Layer-by-Layer Self-Assembled Metal-Ion- (Ag-, Co-, Ni-, and Pd-) Doped TiO2 Nanoparticles: Synthesis, Characterisation, and Visible Light Degradation of Rhodamine B

Metal-ion- (Ag, Co, Ni and Pd) doped titania nanocatalysts were successfully deposited on glass slides by layer-by-layer (LbL) self-assembly technique using a poly(styrene sulfonate sodium salt) (PSS) and poly(allylamine hydrochloride) (PAH) polyelectrolyte system. Solid diffuse reflectance (SDR) studies showed a linear increase in absorbance at 416 nm with increase in the number of m-TiO2 thin films. The LbL assembled thin films were tested for their photocatalytic activity through the degradation of Rhodamine B under visible-light illumination. From the scanning electron microscope (SEM), the thin films had a porous morphology and the atomic force microscope (AFM) studies showed ``rough'' surfaces. The porous and rough surface morphology resulted in high surface areas hence the high photocatalytic degradation (up to 97% over a 6.5 h irradiation period) using visible-light observed. Increasing the number of multilayers deposited on the glass slides resulted in increased film thickness and an increased rate of photodegradation due to increase in the availability of more nanocatalysts (more sites for photodegradation). The LbL assembled thin films had strong adhesion properties which made them highly stable thus displaying the same efficiencies after five (5) reusability cycles.

Selective colorimetric detection of nanomolar Cr (VI) in aqueous solutions using unmodified silver nanoparticles

In this study we present a colorimetric detection method for Cr (VI) in aqueous solution based on as synthesized silver nanoparticles (Ag NPs) without surface functionalization. The method principle involves reduction of Cr (VI) to Cr (III) by excess reductant present in as synthesized Ag NP dispersion, and subsequent aggregation of Ag NPs by Cr (III) leading to red-shift of the surface plasmon resonance (SPR) peak. The UV-vis absorption spectra. Zeta potentials, dynamic light scattering measurements, and scanning electron microscopy (SEM) confirmed the aggregation of the Ag NPs. Under the optimized conditions, a good linear relationship (correlation coefficient r=0.981) was obtained between the ratio of the absorbance at 550 nm to that at 390 nm (A(550/390)) and the concentration of Cr (VI) over the range of 10(-3)-10(-9) M 50 mg/L to 50 ng/L]. The reported probe has a limit of detection down to 1 nM, which, to the best of our knowledge, is the lowest ever reported for the colorimetric detection of Cr (VI). Furthermore, a remarkable feature of this method is that it involves a simple technique exhibiting high selectivity to Cr (VI) over other tested heavy metal ions. (C) 2012 Elsevier BM. All rights reserved.

Enhancing the magnetic characteristics of BiFeO3 nanoparticles by Ca, Ba co-doping

Multiferroic nanoparticles (NPs) of pristine and Ca, Ba co-doped BiFeO3 were synthesized by a facile sal gel route. Co-doping was done by fixing the total dopant concentration at 5 mol% and then the relative concentrations of Ca and Ba was varied. Structural, optical and magnetic properties of the NPs were investigated using different techniques. UV-Vis absorption spectra of BiFeO3 NPs showed a substantial blue shift of similar to 100 nm (530 nm -> 430 nm) on Ca. Ba co-doping which corresponds to increase in band gap by 0.5 eV. Fe-57 Mossbauer spectroscopy confirmed that iron is present only in 3(+) valence state in all co-doped samples. The coercive field increased by 18 times for Bi0.95Ca0.01Ba0.04FeO3 samples, which is the maximum enhancement, observed amongst all the 5 mol% doped samples. At the equimolar (2.5 mol % each) concentration of co-dopants, the coercive field shows a significant enhancement of about 9 times (220 Oe -> 2014 Oe) with concomitant increase in saturation magnetization by 7 times. Thus, equimolar co-doping causes simultaneous enhancement of the twin aspects of magnetic properties thereby making them better suited for device applications. (C) 2012 Elsevier B.V. All rights reserved.

