Gold nanoparticles anchored reduced graphene oxide as catalyst for oxygen electrode of rechargeable Li-O-2 cells

Gold nanoparticles decorated reduced graphene oxide (Au-RGO) catalyst for O-2 electrode is prepared by in situ reduction of Au3+ ions and graphene oxide dispersed in water. The Au nanoparticles are uniformly distributed on the two-dimensional RGO layers. Li-O-2 cells assembled in a non-aqueous electrolyte using Au-RGO catalyst exhibit an initial discharge capacity as high as 5.89 mA h cm-(2) (5230 mA h g(-1))at a current density of 0.1 mA cm(-2). The voltage gap between the charge and discharge curves is less for Li-O-2(Au-RGO) cell in comparison with Li-O-2(RGO) cell. The Li-O-2(Au-RGO) cells are cycled over about 120 charge-discharge cycles. The results suggest that Au-RGO is a promising catalyst for rechargeable Li-O-2 cells.

Enhancing Surface Coverage and Growth in Layer-by-Layer Assembly of Protein Nanoparticles

Thin films of bovine serum albumin (BSA) nanoparticles are fabricated via layer-by-layer assembly. The surface of BSA nanoparticles have two oppositely acting functional groups on the surface: amine (NH2) and carboxylate (COO-). The protonation and deprotonation of these functional groups at different pH vary the charge density on the particle surface, and entirely different growth can be observed by varying the nature of the complementary polymer and the pH of the particles. The complementary polymers used in this study are poly(dimethyldiallylammonium chloride) (PDDAC) and poly(acrylic acid) (PAA). The assembly of BSA nanoparticles based on electrostatic interaction with PDDAC suffers from the poor loading of the nanoparticles. The assembly with PAA aided by a hydrogen bonding interaction shows tremendous improvement in the growth of the assembly over PDDAC. Moreover, the pH of the BSA nanoparticles was observed to affect the loading of nanoparticles in the LbL assembly with PAA significantly.

Polymer template-assisted microemulsion synthesis of large surface area, porous Li2MnO3 and its characterization as a positive electrode material of Li-ion cells

Lithium-rich manganese oxide (Li2MnO3) is prepared by reverse microemulsion method employing Pluronic acid (P123) as a soft template and studied as a positive electrode material. The as-prepared sample possesses good crystalline structure with a broadly distributed mesoporosity but low surface area. As expected, cyclic voltammetry and charge-discharge data indicate poor electrochemical activity. However, the sample gains surface area with narrowly distributed mesoporosity and also electrochemical activity after treating in 4 M H2SO4. A discharge capacity of about 160 mAh g(-1) is obtained. When the acid-treated sample is heated at 300 A degrees C, the resulting porous sample with a large surface area and dual porosity provides a discharge capacity of 240 mAh g(-1). The rate capability study suggests that the sample provides about 150 mAh g(-1) at a specific discharge current of 1.25 A g(-1). Although the cycling stability is poor, the high rate capability is attributed to porous nature of the material.

Synthesis, characterisation and application of an exfoliated graphite-diamond composite electrode in the electrochemical degradation of trichloroethylene

A composite electrode made up of exfoliated graphite (EG) and diamond was prepared for the electrochemical oxidation of trichloroethylene (TCE). The SEM images of the EG-diamond material showed that diamond powders were dispersed on the surface of EG materials. The N-2 adsorption-desorption isotherm of EG-diamond material resulted in a poor adsorption capability due to the insertion of diamond powders into the porous matrix of EG. Raman spectroscopy revealed the presence of characteristic sp(3) bands of diamond confirming good interaction of diamond with EG. Electrochemical characterisation of EG-diamond in 0.1 M Na2SO4 resulted in an enhanced working potential window. The EG-diamond electrode was employed for the electrochemical oxidation of trichloroethylene (0.2 mM) in a Na2SO4 supporting electrolyte. The EG-diamond, in comparison to the pristine EG electrode, exhibited a higher removal efficiency of 94% (EG was 57%) and faster degradation kinetics of 25.3 x 10(-3) min(-1) showing pseudo first order kinetic behaviour. Under the optimised conditions, 73% total organic content (TOC) removal was achieved after 4 h of electrolysis. The degradation of TCE was also monitored with gas chromatography-mass spectrometry. Dichloroacetic acid (DCAA) was identified as a major intermediate product during the electrochemical oxidation of TCE. The electrochemical degradation of TCE at the EG-diamond electrode represents a cost effective method due to the ease of preparation of EG-diamond composite material without the necessity of diamond activation which is normally achieved through doping.

