The role of halide ions on the electrochemical behaviour of iron in alkali solutions

Science.gov (United States)

Begum, S. Nathira; Muralidharan, V. S.; Basha, C. Ahmed

2008-02-01

Active dissolution and passivation of transition metals in alkali solutions is of technological importance in batteries. The performance of alkaline batteries is decided by the presence of halides as they influence passivation. Cyclic voltammetric studies were carried out on iron in different sodium hydroxide solutions in presence of halides. In alkali solutions iron formed hydroxo complexes and their polymers in the interfacial diffusion layer. With progress of time they formed a cation selective layer. The diffusion layer turned into bipolar ion selective layer consisted of halides, a selective inner sublayer to the metal side and cation selective outer layer to the solution side. At very high anodic potentials, dehydration and deprotonation led to the conversion of salt layer into an oxide.

Structure of polyvalent metal halide melts

International Nuclear Information System (INIS)

Tosi, M.P.

1990-12-01

A short review is given of recent progress in determining and understanding the structure of molten halide salts involving polyvalent metal ions. It covers the following three main topics: (i) melting mechanisms and types of liquid structure for pure polyvalent-metal chlorides; (ii) geometry and stability of local coordination for polyvalent metal ions in molten mixtures of their halides with alkali halides; and (iii) structure breaking and electron localization on addition of metal to the melt. (author). 28 refs, 3 figs, 1 tab

Near-UV sensitized 1.06 μm emission of Nd{sup 3+} ions via monovalent copper in phosphate glass

Energy Technology Data Exchange (ETDEWEB)

Jiménez, José A., E-mail: jose.jimenez@unf.edu [Department of Chemistry, University of North Florida, Jacksonville, FL 32224 (United States); Sendova, Mariana [Optical Spectroscopy & Nano-Materials Lab, New College of Florida, Sarasota, FL 34243 (United States)

2015-07-15

Monovalent copper ions effectively incorporated in Nd-containing phosphate glass by a single-step melt-quench method have been established as near-ultraviolet (UV) sensitizers of Nd{sup 3+} ions, resulting in a remarkable {sup 4}F{sub 3/2} → {sup 4}I{sub 11/2} emission at 1.06 μm. The spectroscopic data indicates an efficient energy conversion process. The Cu{sup +} ions first absorb photons broadly around 360 nm, and subsequently transfer the energy from the Stokes-shifted emitting states to resonant Nd{sup 3+} energy levels in the visible. Ultimately, the Nd{sup 3+} electronic excited states decay and the upper lasing state {sup 4}F{sub 3/2} is populated, leading to the enhanced emission at 1.06 μm. The characteristic features of the Cu{sup +} visible emission spectra and the reduced lifetime of the corresponding Cu{sup +} donor states indicate an efficient non-radiative transfer. The Cu{sup +}/Nd{sup 3+} co-doped phosphate glass appears suitable as solid-state laser material with enhanced pump range in the near-UV part of the spectrum and for solar spectral conversion in photovoltaic cells. - Graphical abstract: Display Omitted - Highlights: • Monovalent copper ions effectively stabilized in Nd{sup 3+}-containing phosphate glass. • Enhanced Nd{sup 3+} near-infrared emission observed upon the Cu{sup +} ions incorporation. • Cu{sup +} → Nd{sup 3+} non-radiative energy transfer efficiencies and likely energy transfer pathways evaluated. • Potential for solid-state lasers and solar spectral conversion suggested.

Simultaneous Analysis of Monovalent Anions and Cations with a Sub-Microliter Dead-Volume Flow-Through Potentiometric Detector for Ion Chromatography

Science.gov (United States)

Dumanli, Rukiye; Attar, Azade; Erci, Vildan; Isildak, Ibrahim

2016-01-01

A microliter dead-volume flow-through cell as a potentiometric detector is described in this article for sensitive, selective and simultaneous detection of common monovalent anions and cations in single column ion chromatography for the first time. The detection cell consisted of less selective anion- and cation-selective composite membrane electrodes together with a solid-state composite matrix reference electrode. The simultaneous separation and sensitive detection of sodium (Na+), potassium (K+), ammonium (NH4+), chloride (Cl−) and nitrate (NO3−) in a single run was achieved by using 98% 1.5 mM MgSO4 and 2% acetonitrile eluent with a mixed-bed ion-exchange separation column without suppressor column system. The separation and simultaneous detection of the anions and cations were completed in 6 min at the eluent flow-rate of 0.8 mL/min. Detection limits, at S/N = 3, were ranged from 0.2 to 1.0 µM for the anions and 0.3 to 3.0 µM for the cations, respectively. The developed method was successfully applied to the simultaneous determination of monovalent anions and cations in several environmental and biological samples. PMID:26786906

Balance of unidirectional monovalent ion fluxes in cells undergoing apoptosis: why does Na+/K+ pump suppression not cause cell swelling?

Science.gov (United States)

Yurinskaya, Valentina E; Rubashkin, Andrey A; Vereninov, Alexey A

2011-05-01

Cells dying according to the apoptotic program, unlike cells dying via an unprogrammed mode, are able to avoid swelling and osmotic bursting with membrane disruption.There are indications that apoptosis is accompanied by suppression of the Na+/K+ pump and changes in the K+ and Cl− channels. It remains unclear how ion fluxes through individual ion pathways are integrated so as to induce loss of intracellular ions and concomitant apoptotic volume decrease. A decrease in activity of the sodium pump during apoptosis should cause cell swelling rather than shrinkage. We have made the first systemic analysis of the monovalent ion flux balance in apoptotic cells. Experimental data were obtained for human U937 cells treated with staurosporine for 4–5 h, which is known to induce apoptosis. The data include cellular Cl− content and fluxes, K+, Na+, water content and ouabain-sensitive and -resistant Rb+ fluxes.Unidirectional monovalent ion fluxeswere calculated using these data and a cell model comprising the double Donnan system with the Na+/K+ pump, Cl−, K+, Na+ channels, the Na+–K+–2Cl−cotransporter (NKCC), the Na+–Cl− cotransporter (NC), and the equivalent Cl−/Cl− exchange.Apoptotic cell shrinkage was found to be caused, depending on conditions, either by an increase in the integral channel permeability of membrane for K+ or by suppression of the pump coupledwith a decrease in the integral channel permeability of membrane for Na+. The decrease in the channel permeability of membrane for Na+ plays a crucial role in cell dehydration in apoptosis accompanied by suppression of the pump. Supplemental Table S1 is given for easy calculating flux balance under specified conditions.

