Colorimetric Probes Based on Anthraimidazolediones for Selective Sensing of Fluoride and Cyanide Ion via Intramolecular Charge Transfer

Probes based on anthra[1,2-d]imidazole-6,11-dione were designed and synthesized for selective ion sensing. Each probe acted as strong colorimetric sensors for fluoride and cyanide ions and exhibited intramolecular charge transfer (ICT) band, which showed significant red-shifts after addition of either the F(-) or CN(-) ion. One of the probes (2) showed selective colorimetric sensing for both cyanide and fluoride ions. In organic medium, 2 showed selective color change with fluoride and cyanide, whereas in aqueous organic medium it showed a ratiometric response selectively for cyanide ion.

Scalable processes for fabricating non-volatile memory devices using self-assembled 2D arrays of gold nanoparticles as charge storage nodes

We propose robust and scalable processes for the fabrication of floating gate devices using ordered arrays of 7 nm size gold nanoparticles as charge storage nodes. The proposed strategy can be readily adapted for fabricating next generation (sub-20 nm node) non-volatile memory devices.

Physical chemistry of the reduction of calcium oxide with aluminium in vacuum

The physical chemistry of "aluminothermic" reduction of calcium oxide in vacuum is analyzed. Basic thermodynamic data required for the analysis have been generated by a variety of experiments. These include activity measurements in liquid AI-Ca alloys and determination of the Gibbs energies of formation of calcium aluminates. These data have been correlated with phase relations in the Ca-AI-0 system at 1373 K. The various stages of reduction, the end products and the corresponding equilibrium partial pressures of calcium have been established from thermodynamic considerations. In principle, the recovery of calcium can be improved by reducing the pressure in the reactor. However,, the cost of a high vacuum system and the enhanced time for reduction needed to achieve higher yields makes such a practice uneconomic. Aluminum contamination of calcium also increases at low pressures. The best compromise is to carry the reduction up to the stage where 3CaO-Al,O, is formed as the product. This corresponds to an equilibrium calcium partial pressure of 31.3 Pa at 1373 K and 91.6 Pa at 1460 K. Calcium can be extracted at this pressure using mechanical pumps in approximately 8 to 15 hr, depending on the size and the fill ratio of the retort and porosity of the charge briquettes.

Charge Density Analysis of a Pentaborate Ion in an Ammonium Borate: Toward the Understanding of Topological Features in Borate Minerals

Structural and charge density distribution studies have been carried out on a single crystal data of an ammonium borate, [C(10)H(26)N(4)][B(5)O(6)(OH)(4)](2), synthesized by solvothermal method. Further, the experimentally observed geometry is used for the theoretical charge density calculations using the B3LYP/6-31G** level of theory, and the results are compared with the experimental values. Topological analysis of charge density based on the Atoms in Molecules approach for B-O bonds exhibit mixed covalent/ionic character. Detailed analysis of the hydrogen bonds in the crystal structure in the ammonium borate provides insights into the understanding of the reaction pathways that net atomic charges and electrostatic potential isosurfaces also give additional such systems. could result in the formation of borate minerals. The input to evaluate chemical and physical properties in such systems.

Extending the Supramolecular Synthon Based Fragment Approach (SBFA) for Transferability of Multipole Charge Density Parameters to Monofluorobenzoic Acids and their Cocrystals with Isonicotinamide: Importance of C-H center dot center dot center dot O, C-H center dot center dot center dot F, and F center dot center dot center dot F Intermolecular Regions

An extension of the supramolecular synthon-based fragment approach (SBFA) method for transferability of multipole charge density parameters to include weak supramolecular synthons is proposed. In particular, the SBFA method is applied to C-H center dot center dot center dot O, C-H center dot center dot center dot F, and F center dot center dot center dot F containing synthons. A high resolution charge density study has been performed on 4-fluorobenzoic acid to build a synthon library for C-H center dot center dot center dot F infinite chain interactions. Libraries for C-H center dot center dot center dot O and F center dot center dot center dot F synthons were taken from earlier work. The SBFA methodology was applied successfully to 2- and 3-fluorobenzoic acids, data sets for which were collected in a routine manner at 100 K, and the modularity of the synthons was demonstrated. Cocrystals of isonicotinamide with all three fluorobenzoic acids were also studied with the SBFA method. The topological analysis of inter- and intramolecular interaction regions was performed using Bader's AIM approach. This study shows that the SBFA method is generally applicable to generate charge density maps using information from multiple intermolecular regions.

Weakening of charge order and antiferromagnetic to ferromagnetic switch over in Pr0.5Ca0.5MnO3 nanowires

We have prepared crystalline nanowires (diameter ∼ 50 nm, length ∼ a few microns) of the charge-ordering manganite Pr0.5Ca0.5MnO3 using a low reaction temperature hydrothermal method and characterized them using x-ray diffraction, transmission electron microscopy, superconducting quantum interference device (SQUID) magnetometry and electron magnetic resonance measurements. While the bulk sample shows a charge ordering transition at 245 K and an antiferromagnetic transition at 175 K, SQUID magnetometry and electron magnetic resonance experiments reveal that in the nanowires phase, a ferromagnetic transition occurs at ∼ 105 K. Further, the antiferromagnetic transition disappears and the charge ordering transition is suppressed. This result is particularly significant since the charge order in Pr0.5Ca0.5MnO3 is known to be very robust, magnetic fields as high as 27 T being needed to melt it.

