Direct photocatalytic conversion of aldehydes to esters using supported gold nanoparticles under visible light irradiation at room temperature

Visible light can drive esteri fi cation from aldehydes and alcohols using supported gold nanoparticles (Au/Al 2 O 3 ) as photo- catalysts at ambient temperatures. The gold nanoparticles (AuNPs) absorb visible light due to the localized surface plasmon resonance (LSPR) e ff ect, and the conduction electrons of the AuNPs gain the energy of the incident light. The energetic electrons, which concentrate at the NP surface, facilitate the activation of a range of aldehyde and alcohol substrates. The photocatalytic e ffi ciencies strongly depend on the Au loading, particle sizes of the AuNPs, irradiance, and wavelength of the light irradiation. Finally, a plausible reaction mechanism was proposed, and the Au/Al 2 O 3 catalysts can be reused several times without signi fi cantly losing activity. The knowledge acquired in this study may inspire further studies in new e ffi cient recyclable photocatalysts and a wide range of organic synthesis driven by sunlight.

Direct photocatalysis for organic synthesis by using plasmonic-metal nanoparticles irradiated with visible light

Recent advances in direct-use plasmonic-metal nanoparticles (NPs) as photocatalysts to drive organic synthesis reactions under visible-light irradiation have attracted great interest. Plasmonic-metal NPs are characterized by their strong interaction with visible light through excitation of the localized surface plasmon resonance (LSPR). Herein, we review recent developments in direct photocatalysis using plasmonic-metal NPs and their applications. We focus on the role played by the LSPR of the metal NPs in catalyzing organic transformations and, more broadly, the role that light irradiation plays in catalyzing the reactions. Through this, the reaction mechanisms that these light-excited energetic electrons promote will be highlighted. This review will be of particular interest to researchers who are designing and fabricating new plasmonic-metal NP photocatalysts by identifying important reaction mechanisms that occur through light irradiation.

Efficient photocatalytic Suzuki cross-coupling reactions on Au-Pd alloy nanoparticles under visible light irradiation

We report herein highly efficient photocatalysts comprising supported nanoparticles (NPs) of gold (Au) and palladium (Pd) alloys, which utilize visible light to catalyse the Suzuki cross-coupling reactions at ambient temperature. The alloy NPs strongly absorb visible light, energizing the conduction electrons of NPs which produce highly energetic electrons at the surface sites. The surface of the energized NPs activates the substrates and these particles exhibit good activity on a range of typical Suzuki reaction combinations. The photocatalytic efficiencies strongly depend on the Au:Pd ratio of the alloy NPs, irradiation light intensity and wavelength. The results show that the alloy nanoparticles efficiently couple thermal and photonic energy sources to drive Suzuki reactions. Results of the density functional theory (DFT) calculations indicate that transfer of the light-excited electrons from the nanoparticle surface to the reactant molecules adsorbed on the nanoparticle surface activates the reactants. The knowledge acquired in this study may inspire further studies of new efficient photocatalysts and a wide range of organic syntheses driven by sunlight.

Viable photocatalysts under solar-spectrum irradiation: Nonplasmonic metal nanoparticles

Supported nanoparticles (NPs) of nonplasmonic transition metals (Pd, Pt, Rh, and Ir) are widely used as thermally activated catalysts for the synthesis of important organic compounds, but little is known about their photocatalytic capabilities. We discovered that irradiation with light can significantly enhance the intrinsic catalytic performance of these metal NPs at ambient temperatures for several types of reactions. These metal NPs strongly absorb the light mainly through interband electronic transitions. The excited electrons interact with the reactant molecules on the particles to accelerate these reactions. The rate of the catalyzed reaction depends on the concentration and energy of the excited electrons, which can be increased by increasing the light intensity or by reducing the irradiation wavelength. The metal NPs can also effectively couple thermal and light energy sources to more efficiently drive chemical transformations.

Electrochemical mechanism of eugenol at a Cu doped gold nanoparticles modified glassy carbon electrode and its analytical application in food samples

A simple one-step electrodeposition method was used to construct a glassy carbon electrode (GCE), which has been modified with Cu doped gold nanoparticles (GNPs), i.e. a Cu@AuNPs/GCE. This electrode was characterized with the use of scanning electron microscopy (SEM) and X-ray diffraction (XRD) techniques. The eugenol was electrocatalytically oxidized at the Cu@AuNPs/GCE. At this electrode, in comparison with the behavior at the GCE alone, the corresponding oxidation peak current was enhanced and the shift of the oxidation potentials to lower values was observed. Electrochemical behavior of eugenol at the Cu@AuNPs/GCE was investigated with the use of the cyclic voltammetry (CV) technique, and additionally, in order to confirm the electrochemical reaction mechanism for o-methoxy phenols, CVs for catechol, guaiacol and vanillin were investigated consecutively. Based on this work, an electrochemical reaction mechanism for o-methoxy phenols was suggested, and in addition, the above Cu@AuNPs/GCE was successfully employed for the analysis of eugenol in food samples.