Excited-atom production by electron and ion bombardment of alkali halides

International Nuclear Information System (INIS)

Walkup, R.E.; Avouris, P.; Ghosh, A.P.

1987-01-01

We present experimental results on the production of excited atoms by electron and ion bombardment of alkali halides. For the case of electron bombardment, Doppler shift measurements show that the electronically excited atoms have a thermal velocity distribution in equilibrium with the surface temperature. Measurements of the absolute yield of excited atoms, the distribution of population among the excited states, and the systematic dependence on incident electron current and sample temperature support a model in which the excited atoms are produced by gas-phase collisions between desorbed ground-state atoms and secondary electrons. In contrast, for the case of ion bombardment, the excited atoms are directly sputtered from the surface, with velocity distributions characteristic of a collision cascade, and with typical energies of --10 eV

Unraveling halide hydration: A high dilution approach.

Science.gov (United States)

Migliorati, Valentina; Sessa, Francesco; Aquilanti, Giuliana; D'Angelo, Paola

2014-07-28

The hydration properties of halide aqua ions have been investigated combining classical Molecular Dynamics (MD) with Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy. Three halide-water interaction potentials recently developed [M. M. Reif and P. H. Hünenberger, J. Chem. Phys. 134, 144104 (2011)], along with three plausible choices for the value of the absolute hydration free energy of the proton (ΔG [minus sign in circle symbol]hyd[H+]), have been checked for their capability to properly describe the structural properties of halide aqueous solutions, by comparing the MD structural results with EXAFS experimental data. A very good agreement between theory and experiment has been obtained with one parameter set, namely LE, thus strengthening preliminary evidences for a ΔG [minus sign in circle symbol]hyd[H] value of -1100 kJ mol(-1) [M. M. Reif and P. H. Hünenberger, J. Chem. Phys. 134, 144104 (2011)]. The Cl(-), Br(-), and I(-) ions have been found to form an unstructured and disordered first hydration shell in aqueous solution, with a broad distribution of instantaneous coordination numbers. Conversely, the F(-) ion shows more ordered and defined first solvation shell, with only two statistically relevant coordination geometries (six and sevenfold complexes). Our thorough investigation on the effect of halide ions on the microscopic structure of water highlights that the perturbation induced by the Cl(-), Br(-), and I(-) ions does not extend beyond the ion first hydration shell, and the structure of water in the F(-) second shell is also substantially unaffected by the ion.

Solvated Positron Chemistry. Competitive Positron Reactions with Halide Ions in Water

DEFF Research Database (Denmark)

Christensen, Palle; Pedersen, Niels Jørgen; Andersen, J. R.

1979-01-01

It is shown by means of the angular correlation technique that the binding of positrons to halides is strongly influenced by solvation effects. For aqueous solutions we find increasing values for the binding energies between the halide and the positron with increasing mass of the halide...

Synergistic effect of halide ions on the corrosion inhibition of aluminium in H2SO4 using 2-acetylphenothiazine

International Nuclear Information System (INIS)

Ebenso, E.E.

2003-01-01

The corrosion inhibition of aluminium in H 2 SO 4 in the presence of 2-acetylphenothiazine (2APTZ) at temperature range of 30-60 deg. C was studied using the weight loss and thermometric techniques. The effect of addition of halides (KCl, KBr, KI) is also reported. The inhibition efficiency (I, %) increased with increase in concentration of 2APTZ. The addition of the halides increased the inhibition efficiency to a considerable extent. The temperature increased the corrosion rate and inhibition efficiency in the range 30-60 deg. C in the absence and presence of the inhibitor and halides. Phenomenon of chemical adsorption is proposed. Flory-Huggins adsorption isotherm equation was obeyed at all the concentrations studied. The decrease in inhibition efficiency (and surface coverage values) was found to be in the order I - >Br - >Cl - which clearly indicates that the radii and the electronegativity of halides play a significant role in the adsorption process. All the data acquired reveal that 2APTZ acts as an inhibitor in the acid environment from the two techniques used. The synergistic effect of 2APTZ and halide ions is discussed

Solvation structures of lithium halides in methanol–water mixtures

International Nuclear Information System (INIS)

Sarkar, Atanu; Dixit, Mayank Kumar; Tembe, B.L.

2015-01-01

Highlights: • Potentials of mean force for Li + -halides are calculated in methanol–water mixtures. • Stable CIP for x methanol = 1.0 becomes unstable at and below x methanol = 0.75. • The Li + ion is preferentially solvated by methanol molecules. • The halide ions are preferentially solvated by water molecules. - Abstract: The potentials of mean force (PMFs) for the ion pairs, Li + −Cl − , Li + −Br − and Li + −I − have been calculated in five methanol–water compositions. The results obtained are verified by trailing the trajectories and calculating the ion pair distance residence times. Local structures around the ions are studied using the radial distribution functions, density profiles, orientational correlation functions, running coordination numbers and excess coordination numbers. The major change in PMF is observed as the methanol mole fraction (x methanol ) is changed from 1.0 to 0.75. The stable contact ion pair occurring for x methanol = 1.0 becomes unstable at and below x methanol = 0.75. The preferential solvation data show that the halide ions are always preferentially solvated by water molecules. Although the lithium ion is preferentially solvated by methanol molecules, there is significant affinity towards water molecules as well

Linkage of molecular units in the chemistry of niobium and tantalum cluster halides

International Nuclear Information System (INIS)

Perrin, C.; Sergent, M.

