Graphene oxide based multilayer capsules with unique permeability properties: facile encapsulation of multiple drugs

Novel composite graphene oxide (GO)/poly(allylamine hydrochloride) (PAH) multilayer capsules have been fabricated by layer-by-layer (LbL) assembly. They were found to possess unique permeability properties compared to traditional LbL capsules. These hybrid capsules showed special ``core-shell'' loading property for encapsulation of dual drugs simultaneously into the core and shell of the capsules respectively.

Electron irradiation effects on TGA-capped CdTe quantum dots

8MeV electron irradiation effects on thioglycolic acid (TGA)-capped CdTe quantum dots (QD) are discussed in this study. CdTe QDs were characterized using x-ray diffraction (XRD), transmission electron microscope (TEM) and x-ray photoelectron spectroscopy (XPS). Steady-state and time-resolved emission spectroscopy and UV-visible absorption spectroscopy were performed before and after irradiation with 8MeV electrons. XRD and TEM confirm the growth of TGA-capped CdTe QDs. The photoemission wavelength, intensity and lifetimes were found to vary with electron dose. At lower doses, they were found to be increasing (red-shift of photoluminescence (PL) peak and intensity) while the intensity decreased at higher electron doses. The observed changes in PL property, XPS and XRD analysis suggest possible epitaxial growth of the CdS shell on the CdTe core. This work demonstrates electron beam induced formation of the CdS layer on the CdTe core, which is a key step towards growth of the water soluble CdTe/CdS core-shell structure for biomedical labelling applications.

Cyclodextrin-functionalized Fe3O4@TiO2: reusable, magnetic nanoparticles for photocatalytic degradation of endocrine-disrupting chemicals in water supplies

Water-dispersible, photocatalytic Fe3O4@TiO2 core shell magnetic nanoparticles have been prepared by anchoring cyclodextrin cavities to the TiO2 shell, and their ability to capture and photocatalytically destroy endocrine-disrupting chemicals, bisphenol A and dibutyl phthalate, present in water, has been demonstrated. The functionalized nanoparticles can be magnetically separated from the dispersion after photocatalysis and hence reused. Each component of the cyclodextrin-functionalized Fe3O4@TiO2 core shell nanoparticle has a crucial role in its functioning. The tethered cyclodextrins are responsible for the aqueous dispersibility of the nanoparticles and their hydrophobic cavities for the capture of the organic pollutants that may be present in water samples. The amorphous TiO2 shell is the photocatalyst for the degradation and mineralization of the organics, bisphenol A and dibutyl phthalate, under UV illumination, and the magnetism associated with the 9 nm crystalline Fe3O4 core allows for the magnetic separation from the dispersion once photocatalytic degradation is complete. An attractive feature of these ``capture and destroy'' nanomaterials is that they may be completely removed from the dispersion and reused with little or no loss of catalytic activity.

Liquefied Petroleum Gas Sensing of Polyaniline-Titanium Dioxide Nanocomposites

Polyaniline/titaniurn dioxide nanocomposites were prepared using alpha-dextrose as surfactant and ammonium persulphate as an oxidant. The PANI/TiO2 nanocomposite is characterized by FTIR, XRD and TEM. The FTIR spectra revel that the presence of characteristic peaks of benzenoid, qunoide rings and metal-oxygen stretching. The XRD studies show the monoclinic structure of the nanocomposites. The TEM study shows that the size of TiO2 is in the order of 9 nm where as the composite size is of the order of 13 nm and further it was observed that the TiO2 particles are intercalated to form a core shell of PANI. The maximum sensing response for LPG is found to be 90% for 30 wt.% of PANI/TiO2 nanocomposites at 400 ppm whereas for Benzene and Toluene it is negligibly small (<= 20%) and for the cyclohexane sensing response it is around 30% for different wt.%.