Charge order suppression, emergence of ferromagnetism and absence of exchange bias effect in Bi0.25Ca0.75MnO3 nanoparticles: Electron paramagnetic resonance and magnetization studies

We report the results of magnetization and electron paramagnetic resonance (EPR) studies on nanoparticles (average diameter similar to 30 nm) of Bi0.25Ca0.75MnO3 (BCMO) and compare them with the results on bulk BCMO. The nanoparticles were prepared using the nonaqueous sol-gel technique and characterized by XRD and TEM analysis. Magnetization measurements were carried out with a commercial physical property measurement system (PPMS). While the bulk BCMO exhibits a charge ordering transition at similar to 230 K and an antiferromagnetic (AFM) transition at similar to 130 K, in the nanoparticles, the CO phase is seen to have disappeared and a transition to a ferromagnetic (FM) state is observed at T-c similar to 120 K. However, interestingly, the exchange bias effect observed in other nanomanganite ferromagnets is absent in BCMO nanoparticles. EPR measurements were carried out in the X-band between 8 and 300 K. Lineshape fitting to a Lorentzian with two terms (accounting for both the clockwise and anticlockwise rotations of the microwave field) was employed to obtain the relevant EPR parameters as functions of temperature. The results confirm the occurrence of ferromagnetism in the nanoparticles of BCMO. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.4730612]

Self-Assembly and Catalytic Activity of Metal Nanoparticles Immobilized in Polymer Membrane Prepared via Layer-by-Layer Approach

Densely packed nanoparticles distributed in a stable and robust thin film is a highly preferred system for utilizing the various applications of nanoparticles. Here, we report covalent bond mediated layer-by-layer (LbL) self-assembled thin films of nanoparticles embedded in polymer membrane. Polymer with complementary functional group is utilized for fabrication of thin film via covalent bonding. UV-visible spectroscopy, atomic force microscopy (AFM) and scanning electron microscopy (SEM) were used to monitor the growth of LbL thin film. Subsequently, the composite thin film is used for catalysis of an organic electron transfer reaction of p-nitrophenol to p-aminophenol by sodium borohydride. The catalytic activity of these composite films is assayed multiple times, proving its applicability as a catalyst. The kinetic data obtained by monitoring reduction of p-nitrophenol suggest that the reaction rates are directly related to the sizes of the nanoparticle and porosity of the membrane.

Effect of different fuels on structural, thermo and photoluminescent properties of Gd 2O 3 nanoparticles

Gd 2O 3 nanoparticles (27-60nm) have been synthesized by the low temperature solution combustion method using citric acid, urea, glycine and oxalyl dihydrazide (ODH) as fuels in a short time. The structural and luminescence properties have been carried out using powder X-ray diffraction (PXRD), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), Raman, UV-Vis, photoluminescence (PL) and thermoluminescence (TL) techniques. The optical band gap values were estimated for as formed and 800°C calcined samples. The band gap values in as-formed and calcined samples were found to be in the range 4.89-5.59eV. It is observed that, the band gap values are lower for as-formed products and it has been attributed to high degree of structural defects. However, in calcined samples, structure becomes more order with reduced structure defects. Upon 270nm excitation, deep blue UV-band at �390nm along with blue (420-482nm), green (532nm) and red emission (612nm) was observed. The 390nm emission peak may be attributed to recombination of delocalized electron close to the conduction band with a single charged state of surface oxygen vacancy. TL measurements were carried out on Gd 2O 3 prepared by different fuels by irradiating with γ-rays (1kGy). A well resolved glow peak at 230°C was observed for all the samples. It is observed that TL intensity is found to be higher in for urea fuel when compared to others. From TL glow curves the kinetic parameters were estimated using Chen's peak shape method and results are discussed in detail. © 2012 Elsevier B.V.

Dispersed ZrO2 nanoparticles in MCM-48 with high adsorption activity

A new two-step synthesis of ZrO2-MCM nanocomposites using the gel combustion technique was accomplished; the resulting material had a high-surface area and showed very high adsorption activity. The deposition of 25 nm ZrO2 particles over MCM was achieved using gel combustion technique with glycine as a fuel, and the formation of nanocomposites was confirmed using transmission electron microscopy. The composites were also characterized by XRD, SEM, FTIR and N2 adsorption-desorption analysis. The nanocomposites were tested for the adsorption of cationic dyes. High rates of adsorption and large dye uptake were observed over the nanocomposites. The rate of adsorption over the nanocomposites was higher than that observed for physical ZrO2-MCM mixtures and commercial activated carbon. The nanocomposite with 10 wt % ZrO2 showed the highest rate of adsorption owing to the synergistic effects of ZrO2 surface groups, smaller particle size, fine dispersion and high-surface area of the composite. (c) 2012 American Institute of Chemical Engineers AIChE J, 58: 29872996, 2012

Multilayer assemblies of polyelectrolyte-gold nanoparticles for the electrocatalytic oxidation and detection of arsenic(III)

