Formation and Thermal Stability of Gold-Silica Nanohybrids: Insight into the Mechanism and Morphology by Electron Tomography

Gold-silica hybrids are appealing in different fields of applications like catalysis, sensorics, drug delivery, and biotechnology. In most cases, the morphology and distribution of the heterounits play significant roles in their functional behavior. Methods of synthesizing these hybrids, with variable ordering of the heterounits, are replete; however, a complete characterization in three dimensions could not be achieved yet. A simple route to the synthesis of Au-decorated SiO2 spheres is demonstrated and a study on the 3D ordering of the heterounits by scanning transmission electron microscopy (STEM) tomography is presentedat the final stage, intermediate stages of formation, and after heating the hybrid. The final hybrid evolves from a soft self-assembled structure of Au nanoparticles. The hybrid shows good thermal stability up to 400 degrees C, beyond which the Au particles start migrating inside the SiO2 matrix. This study provides an insight in the formation mechanism and thermal stability of the structures which are crucial factors for designing and applying such hybrids in fields of catalysis and biotechnology. As the method is general, it can be applied to make similar hybrids based on SiO2 by tuning the reaction chemistry as needed.

Spontaneous Breaking of Time-Reversal Symmetry in Strongly Interacting Two-Dimensional Electron Layers in Silicon and Germanium

We report experimental evidence of a remarkable spontaneous time-reversal symmetry breaking in two-dimensional electron systems formed by atomically confined doping of phosphorus (P) atoms inside bulk crystalline silicon (Si) and germanium (Ge). Weak localization corrections to the conductivity and the universal conductance fluctuations were both found to decrease rapidly with decreasing doping in the Si: P and Ge: P delta layers, suggesting an effect driven by Coulomb interactions. In-plane magnetotransport measurements indicate the presence of intrinsic local spin fluctuations at low doping, providing a microscopic mechanism for spontaneous lifting of the time-reversal symmetry. Our experiments suggest the emergence of a new many-body quantum state when two-dimensional electrons are confined to narrow half-filled impurity bands.

Nanostructure Patterning on Flexible Substrates Using Electron Beam Lithography

Patterning nanostructures on flexible substrates plays a key role in the emerging flexible electronics technology. The flexible electronic devices are inexpensive and can be conformed to any shape. The potential applications for such devices are sensors, displays, solar cells, RFID, high-density biochips, optoelectronics etc. E-beam lithography is established as a powerful tool for nanoscale fabrication, but its applicability on insulating flexible substrates is often limited because of surface charging effects. This paper presents the fabrication of nanostructures on insulating flexible substrates using low energy E-beam lithography along with metallic layers for charge dissipation. Nano Structures are patterned on different substrates of materials such as acetate and PET foils. The fabrication process parameters such as the proximity gap of exposure, the exposure dosage and developing conditions have been optimized for each substrate.

Electron microscopy of Ag-(Ni-O) core-shell nanowires

This report provides information about an electrodeposition based two-step synthesis methodology for producing core-shell Ag-(Ni-O) nanowires and their detailed structural and compositional characterization using electron microscopy technique. Nanowires were produced by employing anodic alumina templates with a pore diameter of 200 nm. In the first step of the synthesis process, nanocrystalline Ni-O was electrodeposited in a controlled manner such that it heterogeneously nucleated and grew only on the template pore walls without filling the pores from bottom upwards. This alumina template with pore walls coated with Ni-O was then utilized as a template during the electrodeposition of Ag in the second step. Electrodeposited Ag filled the template pores to finally produce Ag-(Ni-O) core-shell nanowires with an overall diameter of 200 nm.

Explosives Sensing by Using Electron-Rich Supramolecular Polymers: Role of Intermolecular Hydrogen Bonding in Significant Enhancement of Sensitivity

We demonstrate here that supramolecular interactions enhance the sensitivity towards detection of electron-deficient nitro-aromatic compounds (NACs) over discrete analogues. NACs are the most commonly used explosive ingredients and are common constituents of many unexploded landmines used during World WarII. In this study, we have synthesised a series of pyrene-based polycarboxylic acids along with their corresponding discrete esters. Due to the electron richness and the fluorescent behaviour of the pyrene moiety, all the compounds act as sensors for electron-deficient NACs through a fluorescence quenching mechanism. A Stern-Volmer quenching constant determination revealed that the carboxylic acids are more sensitive than the corresponding esters towards NACs in solution. The high sensitivity of the acids was attributed to supramolecular polymer formation through hydrogen bonding in the case of the acids, and the enhancement mechanism is based on an exciton energy migration upon excitation along the hydrogen-bond backbone. The presence of intermolecular hydrogen bonding in the acids in solution was established by solvent-dependent fluorescence studies and dynamic light scattering (DLS) experiments. In addition, the importance of intermolecular hydrogen bonds in solid-state sensing was further explored by scanning tunnelling microscopy (STM) experiments at the liquid-solid interface, in which structures of self-assembled monolayer of the acids and the corresponding esters were compared. The sensitivity tests revealed that these supramolecular sensors can even detect picric acid and trinitrotoluene in solution at levels as low as parts per trillion (ppt), which is much below the recommended permissible level of these constituents in drinking water.

