Time-resolved Fourier transform infrared spectroscopic imaging

Fourier transform infrared (FT-IR) imaging allows simultaneous spectral characterization of large spatial areas due to its multichannel detection advantage. The acquisition of large amounts of data in the multichannel configuration results, however, in a poor temporal resolution of sequentially acquired data sets, which limits the examination of dynamic processes to processes that have characteristic time scales of the order of minutes. Here, we introduce the concept and instrumental details of a time-resolved infrared spectroscopic imaging modality that permits the examination of repetitive dynamic processes whose half-lives are of the order of milli-seconds. As an illustration of this implementation of step-scan FT-IR imaging, we examine the molecular responses to external electric-field perturbations of a microscopically heterogeneous polymer-liquid crystal composite. Analysis of the spectroscopic data using conventional univariate and generalized two-dimensional (2D) correlation methods emphasizes an additional capability for accessing of simultaneous spatial and temporal chemical measurements of molecular dynamic processes.     

A continuous-flow system for high-precision kinetics using small volumes

A generally applicable continuous-flow kinetic analysis system that gives data of a precision high enough to measure small kinetic isotope effects for enzymatic and nonenzymatic reactions is described. It employs commercially available components that are readily assembled into an apparatus that is easy to use. It operates under laminar flow conditions, which requires that the time between the initiation of the reaction in the mixer and the observation be long enough that molecular diffusion can effect a symmetrization of the concentration profile that results from a thin plug of reagents introduced at the mixer. The analysis of a second-order irreversible reaction under pseudo-first-order conditions is presented. The Yersinia pestis protein tyrosine phosphatase catalyzed hydrolysis of p-nitrophenyl phosphate is characterized with the system, and a proton inventory on kcat is presented.     

In-Place Stabilization of Pond Ash Deposits by Hydrated Lime Columns

Abandoned coal ash ponds cover up vast stretches of precious land and cause environmental problems. Application of suitable in situ stabilization methods may bring about improvement in the geotechnical properties of the ash deposit as a whole, converting it to a usable site. In this study, a technique of in-place stabilization by hydrated lime columns was applied to large-scale laboratory models of ash ponds. Samples collected from different radial distances and different depths of the ash deposit were tested to study the improvements in the water content, dry density, particle size distribution, unconfined compressive strength, pH, hydraulic conductivity, and leachate characteristics over a period of one year. The in-place stabilization by lime column technique has been found effective in increasing the unconfined compressive strength and reducing hydraulic conductivity of pond ash deposits in addition to modifying other geotechnical parameters. The method has also proved to be useful in reducing the contamination potential of the ash leachates, thus mitigating the adverse environmental effects of ash deposits.     

Two-stage Robust Network Design with Exponential Scenarios

We study two-stage robust variants of combinatorial optimization problems on undirected graphs, like Steiner tree, Steiner forest, and uncapacitated facility location. Robust optimization problems, previously studied by Dhamdhere et al. (Proc. of 46th Annual IEEE Symposium on Foundations of Computer Science (FOCS’05), pp. 367–378, 2005), Golovin et al. (Proc. of the 23rd Annual Symposium on Theoretical Aspects of Computer Science (STACS), 2006), and Feige et al. (Proc. of the 12th International Integer Programming and Combinatorial Optimization Conference, pp. 439–453, 2007), are two-stage planning problems in which the requirements are revealed after some decisions are taken in Stage 1. One has to then complete the solution, at a higher cost, to meet the given requirements. In the robust k-Steiner tree problem, for example, one buys some edges in Stage 1. Then k terminals are revealed in Stage 2 and one has to buy more edges, at a higher cost, to complete the Stage 1 solution to build a Steiner tree on these terminals. The objective is to minimize the total cost under the worst-case scenario. In this paper, we focus on the case of exponentially many scenarios given implicitly. A scenario consists of any subset of k terminals (for k-Steiner tree), or any subset of k terminal-pairs (for k-Steiner forest), or any subset of k clients (for facility location). Feige et al. (Proc. of the 12th International Integer Programming and Combinatorial Optimization Conference, pp. 439–453, 2007) give an LP-based general framework for approximation algorithms for a class of two stage robust problems. Their framework cannot be used for network design problems like k-Steiner tree (see later elaboration). Their framework can be used for the robust facility location problem, but gives only a logarithmic approximation. We present the first constant-factor approximation algorithms for the robust k-Steiner tree (with exponential number of scenarios) and robust uncapacitated facility location problems. Our algorithms are combinatorial and are based on guessing the optimum cost and clustering to aggregate nearby vertices. For the robust k-Steiner forest problem on trees and with uniform multiplicative increase factor for Stage 2 (also known as inflation), we present a constant approximation. We show APX-hardness of the robust min-cut problem (even with singleton-set scenarios), resolving an open question of (Dhamdhere et al. in Proc. of 46th Annual IEEE Symposium on Foundations of Computer Science (FOCS’05), pp. 367–378, 2005) and (Golovin et al. in Proc. of the 23rd Annual Symposium on Theoretical Aspects of Computer Science (STACS), 2006).     