Multilayers of poly(diallyldimethylammonium chloride) (PDDA) and citrate capped Au nanoparticles (AuNPs) anchored on sodium 3-mercapto-1-propanesulfonate modified gold electrode by electrostatic layer-by-layer assembly (LbL) technique are shown to be an excellent architecture for the direct electrochemical oxidation of As(III) species. The growth of successive layers in the proposed LbL architecture is followed by atomic force microscopy, UV-vis spectroscopy, quartz crystal microbalance with energy dissipation, and electrochemistry. The first bilayer is found to show rather different physico-chemical characteristics as compared to the subsequent bilayers, and this is attributed to the difference in the adsorption environments. The analytical utility of the architecture with five bilayers is exploited for arsenic sensing via the direct electrocatalytic oxidation of As(III), and the detection limit is found to be well below the WHO guidelines of 10 ppb. When the non-redox active PDDA is replaced by the redoxactive Os(2,2'-bipyridine)(2)Cl-poly(4-vinylpyridine) polyelectrolyte (PVPOs) in the LbL assembly, the performance is found to be inferior, demonstrating that the redox activity of the polyelectrolyte is futile as far as the direct electro-oxidation of As(III) is concerned. (C) 2012 Elsevier Inc. All rights reserved.

Porous Three Dimensional Arrays of Plasmonic Nanoparticles

Plasmonic interactions in a well-defined array of metallic nanoparticles can lead to interesting optical effects, such as local electric field enhancement and shifts in the extinction spectra, which are of interest in diverse technological applications, including those pertaining to biochemical sensing and photonic circuitry. Here, we report on a single-step wafer scale fabrication of a three-dimensional array of metallic nanoparticles whose sizes and separations can be easily controlled to be anywhere between fifty to a few hundred nanometers, allowing the optical response of the system to be tailored with great control in the visible region of the spectrum. The substrates, apart from having a large surface area, are inherently porous and therefore suitable for optical sensing applications, such as surface enhanced Raman scattering, containing a high density of spots with enhanced local electric fields arising from plasmonic couplings.

Carbonization of solvent and capping agent based enhancement in the stabilization of cobalt nanoparticles and their magnetic study

We describe a hybrid synthetic protocol, the solvated metal atom dispersion (SMAD) method, for the synthesis and stabilization of monodisperse amorphous cobalt nanoparticles. By employing an optimized ratio of a weakly coordinating solvent and a capping agent monodisperse colloidal cobalt nanoparticles (2 +/- 0.5 nm) have been prepared by the SMAD method. However, the as-prepared samples were found to be oxidatively unstable which was elucidated by their magnetic studies. Oxidative stability in our case was achieved via a pyrolysis process that led to the decomposition of the organic solvent and the capping agent resulting in the formation of carbon encapsulated cobalt nanoparticles which was confirmed by Raman spectroscopy. Controlled annealing at different temperatures led to the phase transformation of metallic cobalt from the hcp to fcc phase. The magnetic behaviour varies with the phase and the particle size; especially, the coercivity of nanoparticles exhibited strong dependence on the phase transformation of cobalt. The high saturation magnetization close to that of the bulk value was achieved in the case of the annealed samples. In addition to detailed structural and morphological characterization, the results of thermal and magnetic studies are also presented.

Silver nanoparticles modified nanocapsules for ultrasonically activated drug delivery

Novel ultrasound-sensitive nanocapsules were designed via layer-by-layer assembly (LbL) of polyelectrolytes for remote activated release of biomolecules/drug. Nanocapsules embedded with silver nanoparticles in the walls were synthesized by alternate assembly of poly(allylamine hydrochloride) (PAH) and dextran sulfate (DS) on silica template followed by nanoparticle synthesis and subsequent template removal thus yielding nanocapsules. The silver NPs were synthesized in situ within the capsule walls under controlled conditions. The nanocapsules were found to be well dispersed and the silver NPs were evenly distributed within the shell. FITC-dextran permeated easily into the capsules containing silver NP's due to the pores generated during the formation of NP's. When the loaded nanocapsules were sonicated, the presence of the silver NPs in the shell structure led to rupturing of the shell into smaller fragments thus releasing the FITC-dextran. Such nanocapsules have the potential to be used as drug delivery vehicles and offer the scope for further development in the areas of modern medicine, material science, and biochemistry. (C) 2012 Elsevier B.V. All rights reserved.

