Heterogeneity in Dye-TiO2 Interactions Dictate Charge Transfer Efficiencies for Diketopyrrolopyrrole-Based Polymer Sensitized Solar Cells

Power conversion efficiency of a solar cell is a complex parameter which usually hides the molecular details of the charge generation process. For rationally tailoring the overall device efficiency of the dye-sensitized solar cell, detailed molecular understanding of photoinduced reactions at the dye-TiO2 interface has to be achieved. Recently, near-IR absorbing diketopyrrolopyrrole-based (DPP) low bandgap polymeric dyes with enhanced photostabilities have been used for TiO2 sensitization with moderate efficiencies. To improve the reported device performances, a critical analysis of the polymerTiO(2) interaction and electron transfer dynamics is imperative. Employing a combination of time-resolved optical measurements complemented by low temperature EPR and steady-state Raman spectroscopy on polymerTiO(2) conjugates, we provide direct evidence for photoinduced electron injection from the TDPP-BBT polymer singlet state into TiO2 through the C-O group of the DPP-core. A detailed excited state description of the electron transfer process in films reveals instrument response function (IRF) limited (<110 fs) charge injection from a minor polymer fraction followed by a picosecond recombination. The major fraction of photoexcited polymers, however, does not show injection indicating pronounced ground state heterogeneity induced due to nonspecific polymerTiO(2) interactions. Our work therefore underscores the importance of gathering molecular-level insight into the competitive pathways of ultrafast charge generation along with probing the chemical heterogeneity at the nanoscale within the polymerTiO2 films for optimizing photovoltaic device efficiencies.

Evolution of Aromatic beta-Glucoside Utilization by Successive Mutational Steps in Escherichia coli

The bglA gene of Escherichia coli encodes phospho-beta-glucosidase A capable of hydrolyzing the plant-derived aromatic beta-glucoside arbutin. We report that the sequential accumulation of mutations in bglA can confer the ability to hydrolyze the related aromatic beta-glucosides esculin and salicin in two steps. In the first step, esculin hydrolysis is achieved through the acquisition of a four-nucleotide insertion within the promoter of the bglA gene, resulting in enhanced steady-state levels of the bglA transcript. In the second step, hydrolysis of salicin is achieved through the acquisition of a point mutation within the bglA structural gene close to the active site without the loss of the original catabolic activity against arbutin. These studies underscore the ability of microorganisms to evolve additional metabolic capabilities by mutational modification of preexisting genetic systems under selection pressure, thereby expanding their repertoire of utilizable substrates.

Seventeen-Level Inverter Formed by Cascading Flying Capacitor and Floating Capacitor H-Bridges

A multilevel inverter for generating 17 voltage levels using a three-level flying capacitor inverter and cascaded H-bridge modules with floating capacitors has been proposed. Various aspects of the proposed inverter like capacitor voltage balancing have been presented in the present paper. Experimental results are presented to study the performance of the proposed converter. The stability of the capacitor balancing algorithm has been verified both during transients and steady-state operation. All the capacitors in this circuit can be balanced instantaneously by using one of the pole voltage combinations. Another advantage of this topology is its ability to generate all the voltages from a single dc-link power supply which enables back-to-back operation of converter. Also, the proposed inverter can be operated at all load power factors and modulation indices. Additional advantage is, if one of the H-bridges fail, the inverter can still be operated at full load with reduced number of levels. This configuration has very low dv/dt and common-mode voltage variation.

Mycobacterium tuberculosis has diminished capacity to counteract redox stress induced by elevated levels of endogenous superoxide

Mycobacterium tuberculosis (Mtb) has evolved protective and detoxification mechanisms to maintain cytoplasmic redox balance in response to exogenous oxidative stress encountered inside host phagocytes. In contrast, little is known about the dynamic response of this pathogen to endogenous oxidative stress generated within Mtb. Using a noninvasive and specific biosensor of cytoplasmic redox state of Mtb, we for first time discovered a surprisingly high sensitivity of this pathogen to perturbation in redox homeostasis induced by elevated endogenous reactive oxygen species (ROS). We synthesized a series of hydroquinone-based small molecule ROS generators and found that ATD-3169 permeated mycobacteria to reliably enhance endogenous ROS including superoxide radicals. When Mtb strains including multidrug-resistant (MDR) and extensively drug-resistant (XDR) patient isolates were exposed to this compound, a dose-dependent, long-lasting, and irreversible oxidative shift in intramycobacterial redox potential was detected. Dynamic redox potential measurements revealed that Mtb had diminished capacity to restore cytoplasmic redox balance in comparison with Mycobacterium smegmatis (Msm), a fast growing nonpathogenic mycobacterial species. Accordingly, Mtb strains were extremely susceptible to inhibition by ATD-3169 but not Msm, suggesting a functional linkage between dynamic redox changes and survival. Microarray analysis showed major realignment of pathways involved in redox homeostasis, central metabolism, DNA repair, and cell wall lipid biosynthesis in response to ATD-3169, all consistent with enhanced endogenous ROS contributing to lethality induced by this compound. This work provides empirical evidence that the cytoplasmic redox poise of Mtb is uniquely sensitive to manipulation in steady-state endogenous ROS levels, thus revealing the importance of targeting intramycobacterial redox metabolism for controlling TB infection. (C) 2015 The Authors. Published by Elsevier Inc.