Phenyl carbohydrazone conjugated 2-oxoindoline as a new scaffold that augments the DNA and BSA binding affinity and anti-proliferative activity of a 1,10-phenanthroline based copper(II) complex

A new type of copper(II) complex, CuL(phen)(2)](NO3) (CuIP), where L ((E)-N'-(2-oxoindolin-3-ylidene) benzohydrazide) is a N donor ligand and phen is the N, N-donor heterocyclic 1,10-phenanthroline, has been synthesized. The phenyl carbohydrazone conjugated isatin-based ligand L and CuIP were characterized by elemental analysis, infrared, UV-Vis, H-1 and C-13 NMR and ESI-mass spectral data, as well as single-crystal X-ray diffraction. The interaction of calf thymus DNA (CT DNA) with L and CuIP has been investigated by absorption, fluorescence and viscosity titration methods. The complex CuIP displays better binding affinity than the ligand L. The observed DNA binding constant (K-b = 4.15(+/- 0.18) x 10(5) M-1) and binding site size (s = 0.19), viscosity data together with molecular docking studies of CuIP suggest groove binding and/or a partial intercalative mode of binding to CT DNA. In addition, CuIP shows good binding propensity to the bovine serum albumin (BSA) protein, giving a K-BSA value of 1.25(+/- 0.24) x 10(6) M-1. In addition, the docking studies on DNA and human serum albumin (HSA) CuIP interactions are consistent with the consequence of binding experiments. The in vitro anti-proliferative study establishes the anticancer potency of the CuIP against the human cervical (HeLa) and breast (MCF7) cancer cells; noncancer breast epithelial (MCF10a) cells have also been investigated. CuIP shows better cytotoxicity and sensitivity towards cancer cells over noncancer ones than L under identical conditions, with the appearance of apoptotic bodies. (C) 2014 Elsevier B.V. All rights reserved.

Synthesis and Electron Microscopy of Superalloy Nanowires

An electrodeposition based methodology for synthesizing Ni-Cr-Fe nanowires is provided. As-synthesized nanowires were 200 nm in diameter and more than 5 mu m in length. Detailed characterization of the nanowires using electron microscopy technique revealed an amorphous microstructure for the nanowires with uniform distribution of Ni, Fe and Cr atoms. Annealing of the nanowire using the electron beam inside electron microscope resulted in gradual crystallization of amorphous microstructure into a nanocrystalline one which illustrated the potential for microstructural engineering of the nanowires. (C) 2014 The Electrochemical Society. All rights reserved.

Ferrimagnetism and magnetic phase separation in Nd1-xYxMnO3 studied by magnetization and high frequency electron paramagnetic resonance

Ferrimagnetism and metamagnetic features tunable by composition are observed in the magnetic response of Nd1-xYxMnO3, for x=0.1-0.5. For all values of x in the series, the compound crystallizes in orthorhombic Pbnm space group similar to NdMnO3. Magnetization studies reveal a phase transition of the Mn-sublattice below T-N(Mn) approximate to 80 K for all compositions, which, decreases up on diluting the Nd-site with Yttrium. For x=0.35, ferrimagnetism is observed. At 5 K, metamagnetic transition is observed for all compositions x < 0.4. The evolution of magnetic ground states and appearance of ferrimagnetism in Nd1-xYxMnO3 can be accounted for by invoking the scenario of magnetic phase separation. The high frequency electron paramagnetic resonance measurements on x=0.4 sample, which is close to the critical composition for phase separation, revealed complex temperature dependent lineshapes clearly supporting the assumption of magnetic phase separation. (C) 2014 Elsevier B.V. All rights reserved.

Reply to ``Comment on `Strongly magnetized cold degenerate electron gas: Mass-radius relation of the magnetized white dwarf'''

We show that the upper bound for the central magnetic field of a super-Chandrasekhar white dwarf calculated by Nityananda and Konar Phys. Rev. D 89, 103017 (2014)] and in the concerned comment, by the same authors, against our work U. Das and B. Mukhopadhyay, Phys. Rev. D 86, 042001 (2012)] is erroneous. This in turn strengthens the argument in favor of the stability of the recently proposed magnetized super-Chandrasekhar white dwarfs. We also point out several other numerical errors in their work. Overall we conclude that the arguments put forth by Nityananda and Konar are misleading.

Jacalin-carbohydrate interactions: distortion of the ligand molecule as a determinant of affinity

Jacalin is among the most thoroughly studied lectins. Its carbohydrate-binding site has also been well characterized. It has been postulated that the lower affinity of beta-galactosides for jacalin compared with beta-galactosides is caused by steric interactions of the substituents in the former with the protein. This issue has been explored energetically and structurally using different appropriate carbohydrate complexes of jacalin. It turns out that the earlier postulation is not correct. The interactions of the substituent with the binding site remain essentially the same irrespective of the anomeric nature of the substitution. This is achieved through a distortion of the sugar ring in beta-galactosides. The difference in energy, and therefore in affinity, is caused by a distortion of the sugar ring in beta-galactosides. The elucidation of this unprecedented distortion of the ligand as a strategy for modulating affinity is of general interest. The crystal structures also provide a rationale for the relative affinities of the different carbohydrate ligands for jacalin.