Enhancement of charge and energy storage in sol-gel derived pure and La-modified PbZrO3 thin films

Antiferroelectric lanthanum-modified PbZrO3 thin films with La contents between 0 and 6 at. % have been deposited on Pt(111)/Ti/SiO2/Si substrate by sol-gel route. On the extent of La-modification, maximum polarization (Pmax) and recoverable energy density (W) have been enhanced followed by their subsequent reduction. A maximum Pmax ( ∼ 0.54 C/m2 at ∼ 60 MV/m) as well as a maximum W ( ∼ 14.9 J/cc at ∼ 60 MV/m) have been achieved on 5% La modification. Both Pmax and W have been found to be strongly dependent on La-induced crystallographic orientations.

C:N ratio of Sediments in a sewage fed Urban Lake

C:N ratio of lake sediments provide valuable information about the source and proportions of terrestrial, phytogenic and phycogenic carbon and nitrogen. This study has been carried out in Varthur lake which is receiving sewage since many decades apart from large scale land cover changes. C:N profile of the surficial sediment layer collected in the rainy and the dry seasons revealed higher C:N values[43] due to the accumulation of autochthonous organic material mostly at the deeper portions of the lake. This also highlights N limitation in the sludge either due to uptake by micro and macro-biota or rapid volatilization, denitrification and possible leaching in water. Organic Carbon was lower towards the inlets and higher near the deeper zones. This pattern of Organic C deposition was aided by gusty winds and high flow conditions together with impacts by the land use land cover changes in the watershed. Spatial variability of C:N in surficial sediments is significant compared to its seasonal variability. This communication provides an insight to the pattern in which nutrients are distributed in the sludge/sediment and its variation across seasons and space impacted by the biotic process accompanied by the hydrodynamic changes in the lake.

Charge transfer complex states in diketopyrrolopyrrole polymers and fullerene blends: Implications for organic solar cell efficiency

The spectral photocurrent characteristics of two donor-acceptor diketopyrrolopyrrole (DPP)-based copolymers (PDPP-BBT and TDPP-BBT) blended with a fullerene derivative [6,6]-phenyl C-61-butyric acid methyl ester (PCBM) were studied using Fourier-transform photocurrent spectroscopy (FTPS) and monochromatic photocurrent (PC) method. PDPP-BBT: PCBM shows the onset of the lowest charge transfer complex (CTC) state at 1.42 eV, whereas TDPP-BBT: PCBM shows no evidence of the formation of a midgap CTC state. The FTPS and PC spectra of P3HT:PCBM are also compared. The larger singlet state energy difference of TDPP-BBT and PCBM compared to PDPP-BBT/P3HT and PCBM obliterates the formation of a midgap CTC state resulting in an enhanced photovoltaic efficiency over PDPP-BBT: PCBM. (C) 2011 American Institute of Physics. [doi:10.1063/1.3670043]

Real-time density matrix renormalization group dynamics of spin and charge transport in push-pull polyenes and related systems

In this paper we investigate the effect of terminal substituents on the dynamics of spin and charge transport in donor-acceptor substituted polyenes [D-(CH)(x)-A] chains, also known as push-pull polyenes. We employ a long-range correlated model Hamiltonian for the D-(CH)(x)-A system, and time-dependent density matrix renormalization group technique for time propagating the wave packet obtained by injecting a hole at a terminal site, in the ground state of the system. Our studies reveal that the end groups do not affect spin and charge velocities in any significant way, but change the amount of charge transported. We have compared these push-pull systems with donor-acceptor substituted polymethine imine (PMI), D-(CHN)(x)-A, systems in which besides electron affinities, the nature of p(z) orbitals in conjugation also alternate from site to site. We note that spin and charge dynamics in the PMIs are very different from that observed in the case of push-pull polyenes, and within the time scale of our studies, transport of spin and charge leads to the formation of a ``quasi-static'' state.

Shear-enhanced diffusion in charge-stabilised colloids

The generalised Langevin equation method for the dynamics of interacting colloids presented in my previous lecture is extended here to the case of a sheared suspension. A calculation of shear-dependent diffusivities using these methods is found to account for puzzling observations in experiments and simulations. The limitations of the method are discussed, and important unresolved questions presented. This lecture summarises work done in collaboration with A.V. Indrani [1].

Molecular charge-transfer interaction with single-layer graphene

While the effect of electrochemical doping on single-layer graphene (SG) with holes and electrons has been investigated, the effect of charge-transfer doping on SG has not been examined hitherto. Effects of varying the concentration of electron donor and acceptor molecules such as tetrathiafulvalene (TTF) and tetracyanoethylene (TCNE) on SG produced by mechanical exfoliation as well as by the reduction of single-layer graphene oxide have been investigated. TTF softens the G-band in the Raman spectrum, whereas TCNE stiffens the G-band. The full-width-at-half-maximum of the G-band increases on interaction with both TTF and TCNE. These effects are similar to those found with few-layer graphene, but in contrast to those found with electrochemical doping. A common feature between the two types of doping is found in the case of the 2-D band, which shows softening and stiffening on electron and hole doping, respectively. The experimental results are explained on the basis of the frequency shifts, electron-phonon coupling and structural inhomogeneities that are relevant to molecule-graphene interaction.