1991-01-01

In low valency niobium and tantalum halides, interunit linkages are observed between the (Me 6 X 12 )X 6 units. They are insulators and interesting magnetic properties are observed, due to the intrinsic potential magnetism of the Me 6 cluster and depending on the inserted cations, for instance rare earths in MM'Nb 6 Cl 18 (M = monovalent cation, M' = rare earth). Of special interest are the niobium iodides which exhibit (Me 6 X 8 )X 6 units, an exception in the niobium chemistry; interesting properties have been reported for some of these iodides

Direct ToF-SIMS analysis of organic halides and amines on TLC plates

Energy Technology Data Exchange (ETDEWEB)

Parent, Alexander A. [Department of Chemistry and Biochemistry, Brigham Young University, Provo, UT 84602 (United States); Anderson, Thomas M. [Department of Chemistry and Biochemistry, Brigham Young University, Provo, UT 84602 (United States); Michaelis, David J. [Department of Chemistry and Biochemistry, Brigham Young University, Provo, UT 84602 (United States); Jiang, Guilin [Department of Chemistry and Biochemistry, Brigham Young University, Provo, UT 84602 (United States); Savage, Paul B. [Department of Chemistry and Biochemistry, Brigham Young University, Provo, UT 84602 (United States); Linford, Matthew R. [Department of Chemistry and Biochemistry, Brigham Young University, Provo, UT 84602 (United States)]. E-mail: mrlinford@chem.byu.edu

2006-07-30

It has been reported that: 'direct analysis of thin layer chromatography (TLC) plates with secondary ion mass spectrometry (SIMS) yields no satisfactory results' (J. Chromatogr. A 1084 (2005) 113-118). While this statement appears to be true in general, we have identified two important classes of compounds, organic halides and amines, that appear to yield to such direct analyses. For example, five organic halides with diverse structures were eluted on normal phase TLC plates. In all cases the halide signals in the negative ion time-of-flight secondary ion mass spectrometry (ToF-SIMS) spectra were notably stronger than the background signals. Similarly, a series of five organic amines with diverse structures were directly analyzed by positive ion ToF-SIMS. In all but one of the spectra characteristic, and sometimes even quasi-molecular ions, were observed. Most likely, the good halide ion yields are largely a function of the electronegativity of the halogens. We also propose that direct analysis of amines on normal phase silica gel is facilitated by the acidity, i.e., proton donation, of surface silanol groups.

Direct ToF-SIMS analysis of organic halides and amines on TLC plates

International Nuclear Information System (INIS)

Parent, Alexander A.; Anderson, Thomas M.; Michaelis, David J.; Jiang, Guilin; Savage, Paul B.; Linford, Matthew R.

2006-01-01

It has been reported that: 'direct analysis of thin layer chromatography (TLC) plates with secondary ion mass spectrometry (SIMS) yields no satisfactory results' (J. Chromatogr. A 1084 (2005) 113-118). While this statement appears to be true in general, we have identified two important classes of compounds, organic halides and amines, that appear to yield to such direct analyses. For example, five organic halides with diverse structures were eluted on normal phase TLC plates. In all cases the halide signals in the negative ion time-of-flight secondary ion mass spectrometry (ToF-SIMS) spectra were notably stronger than the background signals. Similarly, a series of five organic amines with diverse structures were directly analyzed by positive ion ToF-SIMS. In all but one of the spectra characteristic, and sometimes even quasi-molecular ions, were observed. Most likely, the good halide ion yields are largely a function of the electronegativity of the halogens. We also propose that direct analysis of amines on normal phase silica gel is facilitated by the acidity, i.e., proton donation, of surface silanol groups

Synergistic effect of halide ions on the corrosion inhibition of aluminium in H{sub 2}SO{sub 4} using 2-acetylphenothiazine

Energy Technology Data Exchange (ETDEWEB)

Ebenso, E.E

2003-03-05

The corrosion inhibition of aluminium in H{sub 2}SO{sub 4} in the presence of 2-acetylphenothiazine (2APTZ) at temperature range of 30-60 deg. C was studied using the weight loss and thermometric techniques. The effect of addition of halides (KCl, KBr, KI) is also reported. The inhibition efficiency (I, %) increased with increase in concentration of 2APTZ. The addition of the halides increased the inhibition efficiency to a considerable extent. The temperature increased the corrosion rate and inhibition efficiency in the range 30-60 deg. C in the absence and presence of the inhibitor and halides. Phenomenon of chemical adsorption is proposed. Flory-Huggins adsorption isotherm equation was obeyed at all the concentrations studied. The decrease in inhibition efficiency (and surface coverage values) was found to be in the order I{sup -}>Br{sup -}>Cl{sup -} which clearly indicates that the radii and the electronegativity of halides play a significant role in the adsorption process. All the data acquired reveal that 2APTZ acts as an inhibitor in the acid environment from the two techniques used. The synergistic effect of 2APTZ and halide ions is discussed.

The coacervation of aqueous solutions of tetraalkylammonium halides

International Nuclear Information System (INIS)

Mugnier de Trobriand, Anne.

1979-09-01

The coacervation of aqueous solutions of tatraalkylammonium halides in the presence of not of inorganic halides and acids has been studied, considering thermodynamic and spectroscopic aspects. The importance of dispersion forces as well as forces resulting from hydrophobic hydration has been assessed. The analogy between these systems and anionic ion exchange resins has been shown especially for Uranium VI extraction [fr

Unveiling the Shape Evolution and Halide-Ion-Segregation in Blue-Emitting Formamidinium Lead Halide Perovskite Nanocrystals Using an Automated Microfluidic Platform.

Science.gov (United States)

Lignos, Ioannis; Protesescu, Loredana; Emiroglu, Dilara Börte; Maceiczyk, Richard; Schneider, Simon; Kovalenko, Maksym V; deMello, Andrew J

2018-02-14

Hybrid organic-inorganic perovskites and in particular formamidinium lead halide (FAPbX 3 , X = Cl, Br, I) perovskite nanocrystals (NCs) have shown great promise for their implementation in optoelectronic devices. Specifically, the Br and I counterparts have shown unprecedented photoluminescence properties, including precise wavelength tuning (530-790 nm), narrow emission linewidths (photoluminescence quantum yields (70-90%). However, the controlled formation of blue emitting FAPb(Cl 1-x Br x ) 3 NCs lags behind their green and red counterparts and the mechanism of their formation remains unclear. Herein, we report the formation of FAPb(Cl 1-x Br x ) 3 NCs with stable emission between 440 and 520 nm in a fully automated droplet-based microfluidic reactor and subsequent reaction upscaling in conventional laboratory glassware. The thorough parametric screening allows for the elucidation of parametric zones (FA-to-Pb and Br-to-Cl molar ratios, temperature, and excess oleic acid) for the formation of nanoplatelets and/or NCs. In contrast to CsPb(Cl 1-x Br x ) 3 NCs, based on online parametric screening and offline structural characterization, we demonstrate that the controlled synthesis of Cl-rich perovskites (above 60 at% Cl) with stable emission remains a challenge due to fast segregation of halide ions.

Relative Free Energies for Hydration of Monovalent Ions from QM and QM/MM Simulations.