Versatility of azide in serendipitous assembly of Copper(II) Magnetic Polyclusters

Engineering at the molecular level is one of the most exciting new developments for the generation of functional materials. However, the concept of designing polynuclear extended structures from bottom up is still not mature. Although progress has been made with secondary building units (SBUs) in metal organic frameworks (MOFs), the control seems to be just an illusion when it comes to bridging ligands such as the azide ion. When we say that the azido ligand is versatile in its bridging capabilities, what we mean is that it would be difficult to predict or control its bridging properties. However, this kind of serendipity is not always bad news. For example, scientists have shown that the azido ligand can mediate magnetic exchanges between paramagnetic metals in a predictable fashion (usually depending upon the bonding geometries). Therefore, it is a well-respected ligand in polynuclear assemblies. Serendipitous assemblies offer new magnetic structures that we may not otherwise even think about synthesizing. The azido ligand forms a variety of complexes with copper(II) using different blocking amines or pyridine based ligands. Its structural nature changes upon changing the substitution on amine, as well as the amount of blocking ligand. In principle, if we take any of these complexes and provide more coordination sites to the bridging azido ligands by removing a fraction of the blocking ligands, we can get new complexes with intricate structural networks and therefore different magnetic properties with the same components as used for the parent complex. In this Account, we mainly discuss the development of a number of new topological and magnetic exchange systems synthesized using this concept. Not all of these new complexes can be grouped according to their basic building structures or even by the ratio of the metal to blocking ligand. Therefore, we divided the discussion by the nuclearity of the basic building structures. Some of the complexes with the same nuclearities have very similar or even almost identical basic structures. However, the way these building units are joined together (by the azido bridges) to form the overall extended structures differ almost in every case. The complexes having the Cu-6 core are particularly interesting from a structural point of view. Although they have almost identical basic structures, some of them are extended in three dimensions, but two of them are extended in two dimensions by two different bridging networks. In the complexes having linear Cu-4 basic units, we find that using similar ligands does not always give the same bridging networks even within the basic building structures. These complexes have also enriched the field of molecular magnetism. One of the complexes with a Cu-3 building unit has provided us with the opportunity to study the competing behavior of two different kinds of magnetic exchange mechanism (ferromagnetic and antiferromagnetic) acting simultaneously between two metal ions. Through density functional theory calculations, we showed how they work independently and their additive nature to produce the overall effect. The exciting methodology for the generation of copper(II) polyclusters presented in this Account will provide the opportunity to explore analogous serendipitous assembly of diverse structures with interesting magnetic behavior using other transition metal ions having more than one unpaired electrons.

Studies on thin film based flexible gold electrode arrays for resistivity imaging in electrical impedance tomography