Enhanced photoabsorption efficiency of incomplete nanoshells

The rather low scattering or extinction efficiency of small nanoparticles, metallic and otherwise, is significantly enhanced when they are adsorbed on a larger core particle. But the photoabsorption by particles with varying surface area fractions on a larger core particle is found to be limited by saturation. It is found that the core-shell particle can have a lower absorption efficiency than a dielectric core with its surface partially nucleated with absorbing particles-an ``incomplete nanoshell'' particle. We have both numerically and experimentally studied the optical efficiencies of titania (TiO2) nucleated in various degrees on silica (SiO2) nanospheres. We show that optimal surface nucleation over cores of appropriate sizes and optical properties will have a direct impact on the applications exploiting the absorption and scattering properties of such composite particles.

Synthesis and Mechanism of Composition and Size Dependent Morphology Selection in Nanoparticles of Ag-Cu Alloys Processed by Laser Ablation Under Liquid Medium

We have synthesized Ag-Cu alloy nanoparticles of four different compositions by using the laser ablation technique with the target under aqueous medium. Following this, we report a morphological transition in the nanoparticles from a normal two-phase microstructure to a structure with random segregation and finally a core shell structure at small sizes as a function of Cu concentration. To illustrate the composition dependence of morphology, we report observations carried out on nanoparticles of two different sizes: similar to 5 and similar to 20 nm. The results could be rationalized through the thermodynamic modeling of free energy of phase mixing and wettability of the alloying phases.

Determination of Internal Structures of Heterogeneous Nanocrystals Using Variable-Energy Photoemission Spectroscopy

This article describes the determination of the internal structure of heterogeneous nanoparticle systems including inverted core-shell (CdS core and CdSe shell) and alloyed (CdSeS) quantum dots using depth-resolved, variable-energy X-ray photoelectron spectroscopy (XPS). A unique feature of this work is the combination of photoelectron spectroscopy performed at lower X-ray energies (400-700 eV), to achieve surface sensitivity, with bulk sensitive measurements at high photon energies (>2000 eV), thereby providing detailed information about the whole nanoparticle structure with a great accuracy. The use of high photon energies furthermore allows us to investigate nanoparticles much larger than those studied thus far. This capability is a consequence of the much-increased mean free path of the photoelectron achieved at high excitation energies. Our results show that the actual structures of the synthesized nanoparticles are considerably different from the nominal, targeted structures, which can be post facto rationalized in terms of the reactivity of different constituents.

Synthesis and characterization of Ag-Co-Ni nanowires

This work provides an electrodeposition-based methodology for synthesizing multicomponent nanowires containing Ag, Co and Ni atoms. Nanowire morphology was obtained by using an anodic alumina membrane with cylindrical pores of similar to 200-nm diameter. Structural, compositional and magnetic characterization revealed that the as-synthesized nanowires adopted a core-shell microstructure. The core (axial region) contained pure Ag phase volumes with a plate-like morphology oriented perpendicular to the nanowire axis. The shell (peripheral region) contained pure Ag nanoparticles along with superparamagnetic Co and Ni rich clusters.

High quality oxide-free metallic nanoparticles: a strategy for synthesis through laser ablation in aqueous medium

The paper explores the synthesis of oxide-free nanoparticles of Ag and Cu through laser ablation of pure targets under aqueous medium and tuning the quality and size through addition of Polyvinylpyrrolidone (PVP) in the medium. The size distribution of nanoparticles reduces from 37 +/- 30 nm and 13 +/- 5 nm to 32 +/- 12 nm and 4 +/- 1 nm for Ag and Cu with changes in PVP concentration from 0.00 to 0.02 M, respectively. Irregular shaped particles of Ag with Ag2O phase and a Cu-Cu2O core-shell particles form without the addition of PVP, while oxide layer is absent with 0.02 M of PVP. The recent understanding of the mechanism of particle formation during laser ablation under liquid medium allows us to rationalize our observation.