Science.gov (United States)

Lev, Bogdan; Roux, Benoît; Noskov, Sergei Yu

2013-09-10

Methods directly evaluating the hydration structure and thermodynamics of physiologically relevant cations (Na(+), K(+), Cl(-), etc.) have wide ranging applications in the fields of inorganic, physical, and biological chemistry. All-atom simulations based on accurate potential energy surfaces appear to offer a viable option for assessing the chemistry of ion solvation. Although MD and free energy simulations of ion solvation with classical force fields have proven their usefulness, a number of challenges still remain. One of them is the difficulty of force field benchmarking and validation against structural and thermodynamic data obtained for a condensed phase. Hybrid quantum mechanical/molecular mechanical (QM/MM) models combined with sampling algorithms have the potential to provide an accurate solvation model and to incorporate the effects from the surrounding, which is often missing in gas-phase ab initio computations. Herein, we report the results from QM/MM free energy simulations of Na(+)/K(+) and Cl(-)/Br(-) hydration where we simultaneously characterized the relative thermodynamics of ion solvation and changes in the solvation structure. The Flexible Inner Region Ensemble Separator (FIRES) method was used to impose a spatial separation between QM region and the outer sphere of solvent molecules treated with the CHARMM27 force field. FEP calculations based on QM/MM simulations utilizing the CHARMM/deMon2k interface were performed with different basis set combinations for K(+)/Na(+) and Cl(-)/Br(-) perturbations to establish the dependence of the computed free energies on the basis set level. The dependence of the computed relative free energies on the size of the QM and MM regions is discussed. The current methodology offers an accurate description of structural and thermodynamic aspects of the hydration of alkali and halide ions in neat solvents and can be used to obtain thermodynamic data on ion solvation in condensed phase along with underlying

Finding New Perovskite Halides via Machine learning

Directory of Open Access Journals (Sweden)

Ghanshyam ePilania

2016-04-01

Full Text Available Advanced materials with improved properties have the potential to fuel future technological advancements. However, identification and discovery of these optimal materials for a specific application is a non-trivial task, because of the vastness of the chemical search space with enormous compositional and configurational degrees of freedom. Materials informatics provides an efficient approach towards rational design of new materials, via learning from known data to make decisions on new and previously unexplored compounds in an accelerated manner. Here, we demonstrate the power and utility of such statistical learning (or machine learning via building a support vector machine (SVM based classifier that uses elemental features (or descriptors to predict the formability of a given ABX3 halide composition (where A and B represent monovalent and divalent cations, respectively, and X is F, Cl, Br or I anion in the perovskite crystal structure. The classification model is built by learning from a dataset of 181 experimentally known ABX3 compounds. After exploring a wide range of features, we identify ionic radii, tolerance factor and octahedral factor to be the most important factors for the classification, suggesting that steric and geometric packing effects govern the stability of these halides. The trained and validated models then predict, with a high degree of confidence, several novel ABX3 compositions with perovskite crystal structure.

Finding New Perovskite Halides via Machine learning

Science.gov (United States)

Pilania, Ghanshyam; Balachandran, Prasanna V.; Kim, Chiho; Lookman, Turab

2016-04-01

Advanced materials with improved properties have the potential to fuel future technological advancements. However, identification and discovery of these optimal materials for a specific application is a non-trivial task, because of the vastness of the chemical search space with enormous compositional and configurational degrees of freedom. Materials informatics provides an efficient approach towards rational design of new materials, via learning from known data to make decisions on new and previously unexplored compounds in an accelerated manner. Here, we demonstrate the power and utility of such statistical learning (or machine learning) via building a support vector machine (SVM) based classifier that uses elemental features (or descriptors) to predict the formability of a given ABX3 halide composition (where A and B represent monovalent and divalent cations, respectively, and X is F, Cl, Br or I anion) in the perovskite crystal structure. The classification model is built by learning from a dataset of 181 experimentally known ABX3 compounds. After exploring a wide range of features, we identify ionic radii, tolerance factor and octahedral factor to be the most important factors for the classification, suggesting that steric and geometric packing effects govern the stability of these halides. The trained and validated models then predict, with a high degree of confidence, several novel ABX3 compositions with perovskite crystal structure.

Sodium-metal halide and sodium-air batteries.

Science.gov (United States)

Ha, Seongmin; Kim, Jae-Kwang; Choi, Aram; Kim, Youngsik; Lee, Kyu Tae

2014-07-21

Impressive developments have been made in the past a few years toward the establishment of Na-ion batteries as next-generation energy-storage devices and replacements for Li-ion batteries. Na-based cells have attracted increasing attention owing to low production costs due to abundant sodium resources. However, applications of Na-ion batteries are limited to large-scale energy-storage systems because of their lower energy density compared to Li-ion batteries and their potential safety problems. Recently, Na-metal cells such as Na-metal halide and Na-air batteries have been considered to be promising for use in electric vehicles owing to good safety and high energy density, although less attention is focused on Na-metal cells than on Na-ion cells. This Minireview provides an overview of the fundamentals and recent progress in the fields of Na-metal halide and Na-air batteries, with the aim of providing a better understanding of new electrochemical systems. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The creation of defects in ammonium halides by excitons

International Nuclear Information System (INIS)

Kim, L.M.

2002-01-01

The ammonium halides crystals and alkali halides crystals are analogous by kind chemical bonds and crystalline lattices. The anionic sublattice is identical in this crystals. It is known the main mechanism of defect creation by irradiation is radiationless decay of excitons in alkali halides crystals. The F-, H-centers are formation in this processes. However, F, H-centres are not detected in ammonium halides. The goal of this work is investigation the creation of defects in ammonium halides by excitons. We established that excitons in ammonium chlorides and bromides are similar to excitons in alkali halides. It is known excitons are self-trapped and have identical parameters of the exciton-phonon interaction in both kind crystals. It is supposed, that processes of radiationless disintegration of excitons are identical in ammonium and alkali halides. It is necessary to understand why F-, H-centers are absent in ammonium halides. V k -centres are created by the excitation of the ammonium halides crystals in the absorption band of excitons. It was established by thermoluminescence and spectrums of absorption. The V k -centers begin to migrate at 110-120 K in ammonium chlorides and bromides. The curve of thermoluminescence have peak with maximum at this temperatures. It is known V k -centers in ammonium chlorides have the absorption band at 380 nm. We discovered this absorption band after irradiation of crystals by ultra-violet. In alkali halides F-center is anionic vacancy with electron. The wave function of electron are spread ed at the cations around anionic vacancy. We established the cation NH 4 + in ammonium halides can to capture electron. The ion NH 4 2+ is unsteady. It is disintegrated to NH 3 + and H + . We suppose that excitons in ammonium and alkali halides are disintegrated identically. When cation NH 4 + capture electron, in the anionic sublattice the configuration are created in a direction (100) The indicated configuration is unsteady in relation to a

Absorption Spectroscopy Analysis of Calcium-Phosphate Glasses Highly Doped with Monovalent Copper.