Practical phantoms are essential to assess the electrical impedance tomography (EIT) systems for their validation, calibration and comparison purposes. Metal surface electrodes are generally used in practical phantoms which reduce the SNR of the boundary data due to their design and development errors. Novel flexible and biocompatible gold electrode arrays of high geometric precision are proposed to improve the boundary data quality in EIT. The flexible gold electrode arrays are developed on flexible FR4 sheets using thin film technology and practical gold electrode phantoms are developed with different configurations. Injecting a constant current to the phantom boundary the surface potentials are measured by a LabVIEW based data acquisition system and the resistivity images are reconstructed in EIDORS. Boundary data profile and the resistivity images obtained from the gold electrode phantoms are compared with identical phantoms developed with stainless steel electrodes. Surface profilometry, microscopy and the impedance spectroscopy show that the gold electrode arrays are smooth, geometrically precised and less resistive. Results show that the boundary data accuracy and image quality are improved with gold electrode arrays. Results show that the diametric resistivity plot (DRP), contrast to noise ratio (CNR), percentage of contrast recovery (PCR) and coefficient of contrast (COC) of reconstructed images are improved in gold electrode phantoms. (C) 2013 Elsevier Ltd. All rights reserved.

Physical understanding of pore formation on supported lipid bilayer by bacterial toxins

Pore forming toxins are being classified in the protein community based on their ability of forming pores in living cell membranes. Some initial study has apparently pointed out the crystallographic pathway rather can be viewed as a structural as well as morphological changes of proteins in terms of self assembly before and during the pore formation process in surfactant medium. Being a water soluble compound, it changes its conformation and originates some pre-pore complex, which later partially goes inside the cell membrane causing a pore. The physical mechanism for this whole process is still unknown. In this study we have tried to understand these types of biological processes from physical point of view by using supported lipid bilayer as a model system.

Organic device electrode fabricated by aluminum in nanopowder and bulk form and effect on device properties

Schottky barrier devices of metal/semiconductor/metal structure were fabricated using organic semiconductor polyaniline (PANI) and aluminium thin film cathode. Aluminium contacts were made by thermal evaporation technique using two different forms of metals (bulk and nanopowder). The structure and surface morphology of these films were investigated by X-ray diffraction, scanning electron microscopy, and atomic force microscopy. Grain size of the as-deposited films obtained by Scherrer's method, modified Williamson-Hall method, and SEM were found to be different. Current-voltage (I-V) characteristic of Schottky barrier device structure indicates that the calculated current density (J) for device fabricated from aluminium nanopowder is more than that from aluminium in bulk form.

Efficacious Anticancer Drug Delivery Mediated by a pH-Sensitive Self-Assembly of a Conserved Tripeptide Derived from Tyrosine Kinase NGF Receptor

We present herein a short tripeptide sequence (Lys-Phe-Gly or KFG) that is situated in the juxtamembrane region of the tyrosine kinase nerve growth factor (Trk NGF) receptors. KFG self-assembles in water and shows a reversible and concentration-dependent switching of nanostructures from nanospheres (vesicles) to nanotubes, as evidenced by dynamic light scattering, transmission electron microscopy, and atomic force microscopy. The morphology change was associated with a transition in the secondary structure. The tripeptide vesicles have inner aqueous compartments and are stable at pH7.4 but rupture rapidly at pH approximate to 6. The pH-sensitive response of the vesicles was exploited for the delivery of a chemotherapeutic anticancer drug, doxorubicin, which resulted in enhanced cytotoxicity for both drug-sensitive and drug-resistant cells. Efficient intracellular release of the drug was confirmed by fluorescence-activated cell sorting analysis, fluorescence microscopy, and confocal microscopy.

Self-assembly of discrete metallamacrocycles employing half-sandwich octahedral diruthenium(II) building units and imidazole-based ligands