Reduction in DNA topoisomerase I level affects growth, phenotype and nucleoid architecture of Mycobacterium smegmatis

The steady-state negative supercoiling of eubacterial genomes is maintained by the action of DNA topoisomerases. Topoisomerase distribution varies in different species of mycobacteria. While Mycobacterium tuberculosis (Mtb) contains a single type I (Topol) and a single type II (Gyrase) enzyme, Mycobacterium smegmatis (Msm) and other members harbour additional relaxases. Topol is essential for Mtb survival. However, the necessity of Topol or other relaxases in Msm has not been investigated. To recognize the importance of Topol for growth, physiology and gene expression of Msm, we have developed a conditional knock-down strain of Topol in Msm. The Topol-depleted strain exhibited extremely slow growth and drastic changes in phenotypic characteristics. The cessation of growth indicates the essential requirement of the enzyme for the organism in spite of having additional DNA relaxation enzymes in the cell. Notably, the imbalance in Topol level led to the altered expression of topology modulatory proteins, resulting in a diffused nucleoid architecture. Proteomic and transcript analysis of the mutant indicated reduced expression of the genes involved in central metabolic pathways and core DNA transaction processes. RNA polymerase (RNAP) distribution on the transcription units was affected in the Topol-depleted cells, suggesting global alteration in transcription. The study thus highlights the essential requirement of Topol in the maintenance of cellular phenotype, growth characteristics and gene expression in mycobacteria. A decrease in Topol level led to altered RNAP occupancy and impaired transcription elongation, causing severe downstream effects.

HYDROMAGNETICS OF ADVECTIVE ACCRETION FLOWS AROUND BLACK HOLES: REMOVAL OF ANGULAR MOMENTUM BY LARGE-SCALE MAGNETIC STRESSES

We show that the removal of angular momentum is possible in the presence of large-scale magnetic stresses in geometrically thick, advective, sub-Keplerian accretion flows around black holes in steady state, in the complete absence of alpha-viscosity. The efficiency of such an angular momentum transfer could be equivalent to that of alpha-viscosity with alpha = 0.01-0.08. Nevertheless, the required field is well below its equipartition value, leading to a magnetically stable disk flow. This is essentially important in order to describe the hard spectral state of the sources when the flow is non/sub-Keplerian. We show in our simpler 1.5 dimensional, vertically averaged disk model that the larger the vertical-gradient of the azimuthal component of the magnetic field is, the stronger the rate of angular momentum transfer becomes, which in turn may lead to a faster rate of outflowing matter. Finding efficient angular momentum transfer in black hole disks via magnetic stresses alone, is very interesting when the generic origin of alpha-viscosity is still being explored.

Internal noise-driven generalized Langevin equation from a nonlocal continuum model

Starting with a micropolar formulation, known to account for nonlocal microstructural effects at the continuum level, a generalized Langevin equation (GLE) for a particle, describing the predominant motion of a localized region through a single displacement degree of freedom, is derived. The GLE features a memory-dependent multiplicative or internal noise, which appears upon recognizing that the microrotation variables possess randomness owing to an uncertainty principle. Unlike its classical version, the present GLE qualitatively reproduces the experimentally measured fluctuations in the steady-state mean square displacement of scattering centers in a polyvinyl alcohol slab. The origin of the fluctuations is traced to nonlocal spatial interactions within the continuum, a phenomenon that is ubiquitous across a broad class of response regimes in solids and fluids. This renders the proposed GLE a potentially useful model in such cases.