Science.gov (United States)

Jiménez, José A

2016-06-03

CaO-P2 O5 glasses with high concentrations of monovalent copper ions were prepared by a simple melt-quench method through CuO and SnO co-doping. Spectroscopic characterization was carried out by optical absorption with the aim of analyzing the effects of Cu(+) ions on the optical band-gap energies, which were estimated on the basis of indirect-allowed transitions. The copper(I) content is estimated in the CuO/SnO-containing glasses after the assessment of the concentration dependence of Cu(2+) absorption in the visible region for CuO singly doped glasses. An exponential dependence of the change in optical band gaps (relative to the host) with Cu(+) concentration is inferred up to about 10 mol %. However, the entire range is divided into two distinct linear regions that are characterized by different rates of change with respect to concentration: 1) below 5 mol %, where the linear dependence presents a relatively high magnitude of the slope; and 2) from 5-10 mol %, where a lower magnitude of the slope is manifested. With increasing concentration, the mean Cu(+) -Cu(+) interionic distance decreases, thereby decreasing the sensitivity of monovalent copper for light absorption. The decrease in optical band-gap energies is ultimately shown to follow a linear dependence with the interionic distance, suggesting the potential of the approach to gauge the concentration of monovalent copper straightforwardly in amorphous hosts. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effects of Halide Ions on the Carbamidocyclophane Biosynthesis in Nostoc sp. CAVN2

Science.gov (United States)

Preisitsch, Michael; Heiden, Stefan E.; Beerbaum, Monika; Niedermeyer, Timo H. J.; Schneefeld, Marie; Herrmann, Jennifer; Kumpfmüller, Jana; Thürmer, Andrea; Neidhardt, Inga; Wiesner, Christoph; Daniel, Rolf; Müller, Rolf; Bange, Franz-Christoph; Schmieder, Peter; Schweder, Thomas; Mundt, Sabine

2016-01-01

In this study, the influence of halide ions on [7.7]paracyclophane biosynthesis in the cyanobacterium Nostoc sp. CAVN2 was investigated. In contrast to KI and KF, supplementation of the culture medium with KCl or KBr resulted not only in an increase of growth but also in an up-regulation of carbamidocyclophane production. LC-MS analysis indicated the presence of chlorinated, brominated, but also non-halogenated derivatives. In addition to 22 known cylindrocyclophanes and carbamidocyclophanes, 27 putative congeners have been detected. Nine compounds, carbamidocyclophanes M−U, were isolated, and their structural elucidation by 1D and 2D NMR experiments in combination with HRMS and ECD analysis revealed that they are brominated analogues of chlorinated carbamidocyclophanes. Quantification of the carbamidocyclophanes showed that chloride is the preferably utilized halide, but incorporation is reduced in the presence of bromide. Evaluation of the antibacterial activity of 30 [7.7]paracyclophanes and related derivatives against selected pathogenic Gram-positive and Gram-negative bacteria exhibited remarkable effects especially against methicillin- and vancomycin-resistant staphylococci and Mycobacterium tuberculosis. For deeper insights into the mechanisms of biosynthesis, the carbamidocyclophane biosynthetic gene cluster in Nostoc sp. CAVN2 was studied. The gene putatively coding for the carbamoyltransferase has been identified. Based on bioinformatic analyses, a possible biosynthetic assembly is discussed. PMID:26805858

Superconducting state parameters of monovalent and polyvalent amorphous

Energy Technology Data Exchange (ETDEWEB)

Sonvane, Y. A., E-mail: yas@ashd.svnit.ac.in [Department of Applied Physics, S. V. National Institute of Technology, Surat 395 007, Gujarat (India); Patel, H. P., E-mail: patel.harshal2@gmail.com; Thakor, P. B., E-mail: pbthakor@rediffmail.com [Department of Physics, Veer Narmad South Gujarat University, Surat 395 007, Gujarat (India)

2015-08-28

In the present study deals, we have calculated superconducting state parameter (SSP) like electron-phonon coupling strength λ, coulomb pseudo potential, μ*, transition temperature Tc, isotope effect exponent α and effective interaction strength N{sub 0}V of monovalent (Li), divalent (Zn), trivalent (In) and tetravalent (Pb) amorphous. To carry out this work we have used our newly constructed model pseudo potential to describe electron ion interaction along with three different local field correction functions like Hartree, Taylor and Sarkar et al. The present results are found in good agreement with other available theoretical as well as experimental data.

Systemic analysis of thermodynamic properties of lanthanide halides

International Nuclear Information System (INIS)

Mirsaidov, U.; Badalov, A.; Marufi, V.K.

1992-01-01

System analysis of thermodynamic characteristics of lanthanide halides was carried out. A method making allowances for the influence of spin and orbital moments of momentum of the main states of lanthanide trivalent ions in their natural series was employed. Unknown in literature thermodynamic values were calculated and corrected for certain compounds. The character of lanthanide halide thermodynamic parameter change depending on ordinal number of the metals was ascertained. Pronouncement of tetrad-effect in series of compounds considered was pointed out

Fouling prevention of peptides from a tryptic whey hydrolysate during electromembrane processes by use of monovalent ion permselective membranes

OpenAIRE

Persico, Mathieu; Bazinet, Laurent

2017-01-01

Peptide adsorption occurring on conventional anion- and cation-exchange membranes is one of the main technological locks in electrodialysis (ED) for hydrolysate demineralization. Hence, the peptide fouling of monovalent anion (MAP) and monovalent cation (MCP) permselective membranes was studied and compared to conventional membranes (AMX-SB and CMX-SB). It appeared that the main peptide sequences responsible for fouling were TPEVDDEALEKFDK, VAGTWY and VLVLDTDYK for both anionic membranes; and...

Maximizing and stabilizing luminescence from halide perovskites with potassium passivation

Science.gov (United States)

Abdi-Jalebi, Mojtaba; Andaji-Garmaroudi, Zahra; Cacovich, Stefania; Stavrakas, Camille; Philippe, Bertrand; Richter, Johannes M.; Alsari, Mejd; Booker, Edward P.; Hutter, Eline M.; Pearson, Andrew J.; Lilliu, Samuele; Savenije, Tom J.; Rensmo, Håkan; Divitini, Giorgio; Ducati, Caterina; Friend, Richard H.; Stranks, Samuel D.