Tailoring the interface of an immiscible polymer blend by a mutually miscible homopolymer grafted onto graphene oxide: outstanding mechanical properties

A unique strategy was adopted here to improve the compatibility between the components of an immiscible polymer blend and strengthen the interface. PMMA, a mutually miscible polymer to both PVDF and ABS, improved the compatibility between the phases by localizing at the blends interface. This was supported by the core-shell formation with PMMA as the shell and ABS as the core as observed from the SEM micrographs. This phenomenon was strongly contingent on the concentration of PMMA in the blends. This strategy was further extended to localize graphene oxide (GO) sheets at the blends interface by chemically coupling it to PMMA (PMMA-g-GO). A dramatic increment of ca. 84% in the Young's modulus and ca. 124% in the yield strength was observed in the presence of PMMA-g-GO with respect to the neat blends. A simultaneous increment in both the strength and the modulus was observed in the presence of PMMA-g-GO whereas, only addition of GO resulted in a moderate improvement in the yield strength. This study reveals that a mutually miscible polymer can render compatibility between the immiscible pair and can improve the stress transfer at the interface.

Phase formation and stability of alloy phases in free nanoparticles: some insights

This paper explores phase formation and phase stability in free nanoparticles of binary alloys. A procedure for estimating the size and composition dependent free energies incorporating the contributions from the interfaces has been presented. Both single phase solid solution and two phase morphology containing interphase interfaces have been considered. A free energy scenario has been evaluated for two binary alloy systems Ag-Ni and Ag-Cu to predict the microstructure of the alloy nanoparticles at different size ranges as a function of composition. Both Ag-Cu and Ag-Ni systems exhibit wide bulk immiscibility. Ag-Ni nanoparticles were synthesized using the wet chemical synthesis technique whereas Ag-Cu nanoparticles were synthesized using laser ablation of a Ag-Cu target immersed in distilled water. Microstructural and compositional characterization of Ag-Ni and Ag-Cu nanoparticles on a single nanoparticle level was conducted using transmission electron microscopy. Nanoparticle microstructures observed from the microscopic investigation have been correlated with thermodynamic calculation results. It is shown that the observed two phase microstructure consisting of Ag-Ni solid solution in partial decomposed state coexisting with pure Ag phases in the case of Ag-Ni nanoparticles can be only be rationalized by invoking the tendency for phase separation of an initial solid solution with increase in nanoparticle size. Smaller sized Ag-Ni nanoparticles prefer a single phase solid solution microstructure. Due to an increase in particle size during the synthesis process the initial solid solution decomposes into an ultrafine scale phase separated microstructure. We have shown that it is necessary to invoke critical point phenomenon and wetting transition in systems showing a critical point that leads to phase separated Ag-Ni nanoparticles providing a catalytic substrate for the nucleation of equilibrium Ag over it. In the case of the Ag-Cu system, we report the experimental observation of a core shell structure at small sizes. This can be rationalized in terms of a metastable solid solution. It is argued that the nucleation barrier can prevent the formation of biphasic morphology with an internal interface. In such a situation, demixing of the solid solution can bring the system to a lower energy configuration. This has lead to the observed core-shell morphology in the Ag-Cu system during room temperature synthesis.

Comparative study of magnetic ordering in bulk and nanoparticles of Sm0.65Ca0.35MnO3: Magnetization and electron magnetic resonance measurements

To explore the effect of size reduction to nanoscale on the hole doped Sm0.65Ca0.35MnO3 compound, dc magnetic measurements and electron magnetic resonance (EMR) were done on bulk and nanoparticle samples in the temperature range 10 <= T <= 300 K. Magnetization measurement showed that the bulk sample undergoes a charge ordering transition at 240K and shows a mixed magnetic phase at low temperature. However, the nanosample underwent a ferromagnetic transition at 75 K, and the charge ordered state was destabilized on size reduction down to nanoscale. The low-temperature ferromagnetic component is found to be enhanced in nanoparticles as compared to their bulk counterpart. Interestingly around room temperature, bulk particles show higher magnetization where as at low temperature nanoparticles show higher magnetization. Ferromagnetism in the bulk is due to super exchange where as ferromagnetism in nanoparticles is due to uncompensated spins of the surface layer. Temperature variation of EMR parameters correlates well with the results of magnetic measurements. The magnetic behaviour of the nanoparticles is understood in terms of the core shell scenario. (C) 2015 AIP Publishing LLC.