The in vivo fate of nanoparticles and nanoparticle-loaded microcapsules after oral administration in mice: Evaluation of their potential for colon-specific delivery

Anti-cancer drug loaded-nanoparticles (NPs) or encapsulation of NPs in colon-targeted delivery systems shows potential for increasing the local drug concentration in the colon leading to improved treatment of colorectal cancer. To investigate the potential of the NP-based strategies for colon-specific delivery, two formulations, free Eudragit® NPs and enteric-coated NP-loaded chitosan–hypromellose microcapsules (MCs) were fluorescently-labelled and their tissue distribution in mice after oral administration was monitored by multispectral small animal imaging. The free NPs showed a shorter transit time throughout the mouse digestive tract than the MCs, with extensive excretion of NPs in faeces at 5 h. Conversely, the MCs showed complete NP release in the lower region of the mouse small intestine at 8 h post-administration. Overall, the encapsulation of NPs in MCs resulted in a higher colonic NP intensity from 8 h to 24 h post-administration compared to the free NPs, due to a NP ‘guarding’ effect of MCs during their transit along mouse gastrointestinal tract which decreased NP excretion in faeces. These imaging data revealed that this widely-utilised colon-targeting MC formulation lacked site-precision for releasing its NP load in the colon, but the increased residence time of the NPs in the lower gastrointestinal tract suggests that it is still useful for localised release of chemotherapeutics, compared to NP administration alone. In addition, both formulations resided in the stomach of mice at considerable concentrations over 24 h. Thus, adhesion of NP- or MC-based oral delivery systems to gastric mucosa may be problematic for colon-specific delivery of the cargo to the colon and should be carefully investigated for a full evaluation of particulate delivery systems.

Multimodal polymer nanoparticles with combined 19F magnetic resonance and optical detection for tunable, targeted, multimodal imagingin vivo

Understanding the complex nature of diseased tissue in vivo requires development of more advanced nanomedicines, where synthesis of multifunctional polymers combines imaging multimodality with a biocompatible, tunable, and functional nanomaterial carrier. Here we describe the development of polymeric nanoparticles for multimodal imaging of disease states in vivo. The nanoparticle design utilizes the abundant functionality and tunable physicochemical properties of synthetically robust polymeric systems to facilitate targeted imaging of tumors in mice. For the first time, high-resolution 19F/1H magnetic resonance imaging is combined with sensitive and versatile fluorescence imaging in a polymeric material for in vivo detection of tumors. We highlight how control over the chemistry during synthesis allows manipulation of nanoparticle size and function and can lead to very high targeting efficiency to B16 melanoma cells, both in vitro and in vivo. Importantly, the combination of imaging modalities within a polymeric nanoparticle provides information on the tumor mass across various size scales in vivo, from millimeters down to tens of micrometers.

Sizable photocurrent and emission from solid state devices based on CdS nanoparticles

CdS nanoparticles exhibit size dependent optical and electrical properties. We report here the photocurrent and I-V characteristic studies of CdS nanoparticle devices. A sizable short circuit photocurrent was observed in the detection range governed by the size of the clusters. We speculate on the mechanisms leading to the photocurrent and emission in these nanometer scale systems.

A.c. conductivity studies on the silver molybdo-arsenate glassy system

A new quaternary fast-ion conducting silver molybdo-arsenate [Agl-Ag2O-(MoO3 + As2O5)] (SMA) glassy system has been prepared using the melt-quenching technique for various dopant salt (Agl) concentrations by fixing the formers (MoO3 + As2O5) composition and the modifier (Ag2O) to formers (M/F) ratio. The prepared compounds were characterized by X-ray diffraction. The impedance measurements were made on different Agl compositions of the SMA glasses as a function of frequency (6.5 Hz-65 kHz) and temperature (303-343 K), using the Solatron frequency-response analyser(model 1250). The bulk conductivity and the appropriate physical model (equivalent circuit) of the SMA glass were obtained from the impedance analysis. The a.c. conductivity was calculated for different Agl compositions of SMA glasses at various temperatures and the obtained a.c. conductivity results were analysed using Jonscher's Universal Law. The conduction mechanism for the highest conducting SMA glassy compound has been explained using the diffusion path model.