2018-03-01

Metal halide perovskites are of great interest for various high-performance optoelectronic applications. The ability to tune the perovskite bandgap continuously by modifying the chemical composition opens up applications for perovskites as coloured emitters, in building-integrated photovoltaics, and as components of tandem photovoltaics to increase the power conversion efficiency. Nevertheless, performance is limited by non-radiative losses, with luminescence yields in state-of-the-art perovskite solar cells still far from 100 per cent under standard solar illumination conditions. Furthermore, in mixed halide perovskite systems designed for continuous bandgap tunability (bandgaps of approximately 1.7 to 1.9 electronvolts), photoinduced ion segregation leads to bandgap instabilities. Here we demonstrate substantial mitigation of both non-radiative losses and photoinduced ion migration in perovskite films and interfaces by decorating the surfaces and grain boundaries with passivating potassium halide layers. We demonstrate external photoluminescence quantum yields of 66 per cent, which translate to internal yields that exceed 95 per cent. The high luminescence yields are achieved while maintaining high mobilities of more than 40 square centimetres per volt per second, providing the elusive combination of both high luminescence and excellent charge transport. When interfaced with electrodes in a solar cell device stack, the external luminescence yield—a quantity that must be maximized to obtain high efficiency—remains as high as 15 per cent, indicating very clean interfaces. We also demonstrate the inhibition of transient photoinduced ion-migration processes across a wide range of mixed halide perovskite bandgaps in materials that exhibit bandgap instabilities when unpassivated. We validate these results in fully operating solar cells. Our work represents an important advance in the construction of tunable metal halide perovskite films and interfaces that can

Differential Deformability of the DNA Minor Groove and Altered BI/BII Backbone Conformational Equilibrium by the Monovalent Ions Li+, Na+, K+ and Rb+ via Water-Mediated Hydrogen Bonding

Science.gov (United States)

Savelyev, Alexey; MacKerell, Alexander D.

2015-01-01

Recently, we reported the differential impact of the monovalent cations Li+, Na+, K+ and Rb+ on DNA conformational properties. These were identified from variations in the calculated solution-state X-ray DNA spectra as a function of the ion type in the solvation buffer in MD simulations using our recently developed polarizable force field based on the classical Drude oscillator. Changes in the DNA structure were found to mainly involve variations in the minor groove width. Because minor groove dimensions vary significantly in protein-DNA complexes and have been shown to play a critical role in both specific and nonspecific DNA readout, understanding the origins of the observed differential DNA modulation by the first-group monovalent ions is of great biological importance. In the present study we show that the primary microscopic mechanism for the phenomenon is the formation of the water-mediated hydrogen bonds between solvated cations located inside the minor groove and simultaneously to two DNA strands, a process whose intensity and impact on DNA structure depends on both the type of the ion and DNA sequence. Additionally, it is shown that formation of such ion-DNA hydrogen bond complexes appreciably modulates the conformation of the backbone by increasing the population of the BII substate. Notably, the differential impact of the ions on DNA conformational behavior is only predicted by the Drude polarizable model for DNA, with virtually no effect observed from MD simulations utilizing the additive CHARMM36 model. Analysis of dipole moments of the water shows the Drude SWM4 model to possess high sensitivity to changes in the local environment, which indicates the important role of electronic polarization in the salt-dependent conformational properties. This also suggests that inclusion of polarization effects is required to model even relatively simple biological systems such as DNA in various ionic solutions. PMID:26575937

Surface and zeta-potentials of silver halide single crystals: pH-dependence in comparison to particle systems

International Nuclear Information System (INIS)

Selmani, Atiða; Kallay, Nikola; Preočanin, Tajana; Lützenkirchen, Johannes

2014-01-01

We have carried out surface and zeta-potential measurements on AgCl and AgBr single crystals. As for particle systems we find that, surprisingly and previously unnoted, the zeta-potential exhibits pH-dependence, while the surface potential does not. A possible interpretation of these observations is the involvement of water ions in the interfacial equilibria and in particular, stronger affinity of the hydroxide ion compared to the proton. The pH-dependence of the zeta-potential can be suppressed at sufficiently high silver concentrations, which agrees with previous measurements in particle systems where no pH-dependence was found at high halide ion concentrations. The results suggest a subtle interplay between the surface potential determining the halide and silver ion concentrations, and the water ions. Whenever the charge due to the halide and silver ions is sufficiently high, the influence of the proton/hydroxide ion on the zeta-potential vanishes. This might be related to the water structuring at the relevant interfaces which should be strongly affected by the surface potential. Another interesting observation is accentuation of the assumed water ion effect on the zeta-potential at the flat single crystal surfaces compared to the corresponding silver halide colloids. Previous generic MD simulations have indeed predicted that hydroxide ion adsorption is accentuated on flat/rigid surfaces. A thermodynamic model for AgI single crystals was developed to describe the combined effects of iodide, silver and water ions, based on two independently previously published models for AgI (that only consider constituent and background electrolyte ions) and inert surfaces (that only consider water and background electrolyte ions). The combined model correctly predicts all the experimentally observed trends. (paper)

Reactivity of halide and pseudohalide ligands

International Nuclear Information System (INIS)

Kukushkin, Yu.N.

1987-01-01

Reactivity of halide and pseudohalide (cyanide, azide, thiocyanate, cyanate) ligands tending to form bridge bonds in transition metal (Re, Mo, W) complexes is considered. Complexes where transition metal salts are ligands of other, complex-forming ion, are described. Transformation of innerspheric pseudohalide ligands is an important way of directed synthesis of these metal coordination compounds

Halide ions complex and deprotonate dipicolinamides and isophthalamides: assessment by mass spectrometry and UV-visible spectroscopy.

Science.gov (United States)

Carasel, I Alexandru; Yamnitz, Carl R; Winter, Rudolph K; Gokel, George W

2010-12-03

The F(-), Cl(-), and Br(-) binding selectivity of bis(p-nitroanilide)s of dipicolinic and isophthalic acids was studied by using competitive electrospray mass spectrometry and UV-Visible spectroscopy. Both hosts prefer binding Cl(-) over either F(-) or Br(-). Host deprotonation was observed to some extent in all experiments in which the host was exposed to halide ions. When F(-) was present, host deprotonation was often the major process, whereas little deprotonation was observed by Cl(-) or Br(-), which preferred complexation. A solution of either host changed color when mixed with a F(-), H(2)PO(4)(-), di- or triphenylacetate solution.

