Shobha V. Ramagiri

Enhancing Cubosome Functionality by Coating with a Single Layer of Poly-ε-lysine

We report the preparation and characterization of monoolein cubosomes that can be easily surface modified through adsorption of a single layer of cationic poly-ε-lysine. Poly-ε-lysine coated cubosomes show remarkable stability in serum solution, are nontoxic and, are readily internalized by HeLa cells. The poly-ε-lysine coating provides chemical handles for further bioconjugation of the cubosome surface. We also demonstrate that the initial release rate of a hydrophilic drug, Naproxen sodium, from the cubosomes is retarded with just a single layer of polymer. Interestingly, cubosomes loaded with Naproxen sodium, recently shown to have anticancer properties, cause more apoptosis in HeLa cells when compared to free unencapsulated drug.

Redox Decomposition of Silver Citrate Complex in Nanoscale Confinement: An Unusual Mechanism of Formation and Growth of Silver Nanoparticles

We demonstrate for the first time the intrinsic role of nanoconfinement in facilitating the chemical reduction of metal ion precursors with a suitable reductant for the synthesis of metal nanoparticles, when the identical reaction does not occur in bulk solution. Taking the case of citrate reduction of silver ions under the unusual condition of [citrate]/[Ag(+)] ≫ 1, it has been observed that the silver citrate complex, stable in bulk solution, decomposes readily in confined nanodomains of charged and neutral matrices (ion-exchange film and porous polystyrene beads), leading to the formation of silver nanoparticles. The evolution of growth of silver nanoparticles in the ion-exchange films has been studied using a combination of (110m)Ag radiotracer, small-angle X-ray scattering (SAXS) experiments, and transmission electron microscopy (TEM). It has been observed that the nanoconfined redox decomposition of silver citrate complex is responsible for the formation of Ag seeds, which thereafter catalyze oxidation of citrate and act as electron sink for subsequent reduction of silver ions. Because of these parallel processes, the particle sizes are in the bimodal distribution at some stages of the reaction. A continuous seeding with parallel growth mechanism has been revealed. Based on the SAXS data and radiotracer kinetics, the growth mechanism has been elucidated as a combination of continuous autoreduction of silver ions on the nanoparticle surfaces and a sudden coalescence of nanoparticles at a critical number density. However, for a fixed period of reduction, the size, size distribution, and number density of thus-formed Ag nanoparticles have been found to be dependent on physical architecture and chemical composition of the matrix.

Diffusional Transport of Ions in Plasticized Anion-Exchange Membranes

Diffusional transport properties of hydrophobic anion-exchange membranes were studied using the polymer inclusion membrane (PIM). This class of membranes is extensively used in the chemical sensor and membrane based separation processes. The samples of PIM were prepared by physical containment of the trioctylmethylammonium chloride (Aliquat-336) in the plasticized matrix of cellulose triacetate (CTA). The plasticizers 2-nitrophenyl octyl ether, dioctyl phthalate, and tris(2-ethylhexyl)phosphate having different dielectric constant and viscosity were used to vary local environment of the membrane matrix. The morphological structure of the PIM was obtained by atomic force microscopy and transmission electron microscopy (TEM). For TEM, platinum nanoparticles (Pt nps) were formed in the PIM sample. The formation of Pt nps involved in situ reduction of PtCl(6)(2-) ions with BH(4)(-) ions in the membrane matrix. Since both the species are anions, Pt nps thus formed can provide information on spatial distribution of anion-exchanging molecules (Aliquat-336) in the membrane. The glass transitions in the membrane samples were measured to study the effects of plasticizer on physical structure of the membrane. The self-diffusion coefficients (D) of the I(-) ions and water in these membranes were obtained by analyzing the experimentally measured exchange rate profiles of (131)I(-) with (nat)I(-) and tritiated water with H(2)O, respectively, between the membrane and equilibrating solution using an analytical solution of Ficks second law. The values of D(I(-)) in membrane samples with a fixed proportion of CTA, plasticizer, and Aliquat-336 were found to vary significantly depending upon the nature of the plasticizer used. The comparison of values of D with properties of the plasticizers indicated that both dielectric constant and viscosity of the plasticizer affect the self-diffusion mobility of I(-) ions in the membrane. The value of D(I(-)) in the PIM samples did not vary significantly with concentration of Aliquat-336 up to 0.5 mequiv g(-1), and thereafter D(I(-)) increased linearly with Aliquat-336 concentration in the membrane. The self-diffusion coefficients of water D(H(2)O) in PIM samples were found to be 1 order of magnitude higher than the value of D(I(-)) and varied slightly depending upon the plasticizer present in the membrane. It was observed in electrochemical impedance spectroscopic studies of the PIM samples that diffusion mobility of NO(3)(-) ions was 1.66 times higher than that of I(-) ions, and diffusion mobility of SO(4)(2-) ions was half of that for I(-) ions. The theoretical interpretation of experimental counterions exchange rate profiles in terms of the Nernst-Planck equation for interdiffusion also showed higher diffusion mobility of NO(3)(-) ions in the PIM than Cl(-), I(-), and ClO(4)(-) ions, which have comparable diffusion mobility.