Equimolar combination of a series of binuclear half-sandwich p-cymene ruthenium(II) building units Ru-2(mu-eta(4)-C2O4)(MeOH)(2)(eta(6)-p-cymene)(2)](OTf)(2) 1a](OTf)(2), Ru-2(mu-eta(4)-N,N'-diphenyloxamidato)( MeOH)(2)(eta(6)-p-cymene)(2)](OTf)(2) 1b](OTf)(2) and Ru-2(mu-eta(4)-C6H2O4)(MeOH)(2)(eta(6)-p-cymene)(2)](OTf)(2) 1c](OTf)(2) separately with imidazole-based ditopic ligands (L-1-L-2) in methanol yielded a series of tetranuclear metallamacrocycles 2-7](OTf)(4), respectively L-1 = 1,4-bis(imidazole-1-yl)benzene; L-2 = 4,4'-bis(imidazole-1-yl)biphenyl; OTf- = O3SCF3-]. Similarly, the reaction of Ru-2(mu-eta(4)-C2O4)(MeOH)(2)(eta(6)-p-cymene)2](OTf)(2) 1a](OTf)(2) with a triazine-based tritopic ligand 1,3,5-tris(imidazole-1-yl) triazine (L3) in 3: 2 M ratio afforded an unexpected tetranuclear macrocycle 8](OTf)(4) instead of an expected trigonal prismatic cage 8a](OTf)(6). All the self-assembled macrocycles 2-8](OTf)(4) were isolated in moderate to high yields and were fully characterized by multinuclear H-1, F-19] NMR, IR and electrospray ionization mass spectrometry (ESI-MS). In addition, X-ray diffraction study on the single crystals of 3](OTf)(4) and 8](OTf)(4) also indicated the formation 2 + 2] self-assembled macrocycles. Despite the possibility of formation of different conformational isomeric macrocycles (syn-and anti) and polymeric product due to free rotation of ligand sites of imidazole linkers, the selective formation of single conformational isomer (anti) as the only product is quite interesting. Furthermore, the photo-and electrochemical properties of these assemblies have been studied using UV/Vis absorption and cyclic voltammetry analysis. (c) 2013 Elsevier B.V. All rights reserved.

Template-free multicomponent coordination-driven self-assembly of Pd(II)/Pt(II) molecular cages

Recent years have seen a tremendous increase in the interest for constructing hollowed-out molecular frameworks, for their potential uses. Metal-ligand coordination-driven self-assembly has provided multitudes of opportunities in the formation of molecular architectures of desired shapes and sizes, with the help of the information already coded in the components. This article summarizes the recent developments in the construction of multicomponent molecular cages through this process, with a focus on the decreasing relevance of templates, and use of these systems in catalysis/host-guest chemistry.

Polymer Template Assisted Synthesis of Porous Li1.2Mn0.53Ni0.13Co0.13O2 as a High Capacity and High Rate Capability Positive Electrode Material

A porous layered composite of Li2MnO3 and LiMn1/3Co1/3Ni1/3O2 (composition: Li1.2Mn0.53Ni0.13Co0.13O2) is prepared by reverse microemulsion method employing a soft polymer template and studied as a positive electrode material. The precursor is heated at several temperatures between 500 and 900 degrees C. The product samples possess mesoporosity with broadly distributed pores of about 30 nm diameters. There is a decrease in pore volume as well as in surface area by increasing the temperature of preparation. Nevertheless, the electrochemical activity of the composite increases with an increase in temperature. The discharge capacity values of the samples prepared at 800 and 900 degrees C are about 250 mAh g(-1) at a specific current of 40 mA g(-1) with an excellent cycling stability. A value of 225 mAh g(-1) is obtained at the end of 30 charge-discharge cycles. Both these composite samples possess high rate capability, but the 800 degrees C sample is marginally superior to the 900 degrees C sample. A discharge capacity of 100 mAh g(-1) is obtained at a specific current of 1000 mA g(-1). The high rate capability is attributed to porous nature of the composite samples. (C) 2013 The Electrochemical Society. All rights reserved.

A room temperature, templated synthesis of lanthanide trifluoride nanoparticles and their unusual self-assembly

A new methodology has been developed for synthesizing lanthanide trifluoride (LnF(3)) nanoparticles using a simple diffusion technique. The approach uses a lanthanide based hydrogel matrix to control the kinetics of the reaction, which also acts as a stabilizing platform, thus enabling the room temperature, in situ synthesis of finely sized (3-5 nm), monodisperse nanoparticles that were found to form in an ordered pattern on the gel fibers.