Complexes in polyvalent metal - Alkali halide melts

International Nuclear Information System (INIS)

Akdeniz, Z.; Tosi, M.P.

1991-03-01

Experimental evidence is available in the literature on the local coordination of divalent and trivalent metal ions by halogens in some 140 liquid mixtures of their halides with alkali halides. After brief reference to classification criteria for main types of local coordination, we focus on statistical mechanical models that we are developing for Al-alkali halide mixtures. Specifically, we discuss theoretically the equilibrium between (AlF 6 ) 3- and (AlF 4 ) - complexes in mixtures of AlF 3 and NaF as a function of composition in the NaF-rich region, the effect of the alkali counterion on this equilibrium, the possible role of (AlF 5 ) 2- as an intermediate species in molten cryolite, and the origin of the different complexing behaviours of Al-alkali fluorides and chlorides. We also present a theoretical scenario for processes of structure breaking and electron localization in molten cryolite under addition of sodium metal. (author). 26 refs, 2 tabs

Vibrational Spectra of Discrete UO22+ Halide Complexes in the Gas Phase

International Nuclear Information System (INIS)

Groenewold, G.S.; Van Stipdonk, Michael J.; Oomens, Jos; De Jong, Wibe A.; Gresham, Garold L.; Mcilwain, Michael

2010-01-01

The intrinsic binding of halide ions to the metal center in the uranyl molecule is a topic of ongoing research interest in both the actinide separations and theoretical communities. Investigations of structure in the condensed phases is frequently obfuscated by solvent interactions that can alter ligand binding and spectroscopic properties. The approach taken in this study is to move the uranyl halide complexes into the gas phase where they are free from solvent interactions, and then interrogate their vibrational spectroscopy using infrared multiple photon dissociation (IRMPD). The spectra of cationic coordination complexes having the composition (UO 2 (X)(ACO) 3 ) + (where X = F, Cl, Br and I; ACO = acetone) were acquired using electrospray for ion formation, and monitoring the ion signal from the photoelimination of ACO ligands. The studies showed that the asymmetric ν 3 UO 2 frequency was insensitive to halide identity as X was varied from Cl to I, suggesting that in these pseudo-octahedral complexes, changing the nucleophilicity of the halide did not appreciably alter its binding in the complex. The ν 3 peak in the spectrum of the F-containing complex was 9 cm -1 lower indicating stronger coordination in this complex. Similarly the ACO carbonyl stretches showed that the C=O frequency was relatively insensitive to the identity of the halide, although a modest shift to higher wavenumber was seen for the complexes with the more nucleophilic anions, consistent with the idea that they loosen solvent binding. Surprisingly, the ν 1 stretch was activated when the softer anions Cl, Br and I were present in the complexes. IR studies of the anionic complexes (UO 2 X 3 ) - (where X = Cl - , Br - and I - ) compared the ν 3 UO 2 modes versus halide, and showed that the ν 3 values decreased with increasing anion nucleophilicity. This observation was consistent with DFT calculations that indicated that (UO 2 X 2 ) - -X, and (UO 2 X 2 )·-X - dissociation energies

Influence of competing inorganic cations on the ion exchange equilibrium of the monovalent organic cation metoprolol on natural sediment.

Science.gov (United States)

Niedbala, Anne; Schaffer, Mario; Licha, Tobias; Nödler, Karsten; Börnick, Hilmar; Ruppert, Hans; Worch, Eckhard

2013-02-01

The aim of this study was to systematically investigate the influence of the mono- and divalent inorganic ions Na(+) and Ca(2+) on the sorption behavior of the monovalent organic cation metoprolol on a natural sandy sediment at pH=7. Isotherms for the beta-blocker metoprolol were obtained by sediment-water batch tests over a wide concentration range (1-100000 μg L(-1)). Concentrations of the competing inorganic ions were varied within freshwater relevant ranges. Data fitted well with the Freundlich sorption model and resulted in very similar Freundlich exponents (n=0.9), indicating slightly non-linear behavior. Results show that the influence of Ca(2+) compared to Na(+) is more pronounced. A logarithmic correlation between the Freundlich coefficient K(Fr) and the concentration or activity of the competing inorganic ions was found allowing the prediction of metoprolol sorption on the investigated sediment at different electrolyte concentrations. Additionally, the organic carbon of the sediment was completely removed for investigating the influence of organic matter on the sorption of metoprolol. The comparison between the experiments with and without organic carbon removal revealed no significant contribution of the organic carbon fraction (0.1%) to the sorption of metoprolol on the in this study investigated sediment. Results of this study will contribute to the development of predictive models for the transport of organic cations in the subsurface. Copyright © 2012 Elsevier Ltd. All rights reserved.

Line emissions from sonoluminescence in aqueous solutions of halide salts without noble gases

Energy Technology Data Exchange (ETDEWEB)

Liang, Jinfu, E-mail: liang.shi2007@163.com [The Key Laboratory of Modern Acoustics, Ministry of Education, Institution of Acoustics, Nanjing University, Nanjing 210093 (China); School of Physics and Electronic Science, Guizhou Normal University, Guiyang 550001 (China); Chen, Weizhong, E-mail: wzchen@nju.edu.cn [The Key Laboratory of Modern Acoustics, Ministry of Education, Institution of Acoustics, Nanjing University, Nanjing 210093 (China); Zhou, Chao; Cui, Weicheng; Chen, Zhan [The Key Laboratory of Modern Acoustics, Ministry of Education, Institution of Acoustics, Nanjing University, Nanjing 210093 (China)

2015-02-20

Line emissions of trivalent terbium (Tb{sup 3+}) ion were observed from single-bubble sonoluminescence (SL) in an aqueous solution of terbium chloride (TbCl{sub 3}) that contained no noble gas. In addition, sodium (Na) lines were observed in multi-bubble SL in aqueous solutions of various halide salts that contained no noble gas. These observations show that the halide ions, such as Cl{sup −}, Br{sup −}, and I{sup −}, help for line emissions as the noble gases. The intensity of a line emission depends on both the chemical species produced by cavitation bubbles and the temperature of SL bubble that responds to the driving ultrasound pressure. With the increase of driving pressure, some line emissions attached to the continuous spectrum may become increasingly clear, while other line emissions gradually become indistinct. - Highlights: • Line emissions of Tb(III) ions were observed without the presence of noble gases. • The halide ions help to generate a line emission during sonoluminescence. • The intensity of a line emission mainly depends on the bubble's temperature. • The definition of a line emission is related to the temperature of caviation bubble and the kind of host liquid.