A Few Case Studies on the Correlation of Particle Network and Its Stability on the Ionic Conductivity of Solid-Liquid Composite Electrolytes

We discuss here the crucial role of the particle network and its stability on the long-range ion transport in solid liquid composite electrolytes. The solid liquid composite electrolytes chosen for the study here comprise nanometer sized silica (SiO2) particles having various surface chemical functionalities dispersed in nonaqueous lithium salt solutions, viz, lithium perchlorate (LiClO4) in two different polyethylene glycol based solvents. These systems constitute representative examples of an independent class of soft matter electrolytes known as ``soggy sand'' electrolytes, which have tremendous potential in diverse electrochemical devices. The oxide additive acts as a heterogeneous dopant creating free charge carriers and enhancing the local ion transport. For long-range transport, however, a stable spanning particle network is needed. Systematic experimental investigations here reveal that the spatial and time dependent characteristics of the particle network in the liquid solution are nontrivial. The network characteristics are predominantly determined by the chemical makeup of the electrolyte components and the chemical interactions between them. It is noteworthy that in this study the steady state macroscopic ionic conductivity and viscosity of the solid liquid composite electrolyte are observed to be greatly determined by the additive oxide surface chemical functionality, solvent chemical composition, and solvent dielectric constant.

A finite variant of the Toom Model

We present results for a finite variant of the one-dimensional Toom model with closed boundaries. We show that the steady state distribution is not of product form, but is nonetheless simple. In particular, we give explicit formulas for the densities and some nearest neighbour correlation functions. We also give exact results for eigenvalues and multiplicities of the transition matrix using the theory of R-trivial monoids in joint work with A. Schilling, B. Steinberg and N. M. Thiery.

A Voltage Space Vector Diagram Formed by Nineteen Concentric Dodecagons for Medium-Voltage Induction Motor Drive

In this paper, a multilevel dodecagonal voltage space vector structure with nineteen concentric dodecagons is proposed for the first time. This space vector structure is achieved by cascading two sets of asymmetric three-level inverters with isolated H-bridges on either side of an open-end winding induction motor. The dodecagonal structure is made possible by proper selection of dc link voltages and switching states of the inverters. The proposed scheme retains all the advantages of multilevel topologies as well as the advantages of dodecagonal voltage space vector structure. In addition to that, a generic and simple method for calculation of pulsewidth modulation timings using only sampled reference values (v(alpha) and v(beta)) is proposed. This enables the scheme to be used for any closed-loop application such as vector control. In addition, a new method of switching technique is proposed, which ensures minimum switching while eliminating the fifth-and seventh-order harmonics and suppressing the eleventh and thirteenth harmonics, eliminating the need for bulky filters. The motor phase voltage is a 24-stepped wave-form for the entire modulation range thereby reducing the number of switchings of the individual inverter modules. Experimental results for steady-state operation, transient operation, including start-up have been presented and the results of fast Fourier transform analysis is also presented for validating the proposed concept.

Modeling the co-transport of viruses and colloids in unsaturated porous media

A mathematical model is developed to simulate the co-transport of viruses and colloids in unsaturated porous media under steady-state flow conditions. The virus attachment to the mobile and immobile colloids is described using a linear reversible kinetic model. Colloid transport is assumed to be decoupled from virus transport; that is, we assume that colloids are not affected by the presence of attached viruses on their surface. The governing equations,are solved numerically using an alternating three-step operator splitting approach. The model is verified by fitting three sets of experimental data published in the literature: (1) Syngouna and Chrysikopoulos (2013) and (2) Walshe et al. (2010), both on the co-transport of viruses and clay colloids under saturated conditions, and (3) Syngouna and Cluysikopoulos (2015) for the co-transport of viruses and clay colloids under unsaturated conditions. We found a good agreement between observed and fitted breakthrough curves (BTCs) under both saturated and unsaturated conditions. Then, the developed model was used to simulate the co-transport of viruses and colloids in porous media under unsaturated conditions, with the aim of understanding the relative importance of various processes on the co-transport of viruses and colloids in unsaturated porous media. The virus retention in porous media in the presence of colloids is greater during unsaturated conditions as compared to the saturated conditions due to: (1) virus attachment to the air-water interface (AWI), and (2) co-deposition of colloids with attached viruses on its surface to the AWL A sensitivity analysis of the model to various parameters showed that the virus attachment to AWI is the most sensitive parameter affecting the BTCs of both free viruses and total mobile viruses and has a significant effect on all parts of the BTC. The free and the total mobile viruses BTCs are mainly influenced by parameters describing virus attachment to the AIM, virus interaction with mobile and immobile colloids, virus attachment to solid-water interface (SWI), and colloid interaction with SWI and AWL The virus BTC is relatively insensitive to parameters describing the maximum adsorption capacity of the AWI for colloids, inlet colloid concentration, virus detachment rate coefficient from the SW!, maximum adsorption capacity of the AWI for viruses and inlet virus concentration. (C) 2015 Elsevier B.V. All rights reserved.