Electron transfer statistics and thermal fluctuations in molecular junctions

We derive analytical expressions for probability distribution function (PDF) for electron transport in a simple model of quantum junction in presence of thermal fluctuations. Our approach is based on the large deviation theory combined with the generating function method. For large number of electrons transferred, the PDF is found to decay exponentially in the tails with different rates due to applied bias. This asymmetry in the PDF is related to the fluctuation theorem. Statistics of fluctuations are analyzed in terms of the Fano factor. Thermal fluctuations play a quantitative role in determining the statistics of electron transfer; they tend to suppress the average current while enhancing the fluctuations in particle transfer. This gives rise to both bunching and antibunching phenomena as determined by the Fano factor. The thermal fluctuations and shot noise compete with each other and determine the net (effective) statistics of particle transfer. Exact analytical expression is obtained for delay time distribution. The optimal values of the delay time between successive electron transfers can be lowered below the corresponding shot noise values by tuning the thermal effects. (C) 2015 AIP Publishing LLC.

Structural variations in aromatic 2 pi-electron three-membered rings of the main group elements

Structural variations of different Z pi-aromatic three-membered ring systems of main group elements, especially group 14 and 13 elements as compared to the classical description of cyclopropenyl cation has been reviewed in this article. The structures of heavier analogues as well as group 13 analogues of cyclopropenyl cation showed an emergence of dramatic structural patterns which do not conform, to the general norms of carbon chemistry. Isolobal analogies between the main group fragments have been efficiently used to explain the peculiarities observed in these three-membered ring systems.

A transmission electron microscopy and X-ray photoelectron spectroscopy study of annealing induced gamma-phase nucleation, clustering, and interfacial dynamics in reactively sputtered amorphous alumina thin films

Pure alpha-Al2O3 exhibits a very high degree of thermodynamical stability among all metal oxides and forms an inert oxide scale in a range of structural alloys at high temperatures. We report that amorphous Al2O3 thin films sputter deposited over crystalline Si instead show a surprisingly active interface. On annealing, crystallization begins with nuclei of a phase closely resembling gamma-Alumina forming almost randomly in an amorphous matrix, and with increasing frequency near the substrate/film interface. This nucleation is marked by the signature appearance of sharp (400) and (440) reflections and the formation of a diffuse diffraction halo with an outer maximal radius of approximate to 0.23 nm enveloping the direct beam. The microstructure then evolves by a cluster-coalescence growth mechanism suggestive of swift nucleation and sluggish diffusional kinetics, while locally the Al ions redistribute slowly from chemisorbed and tetrahedral sites to higher anion coordinated sites. Chemical state plots constructed from XPS data and simple calculations of the diffraction patterns from hypothetically distorted lattices suggest that the true origins of the diffuse diffraction halo are probably related to a complex change in the electronic structure spurred by the a-gamma transformation rather than pure structural disorder. Concurrent to crystallization within the film, a substantially thick interfacial reaction zone also builds up at the film/substrate interface with the excess Al acting as a cationic source. (C) 2015 AIP Publishing LLC.

Observation of coherent population trapping in a V-type two-electron system

We observe coherent population trapping (CPT) in a two-electron atom-Yb-174-using the S-1(0), F= 0 -> P-3(1), F `= 1 transition. CPT is not possible for such a transition according to one-electron theory because the magnetic sublevels form a V-type system, but in a two-electron atom like Yb, the interaction of the electrons transforms the level structure into a V-type system, which allows the formation of a dark state and hence the observation of CPT. Since the two levels involved are degenerate, we use a magnetic field to lift the degeneracy. The single fluorescence dip then splits into five dips-the central unshifted one corresponds to coherent population oscillation, while the outer four are due to CPT. The linewidth of the CPT resonance is about 300 kHz and is limited by the natural linewidth of the excited state, which is to be expected because the excited state is involved in the formation of the dark state.

Electron-Rich Triphenylamine-Based Sensors for Picric Acid Detection

This paper demonstrates the role of solvent in selectivity and sensitivity of a series of electron-rich compounds for the detection of trace amounts of picric acid. Two new electron-rich fluorescent esters (6, 7) containing a triphenylamine backbone as well as their analogous carboxylic acids (8, 9) have been synthesized and characterized. Fluorescent triphenylamine coupled with an ethynyl moiety constitutes p-electron-rich selective and sensitive probes for electron-deficient picric acid (PA). In solution, the high sensitivity of all the sensors toward PA can be attributed to a combined effect of the ground-state charge-transfer complex formation and resonance energy transfer between the sensor and analyte. The acids 8 and 9 also showed enhanced sensitivity for nitroaromatics in the solid state, and their enhanced sensitivity could be attributed to exciton migration due to close proximity of the neighboring acid molecules, as evident from the X-ray diffraction study. The compounds were found to be quite sensitive for the detection of trace amount of nitroaromatics in solution, solid, and contact mode.