In situ formation of stable gold nanoparticles in polymer inclusion membranes

Gold nanoparticles (Au nps) were synthesized in the matrix of a plasticized anion-exchange membrane. The membrane was prepared by solvent casting of the solution containing a liquid anion exchanger trioctylmethylammonium chloride (Aliquat-336), a matrix-forming polymer cellulose triacetate (CTA), and a plasticizer dioctyl phthalate (DOP) dissolved in CH(2)Cl(2). For in situ synthesis of Au nps, the membrane samples were equilibrated with a well-stirred solution containing 0.01 mol L(-1)HAuCl(4). AuCl(4)(-) ions were transferred to membrane matrix as an ion pair with Aliquat-336 by an ion-exchange mechanism. In a second step, AuCl(4)(-) ion-loaded membrane samples were placed in a well-stirred 0.1 mol L(-1) aqueous solution of NaBH(4) for reduction. It was observed that 80% of the anion-exchange sites were readily available for the exchange process after formation of the Au nps. The content of Au nps in the membrane was increased either by increasing the concentration of the Aliquat-336 in membrane or by repeating sequential cycles of loading of AuCl(4)(-) ions followed by reduction with BH(4)(-) in the membrane matrix. TEM images of a cross section of the membrane showed that Au nps were dispersed throughout the matrix of the membrane but excluded from the surface. The size distribution of the nps was found to be dependent on Au content in the membrane. For example, 7- to 16-nm Au nps with average size 10 nm were observed in the membrane after the first cycle of synthesis. On increasing the Au content in the membrane by repeating the cycle of synthesis, the size dispersion of nps broadened from 5 to 20 nm without affecting the average size. The lambda(max) (530 nm) and intensity of the surface plasmon band of Au nps embedded in the matrix of membrane were found to remain unaltered over a testing period of a month in the samples kept in water as well as in air under ambient conditions. This indicated that Au nps were quite stable in the membrane matrix. The experimental information obtained by the radiotracers and energy-dispersive X-ray fluorescence (EDXRF) analyses has been used to understand the process of Au nps formation in the membrane matrix.

Galvanic reactions involving silver nanoparticles embedded in cation-exchange membrane.

Galvanic reactions of Hg(2+), Rh(3+), and AuCl(4)(-) ions with Ag nanoparticles positioned near the surface and throughout the matrix of host poly(perfluorosulfonic) acid membrane have been studied.