In Situ Crystallographic Probing on Ameliorating Effect of Sulfide Additives and Carbon Grafting in Iron Electrodes

Beneficial effects of carbon grafting into the iron active material for rechargeable alkaline-iron-electrodes with and without Bi2S3 additive is probed by in situ X-ray diffraction in conjunction with Extended X-ray Absorption Fine Structure (EXAFS) and electrochemistry. EXAFS data unravel that the composition of pristine active material (PAM) for iron electrodes comprises 87% of magnetite and 13% of alpha-iron while carbon-grafted active material comprises 60% of magnetite and 40% of alpha-iron. In situ XRD patterns are recorded using a specially designed electrochemical cell. XRD data reflect that magnetite present in PAM iron electrode, without bismuth sulfide additive, is not reduced during charging while PAM iron electrode with bismuth sulfide additive is partially reduced to alpha-Fe/Fe(OH)(2). Interestingly, carbon-grafted-iron electrodes with bismuth sulfide exhibit complete conversion of active material to alpha-Fe/Fe(OH)2. The ameliorating effect of carbon grafting is substantiated by kinetic parameters obtained from steady-state potentiostatic polarization and Tafel plots. The mechanism for iron-electrode charge - discharge reactions are discussed in the light of the potential - pH diagrams for Fe - H2O, S - H2O and FeSads - H2O systems and it is surmised that carbon grafting into iron active material promotes its electrochemical utilization. (C) The Author(s) 2015. Published by ECS. All rights reserved.

Peristaltic pump-based low range pressure sensor calibration system

Peristaltic pumps were normally used to pump liquids in several chemical and biological applications. In the present study, a peristaltic pump was used to pressurize the chamber (positive as well negative pressures) using atmospheric air. In the present paper, we discuss the development and performance study of an automatic pressurization system to calibrate low range (millibar) pressure sensors. The system includes a peristaltic pump, calibrated pressure sensor (master sensor), pressure chamber, and the control electronics. An in-house developed peristaltic pump was used to pressurize the chamber. A closed loop control system has been developed to detect and adjust the pressure leaks in the chamber. The complete system has been integrated into a portable product. The system performance has been studied for a step response and steady state errors. The system is portable, free from oil contaminants, and consumes less power compared to existing pressure calibration systems. The veracity of the system was verified by calibrating an unknown diaphragm based pressure sensor and the results obtained were satisfactory. (C) 2015 AIP Publishing LLC.

Computationally efficient models for simulation of non-ideal DC-DC converters operating in continuous and discontinuous conduction modes

This paper discusses dynamic modeling of non-isolated DC-DC converters (buck, boost and buck-boost) under continuous and discontinuous modes of operation. Three types of models are presented for each converter, namely, switching model, average model and harmonic model. These models include significant non-idealities of the converters. The switching model gives the instantaneous currents and voltages of the converter. The average model provides the ripple-free currents and voltages, averaged over a switching cycle. The harmonic model gives the peak to peak values of ripple in currents and voltages. The validity of all these models is established by comparing the simulation results with the experimental results from laboratory prototypes, at different steady state and transient conditions. Simulation based on a combination of average and harmonic models is shown to provide all relevant information as obtained from the switching model, while consuming less computation time than the latter.

Optimal input cross-power spectra in shake table testing of asymmetric structures

The study considers earthquake shake table testing of bending-torsion coupled structures under multi-component stationary random earthquake excitations. An experimental procedure to arrive at the optimal excitation cross-power spectral density (psd) functions which maximize/minimize the steady state variance of a chosen response variable is proposed. These optimal functions are shown to be derivable in terms of a set of system frequency response functions which could be measured experimentally without necessitating an idealized mathematical model to be postulated for the structure under study. The relationship between these optimized cross-psd functions to the most favourable/least favourable angle of incidence of seismic waves on the structure is noted. The optimal functions are also shown to be system dependent, mathematically the sharpest, and correspond to neither fully correlated motions nor independent motions. The proposed experimental procedure is demonstrated through shake table studies on two laboratory scale building frame models.