Metal and Alloy Nanoparticles by Amine-Borane Reduction of Metal Salts by Solid-Phase Synthesis: Atom Economy and Green Process

A new solid state synthetic route has been developed toward metal and bimetallic alloy nanoparticles from metal salts employing amine-boranes, as the reducing agent. During the reduction, amine-borane plays a dual role: acts as a reducing agent and reduces the metal salts to their elemental form and simultaneously generates a stabilizing agent in situ which controls the growth of the particles and stabilizes them in the nanosize regime. Employing different amine-boranes with differing reducing ability (ammonia borane (AB), dimethylamine borane (DMAB), and triethylamine borane (TMAB)) was found to have a profound effect on the particle size and the size distribution. Usage of AB as the reducing agent provided the smallest possible size with best size distribution. Employment of TMAB also afforded similar results; however, when DMAB was used as the reducing agent it resulted in larger sized nanoparticles that are polydisperse too. In the AB mediated reduction, BNHx polymer generated in situ acts as a capping agent whereas, the complexing amine of the other amine-boranes (DMAB and TMAB) play the same role. Employing the solid state route described herein, monometallic Au, Ag, Cu, Pd, and Ir and bimetallic CuAg and CuAu alloy nanoparticles of <10 nm were successfully prepared. Nucleation and growth processes that control the size and the size distribution of the resulting nanoparticles have been elucidated in these systems.

Size-dependent density of nanoparticles and nanostructured materials

We discuss the size-dependent density of nanoparticles and nanostructured materials keeping the recent experimental results in mind. The density is predicted to increase with decreasing size for nanoparticles but it can decrease with size for nanostructured materials that corroborates the experimental results reported in the literature. (C) 2012 Elsevier B.V. All rights reserved.

Effect of high gold salt concentrations on the size and polydispersity of gold nanoparticles prepared by an extended Turkevich-Frens method

The Turkevich-Frens synthesis starting conditions are expanded, ranging the gold salt concentrations up to 2 mM and citrate/gold(III) molar ratios up to 18:1. For each concentration of the initial gold salt solution, the citrate/gold(III) molar ratios are systematically varied from 2:1 to 18:1 and both the size and size distribution of the resulting gold nanoparticles are compared. This study reveals a different nanoparticle size evolution for gold salt solutions ranging below 0.8 mM compared to the case of gold salt solutions above 0.8 mM. In the case of Au3+]<0.8 mM, both the size and size distribution vary substantially with the citrate/gold(III) ratio, both displaying plateaux that evolve inversely to Au3+] at larger ratios. Conversely, for Au3+]>= 0.8 mM, the size and size distribution of the synthesized gold nanoparticles continuously rise as the citrate/gold(III) ratio is increased. A starting gold salt concentration of 0.6 mM leads to the formation of the most monodisperse gold nanoparticles (polydispersity index<0.1) for a wide range of citrate/gold(III) molar ratios (from 4:1 to 18:1). Via a model for the formation of gold nanoparticles by the citrate method, the experimental trends in size could be qualitatively predicted:the simulations showed that the destabilizing effect of increased electrolyte concentration at high initial Au3+] is compensated by a slight increase in zeta potential of gold nanoparticles to produce concentrated dispersion of gold nanoparticles of small sizes.

Orthogonal biofunctionalization of magnetic nanoparticles via ``clickable'' poly(ethylene glycol) silanes: a ``universal ligand'' strategy to design stealth and target-specific nanocarriers

The present work demonstrates a novel strategy to synthesize orthogonally bio-engineered magnetonanohybrids (MNPs) through the design of versatile, biocompatible linkers whose structure includes: (i) a robust anchor to bind with metal-oxide surfaces; (ii) tailored surface groups to act as spacers and (iii) a general method to implement orthogonal functionalizations of the substrate via ``click chemistry''. Ligands that possess the synthetic generality of features (i)-(iii) are categorized as ``universal ligands''. Herein, we report the synthesis of a novel, azido-terminated poly(ethylene glycol) (PEG) silane that can easily self-assemble on MNPs through hetero-condensation between surface hydroxyl groups and the silane end of the ligand, and simultaneously provide multiple clickable sites for high density, chemoselective bio-conjugation. To establish the universal-ligand-strategy, we clicked alkyl-functionalized folate onto the surface of PEGylated MNPs. By further integrating a near-infrared fluorescent (NIRF) marker (Alexa-Fluor 647) with MNPs, we demonstrated their folate-receptor mediated internalization inside cancer cells and subsequent translocation into lysosomes and mitochondria. Ex vivo NIRF imaging established that the azido-PEG-silane developed in course of the study can effectively reduce the sequestration of MNPs by macrophage organs (viz. liver and spleen). These folate-PEG-MNPs were not only stealth and noncytotoxic but their dual optical and magnetic properties aided in tracking their whereabouts through combined magnetic resonance and optical imaging. Together, these results provided a strong motivation for the future use of the ``universal ligand'' strategy towards development of ``smart'' nanohybrids for theragnostic applications.