Time resolved growth of membrane stabilized silver NPs and their catalytic activity

Formation of highly stable metal nanostructures in a Nafion® membrane with various aspect ratios has been of considerable research interest in recent years. However, there is a need for a proper understanding of the growth mechanism of such nanostructures in Nafion® (sometimes larger than the size of water–sulfonate ionic clusters of the membrane). In this work, the early growth kinetics of silver nanoparticles (NPs) in Nafion®-117 ion-exchange membrane during in situ L-ascorbic acid reduction of Ag+ ions by time resolved in situ small-angle X-ray scattering (SAXS) using synchrotron radiation with a time resolution of 50 ms are revealed for the first time. The SAXS analyses, corroborated by transmission electron microscopy, showed that the sizes of NPs increase rapidly together with their number density until they attain a certain size that could be accommodated in the ∼5 nm water–sulfonate ionic clusters. Further growth takes place either by self-agglomeration of the particles ejected out from the water–sulfonic acid clusters or by continuous reduction of metal ions on the existing NP surfaces (uniformly or on a specific plane) leading to formation of bigger nanostructures with various aspect ratios. The time resolved information of NP growth provides an opportunity for the controlled synthesis of metal NPs with a definite size, shape and size distribution for a specific application. The catalytic properties of Ag NPs formed in the membrane were examined using borohydride reduction of a model dye methylene blue. It was observed that smaller Ag NPs with a mean diameter ∼3 nm, confined in the hydrophilic clusters of the Nafion® matrix, have reasonably good catalytic activity and a lower lag time for the onset of reduction.

Plasticised polymer inclusion membrane as tunable host for stable gold nanoparticles

Stable Au nanoparticles (nps) were synthesised in matrix of the self-supported plasticised polymer inclusion anion-exchange membrane using the ion-exchange route for loading AuCl4− anions in membrane and their subsequent reduction with BH4− anions. The compositions of membrane was varied by changing concentration of the anion exchanger, and also using different plasticiser. X-ray diffraction patterns of the membrane samples embedded with Au nps were taken to study the parameters involved in the formation of Au nps in the plasticised polymer matrix. The content of Au nps in the membrane was increased by: 1) repeating the sequential cycles of loading of AuCl4− ions followed by the reduction with BH4− in the membrane matrix; 2) increasing the concentration of anion exchanger in the membrane matrix. It was observed in TEM images of cross section of membrane that spherical Au nps of 10 nm sizes were dispersed throughout the matrix of membrane. The increase in Au0 content in the membrane did not alter the average size of Au nps significantly, but slightly increased the range of size distribution. The nanostructures like prism, rod, sphere, bipyramid and cuboid were also observed in the membrane matrix, but their number density was 5% of nanoparticles present in the membrane matrix. The analyses of isotopic-exchange rate profiles of iodide ions between the membrane sample and well-stirred equilibrating salt solution indicated that formation of Au nps lead to a significant increase in self-diffusion mobility of the anions in membrane. The surface plasmon band (SPB λmax = 535 nm) of Au nps did not change on equilibration of the membrane samples with the solutions containing Cl−, I−, ClO4−, and CH3COO− anions, but completely disappeared on equilibration with solution containing molecular iodine.

Positioning of Platinum Nanoparticles In Cation‐exchange Membrane By Galvanic Reaction

Platinum nanoparticles were formed at the surface of the poly (perfluorosulfonic) acid membrane (Nafion‐117) by the galvanic reaction of PtCl62− ions with Ag nanoparticles positioned near the surface of the membrane. The reduction with BH4− ions produced Ag nanoparticles (15±4 nm size) mostly positioned near the surface of membrane due to Donnan exclusion of co‐ions (BH4−). Energy Dispersive X‐ray Fluorescence (EDXRF) analysis of the membrane indicated that galvanic reaction proceeded quantitatively. Transmission Electron Microscopy (TEM) of the cross‐sections of membrane samples indicated that the spherical Pt nanoparticles having size 2 to 8 nm were mostly located near the surface of the membrane. The positioning of Pt nanoparticles at surface of the membrane is important for using nano‐composite in catalytical application.