Red emitting MTiO3 (M = Ca or Sr) phosphors doped with Eu3+ or Pr3+ with some cations as co-dopants

Ca (or Sr)TiO₃:Eu³⁺, M (Li⁺ or Na⁺ or K⁺) and CaTiO₃:Pr³⁺, M (Li⁺ or Na⁺ or Ag⁺ or K⁺ or Gd³⁺ or La³⁺) powders were prepared by combustion synthesis method and the samples were further heated to ～1000 °C to improve the crystallinity. The structure and morphology of materials were examined by X-ray diffraction (XRD) and a scanning electron microscopy (SEM). The morphologies of SrTiO₃:Eu³⁺, CaTiO₃:Eu³⁺ or CaTiO₃:Pr³⁺ powders co-doped with other metal ions were very similar. Small and coagulated particles of nearly cubical shapes with small size distribution having smooth and regular surface were formed. Photo-luminescence spectra of CaTiO₃:Pr³⁺ and co-doped either with Li⁺, Na⁺, K⁺, Ag⁺, La³⁺ or Gd³⁺ ions showed red emissions at 613 nm due to the ¹D₂ → ³H₄ transition of Pr³⁺. The variation of intensity of emission peak with different co-doping follows the order: K⁺ > Ag⁺ > Na⁺ > Li⁺ > La³⁺ > Gd³⁺. The characteristic emissions of CaTiO₃:Eu³⁺ lattices had strong emission at 614 and 620 nm for ⁵D₀ → ⁷F₂ with other weak transitions observed at 580, 592, 654, 705 nm for ⁵D₀ → ⁷F_n transitions where n = 0, 1, 3, 4 respectively in all host lattices. Photoluminescence intensity in SrTiO₃:Eu³⁺ is more than CaTiO₃:Eu³⁺ lattices. A remarkable increase of photoluminescence intensity (in ⁵D₀ → ⁷F₂ transition) was observed if co-doped with Li⁺ ions in CaTiO₃:Eu³⁺ and SrTiO3:Eu³⁺.     

Enhanced SO2 concentrations observed over northern India: role of long-range transport

The combustion of fossil fuels (coal and petroleum products) constitutes a source of continuous release of anthropogenic SO₂ into the atmosphere. Furthermore, natural sources such as volcanoes can inject large amounts of SO₂ directly into the troposphere and sometimes even into the stratosphere. These event-based volcanic eruptions provide solitary opportunities to study the transport and transformation of atmospheric constituents. In this study, we present an episode of high SO₂ concentration over northern India as a result of long-range transport from Africa using multiple satellite observations. Monthly averaged column SO₂ values over the Indo-Gangetic Plain (IGP) were observed in the range of 0.6–0.9 Dobson units (DU) during November 2008 using observations from the Ozone Monitoring Instrument (OMI). These concentrations were conspicuously higher than the background concentrations (<0.3 DU) observed during 2005–2010 over this region. The columnar SO₂ loadings were highest on 6 November over most of the IGP region and even exceeded 6 DU, a factor of 10–20 higher than background levels in some places. These enhanced SO₂ levels were not reciprocated in satellite-derived NO₂ or CO columns, indicating transport from a non-anthropogenic SO₂ source. As most of the local aerosols over the IGP region occur below 3 km, a well-separated layer at 4–5 km was observed from the Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observations (CALIPSO) satellite. Wind fields and back-trajectory analysis revealed a strong flow originating from the Dalaffilla volcanic eruption in Ethiopia during 4–6 November 2008. Although volcanic SO₂ plumes have been extensively studied over many parts of Asia, Europe, and the USA, analysis of such events for the IGP region is being reported for the first time in this study.     

Metal oxide nanoparticles for advanced energy applications

Hot-wire chemical vapor deposition (HWCVD) has been employed as an economically scalable method for the deposition of crystalline molybdenum oxide nanoparticles at high density. Under optimal synthesis conditions, only crystalline nanostructures with a smallest dimension of ~ 3-50 nm are observed with extensive transmission electron microscopy analyses. The incorporation of crystalline molybdenum oxide nanoparticles into battery electrodes has led to profound advancements in state-of-the-art negative electrodes (anodes) in lithium-ion batteries. The nanoparticle materials exhibit a high rate capability as anticipated for the reduced solid-state Li-ion diffusion length.