnet fractal aggregates has been investigated by small-angle neutron scattering. Fractal dimension remains invariant with sintering temperature but the extent of the fractal realm is narrowed down significantly. A Monte Carlo simulation, based on Ostwald-ripening type of relaxation of fractal aggregates for a mass conserved system, has been attempted in order to understand the aforementioned novel observation. A local group merge sintering model was adopted for the relaxation of the fractal aggregates. Diffusion driven mass transport over local branches of fractal clusters causes smoothening of branches but keeps the overall shape unaltered at lower resolution. Predictions of the model were found to be consistent, in terms of microstructural evolution, with experimental data. The present simulation was also successful in explaining the evolution of the particle size distribution of the aggregate. To the best of our knowledge this is the first reported experimental and theoretical investigation on the effect of annealing temperature on nano-ceramic fractal aggregates.

Small-angle neutron scattering investigations on sintering behavior of combustion synthesized La0.8Sr0.2CrO3.

Pore morphology of La0.8Sr0.2CrO3 (LSC) powder compacts, sintered between 1200 degrees C and 1450 degrees C for a fixed time, has been characterized by small-angle neutron scattering (SANS) in the scattering wave vector 'q' range, 0.003-0.17 nm(-1) of a double crystal based instrument. Scattering profile of green compact exhibits fractal scaling at two regions of 'q' with magnitudes of fractal dimensionality 1.8 and 2.36. Scattering profiles of sintered pellets have been modeled assuming a random distribution of near spherical pores in the solid matrix. Estimated pore size distributions of sintered pellets indicate decrease in pore volume has taken place by progressive elimination of smallest pores and growth of relatively larger pores with increasing sintering temperature. SANS results are supplemented by light scattering measurement and TEM image of powder and SEM image of the fracture surface of sintered pellet.

Effect of dichlorvos on haemocyte morphology in the male and female P. pictus.

The effect of dichlorvos on the blood cells of P. pictus males and females was studied. The insecticide produced numerous changes in the haemocytes, such as changes in shape and size, displacement of the nucleus, bulging of the cytoplasm, formation of pseudopodia, vacuolation, shrinkage of the nucleus and karyorrhexis. The effect on all the types of haemocytes was not the same, however, some types being more susceptible than others and some not susceptible at all. The effect of the insecticide on the haemocytes was of only short duration and was followed by a return to normal.

Age-related changes in the total protein in the brain of Periplaneta americana (L.).

Quantitative changes in the total protein in the brain of aging male and female Periplaneta americana have been observed. A significant increase of total protein and neurosecretory cells in the brain up to 5 months, followed by a considerable decline in later age, points to a direct relationship between the neurosecretory cell number and reproductive phenomenon. Higher total protein concentration and cell number maintain reproduction up to 5 months while a decline after 6 months of adult life adversely affects reproduction. This suggests that neurosecretory cell number and protein concentration are related to reproduction and thereby aging.