Fabrication and evaluation of 1 Ah silver/metal hydride cells

Silver/metal hydride (Ag/MH) cells of about 1 Ah capacity have been fabricated and their discharge characteristics at different rates of discharge, faradaic efficiency, cycle life and a.c. impedance have been evaluated. These cells comprise metal-hydride electrodes prepared by employing similar to 60 mu m powder of an AB(2)-Laves phase alloy of nominal composition Zr0.5Ti0.5V0.6Cr0.2Ni1.2 with PTFE binder on a nickel-mesh substrate as the negative plates and commercial-grade silver electrodes as the positive plates. The cells are positive limited and exhibit two distinct voltage plateaus characteristic of two-step reduction of AgO to Ag during their low rates of discharge between C/20 and C/10. This feature is, however, absent when the cells are discharged at C/5 rate. On charging the cells to 100% of their capacity, the faradaic efficiency is found to be 100%. The impedance of the Ag/MH cell is essentially due to the impedance of the silver electrodes, since MH electrodes offer negligible impedance. The cells may be subjected to a large number of charge-discharge cycles with little deterioration.

Nanoporous Pt with High Surface Area by Reaction-Limited Aggregation of Nanoparticles

Nanoporous structures with high active surface areas are critical for a variety of applications. Here, we present a general templateless strategy to produce such porous structures by controlled aggregation of nanostructured subunits and apply the principles for synthesizing nanoporous Pt for electrocatalytic oxidation of methanol. The nature of the aggregate produced is controlled by tuning the electrostatic interaction between surfactant-free nanoparticles in the solution phase. When the repulsive force between the particles is very large, the particles are stabilized in the solution while instantaneous aggregation leading to fractal-like structures results when the repulsive force is very low. Controlling the repulsive interaction to an optimum, intermediate value results in the formation of compact structures with very large surface areas. In the case of Pt, nanoporous clusters with an extremely high specific surface area (39 m(2)/g) and high activity for methanol oxidation have been produced. Preliminary investigations indicate that the method is general and can be easily extended to produce nanoporous structures of many inorganic materials.

Magnetization, magnetotransport and electron magnetic resonance studies of nanoparticles and nanowires of Pr0.5Sr0.5MnO3

In this paper, we present the preparation and characterization of nanoparticles and nanowires of Pr0.5Sr0.5MnO3 (PSMO). The main results of this investigation are as follows: (a) a comparison with the properties of the bulk material shows that the ferromagnetic (FM) transition at 270 K remains unaffected but the anti-ferromagnetic (AFM) transition at TN = 150 K disappears in the nanoparticles, (b) the size induced ground state magnetic phase (below 150 K) is predominantly FM, coexisting with a residual AFM phase, and (c) the temperature dependence of magnetic anisotropy shows complex behaviour, being higher in the nanoparticles at high temperatures and lower at moderately lower temperatures in comparison with the bulk. The results obtained from the extensive magnetization, magnetotransport and electron magnetic resonance studies made on various samples are presented and discussed in detail.

X-ray diffraction of permalloy nanoparticles fabricated by laser ablation in water

Permalloy (NiFeMo) nanoparticles were fabricated by laser ablation of bulk material in water with a UV pulsed laser. Transmission electron microscope images showed that approximately spherical particles about 50 nm in diameter were formed in the ablation process. All diffraction peaks corresponding to the bulk material were present in the nanoparticles. In addition to these peaks several new peaks were observed in the nanoparticles, which were attributed to nickel oxide.

Synthesis of nanoparticles of the giant dielectric material, CaCu3Ti4O12 from a precursor route

A complex oxalate precursor, CaCu3(TiO)(4)(C2O4)(8)center dot 9H(2)O, (CCT-OX), was synthesized and the precipitate that obtained was confirmed to be monophasic by the wet chemical analyses, X-ray diffraction, FTIR absorption and TG/DTA analyses. The thermal decomposition of this oxalate precursor led to the formation of phase-pure calcium copper titanate, CaCu3Ti4O12, (CCTO) at a parts per thousand yen680A degrees C. The bright-field TEM micrographs revealed that the size of the as synthesized crystallites to be in the 30-80 nm range. The powders so obtained had excellent sinterability resulting in high density ceramics which exhibited giant dielectric constants upto 40000 (1 kHz) at 25A degrees C, accompanied by low dielectric losses.

Unusual dynamical arrest in polymer grafted nanoparticles

We present results of temperature dependent measurements of dynamics of polymer grafted nanoparticles with high grafting density with star polymerlike morphology. We observed for the low grafting density and hence low functionality sample, a dynamically arrested state with lowering of temperature, similar to what was conjectured earlier. However the high grafting density sample shows liquidlike relaxation at all measured temperatures. Possible origin of dynamical arrest in the two grafting density sample is discussed.