Exciton-phonon scattering and nonradiative relaxation of excited carriers in hydrothermally synthesized CdTe quantum dots

Naturally formed CdTe/CdS core/shell quantum dot (QD) structures in the presence of surface stabilizing agents have been synthesized by a hydrothermal method. Size and temperature dependent photoluminescence (PL) spectra have been investigated to understand the exciton-phonon interaction, and radiative and nonradiative relaxation of carriers in these QDs. The PL of these aqueous CdTe QDs (3.0-4.8 nm) has been studied in the temperature range 15-300 K. The strength of the exciton-LO-phonon coupling, as reflected in the Huang-Rhys parameter `S' is found to increase from 1.13 to 1.51 with the QD size varying from 4.8 to 3.0 nm. The PL linewidth (FWHM) increases with increase in temperature and is found to have a maximum in the case of QDs of 3.0 nm in size, where the exciton-acoustic phonon coupling coefficient is enhanced to 51 mu eV K-1, compared to the bulk value of 0.72 mu eV K-1. To understand the nonradiative processes, which affect the relaxation of carriers, the integrated PL intensity is observed as a function of temperature. The integrated PL intensity remains constant until 50 K for relatively large QDs (3.9-4.8 nm) beyond which a thermally activated process takes over. Below 150 K, a small activation energy, 45-19 meV, is found to be responsible for the quenching of the PL. Above 150 K, the thermal escape from the dot assisted by scattering with multiple longitudinal optical (LO) phonons is the main mechanism for the fast quenching of the PL. Besides this high temperature quenching, interestingly for relatively smaller size QDs (3.4-3.0 nm), the PL intensity enhances as the temperature increases up to 90-130 K, which is attributed to the emission of carriers from interface/trap states having an activation energy in the range of 6-13 meV.

Strain-Induced Hierarchy of Energy Levels in CdS/ZnS Nanocrystals

Aside of size and shape, the strain induced by the mismatch of lattice parameters between core and shell in the nanocrystalline regime is an additional degree of freedom to engineer the electron energy levels. Herein, CdS/ZnS core/shell nanocrystals (NCs) with shell thickness up to four monolayers are studied. As a manifestation of strain, the low temperature radiative lifetime measurements indicate a reduction in Stokes shift from 36 meV for CdS to 5 meV for CdS/ZnS with four monolayers of overcoating. Concomitant crossover of S- and P-symmetric hole levels is observed which can be understood in the framework of theoretical calculations predicting flipping the hierarchy of ground hole state by the strain in CdS NCs. Furthermore, a nonmonotonic variation of higher energy levels in strained CdS NCs is discussed.

Synthesis of Hollow Nanotubes of Zn2SiO4 or SiO2: Mechanistic Understanding and Uranium Adsorption Behavior

We report a facile synthesis of Zn2SiO4 nanotubes using a two-step process consisting of a wet-chemical synthesis of core-shell ZnO@SiO2 nanorods followed by thermal annealing. While annealing in air leads to the formation of hollow Zn2SiO4, annealing under reducing atmosphere leads to the formation of SiO2 nanotubes. We rationalize the formation of the silicate phase at temperatures much lower than the temperatures reported in the literature based on the porous nature of the silica shell on the ZnO nanorods. We present results from in situ transmission electron microscopy experiments to clearly show void nucleation at the interface between ZnO and the silica shell and the growth of the silicate phase by the Kirkendall effect. The porous nature of the silica shell is also responsible for the etching of the ZnO leading to the formation of silica nanotubes under reducing conditions. Both the hollow silica and silicate nanotubes exhibit good uranium sorption at different ranges of pH making them possible candidates for nuclear waste management.