Quantum chemical study of halophilic interactions. Communication 3. Non-empirical study of the ways of tetrachloromethane attack by halide ions

International Nuclear Information System (INIS)

Kobychev, V.B.; Vitkovskaya, N.M.; Abramov, A.V.; Timokhin, B.V.

1999-01-01

It has been shown by means of non-empirical calculations of model reactions between tetrachloromethane and chlorine/iodine anions that in case of attack via carbon atom according to mechanism S N 2 formation of weakly-bound CCl 4 complexes with halide ions is observed at initial state. Further transformation of the complexes is restricted by considerable potential barriers. Attack of nucleophil via chlorine atom with formation of stable complexes CCl 3 -Cl-Hlg - is preferable [ru

Luminescent sulfides of monovalent and trivalent cations

International Nuclear Information System (INIS)

1975-01-01

The invention discloses a family of luminescent materials or phosphors having a rhombohedral crystal structure and consisting essentially of a mixed host sulfide of at least one monovalent host cation and at least one trivalent host cation, and containing, for each mole of phosphor, 0.0005 to 0.05 mole of at least one activating cation. The monovalent host cations may be Na, K or Rb and Cs. The trivalent host cations may be Gd, La, Lu, Sc and Y. The activating cations may be one or more of trivalent As, Bi, Ce, Dy, Er, Pr, Sb, Sm, Tb and Tm; divalent Lu, Mn, Pb and Sn; and monovalent Ag, Cu and Tl. The novel phosphors may be used in devices to convert electron-beam, ultraviolet or x-ray energy to light in the visible spectrum. Such energy conversion can be employed for example in fluoroscopic screens, and in viewing screens of cathode-ray tubes and other electron tubes

Luminescent decay and spectra of impurity-activated alkali halides under high pressure

International Nuclear Information System (INIS)

Klick, D.I.

1977-01-01

The effect of high pressure on the luminescence of alkali halides doped with the transition-metal ions Cu + and Ag + and the heavy-metal ions In + and Tl + was investigated to 140 kbar. Measurement of spectra allowed the prediction of kinetic properties, and the predictions agree with lifetime data

Reaction between aminoalkyl radicals and akyl halides: Dehalogenation by electron transfer?

Science.gov (United States)

Lalevée, J.; Fouassier, J. P.; Blanchard, N.; Ingold, K. U.

2011-07-01

Aminoalkyl radicals, such as Et2NCrad HCH3, have low oxidation potentials and are therefore powerful reducing agents. We have found that Et2NCrad HCH3 reacts with CCl4 and CBr4 in di-tert-butyl peroxide with bimolecular rate constants (measured by LFP) close, or equal, to the diffusion-controlled limit. For the less reactive halide, CH2Br2, the reaction rate is increased substantially by the addition of acetonitrile as a co-solvent. It is tentatively concluded that these reactions occur by electron-transfer from the aminoalkyl to the organohalide with formation of the iminium ion, Et2N+dbnd CHCH3 (NMR detection), halide ion and a halomethyl radical, e.g., rad CCl3 and rad CHCl2 (ESR, spin-trapping detection).

Double Charged Surface Layers in Lead Halide Perovskite Crystals

KAUST Repository

Sarmah, Smritakshi P.

2017-02-01

Understanding defect chemistry, particularly ion migration, and its significant effect on the surface’s optical and electronic properties is one of the major challenges impeding the development of hybrid perovskite-based devices. Here, using both experimental and theoretical approaches, we demonstrated that the surface layers of the perovskite crystals may acquire a high concentration of positively charged vacancies with the complementary negatively charged halide ions pushed to the surface. This charge separation near the surface generates an electric field that can induce an increase of optical band gap in the surface layers relative to the bulk. We found that the charge separation, electric field, and the amplitude of shift in the bandgap strongly depend on the halides and organic moieties of perovskite crystals. Our findings reveal the peculiarity of surface effects that are currently limiting the applications of perovskite crystals and more importantly explain their origins, thus enabling viable surface passivation strategies to remediate them.

Self-trapped holes in alkali silver halide crystals

International Nuclear Information System (INIS)

Awano, T.; Ikezawa, M.; Matsuyama, T.

1995-01-01

γ-Ray irradiation at 77 K induces defects in M 2 AgX 3 (M=Rb, K and NH 4 ; X=Br and I) crystals. The irradiation induces self-trapped holes of the form of I 0 in the case of alkali silver iodides, and (halogen) 2 - and (halogen) 0 in the case of ammonium silver halides. The (halogen) 0 is weakly coupled with the nearest alkali metal ion or ammonium ion. It is able to be denoted as RbI + , KI + , NH 4 I + or NH 4 Br + . The directions of hole distribution of (halogen) 2 - and (halogen) 0 were different in each case of the alkali silver iodides, ammonium silver halides and mixed crystal of them. The (halogen) 0 decayed at 160 K in annealing process. The (halogen) 2 - was converted into another form of (halogen) 2 - at 250 K and this decayed at 310 K. A formation of metallic layers was observed on the crystal surface parallel with the c-plane of (NH 4 ) 2 AgI 3 irradiated at room temperature. (author)

The impact of alkali metal halide electron donor complexes in the photocatalytic degradation of pentachlorophenol

Energy Technology Data Exchange (ETDEWEB)

Khuzwayo, Z., E-mail: zack.khuzwayo@up.ac.za; Chirwa, E.M.N

2017-01-05

Highlights: • Facilitation of photocatalysis using simple metal-halides as VB hole scavengers. • Recombination prevention by coupled valence and conduction band approaches. • Determination of anions critical levels beyond which process retardation occurs. • Determination of the photocatalytic process rate of reaction kinetics. - Abstract: The performance of photocatalytic oxidation of chemical pollutants is subjected to the presence of anion complexes in natural waters. This study investigated the influence of alkali metal (Na{sup +} (sodium), K{sup +} (potassium)) halides (Cl{sup −} (chloride), Br{sup −} (bromide), F{sup −} (fluoride)) as inorganic ion sources in the photocatalytic degradation of pentachlorophenol (PCP) in batch systems. It was found that the exclusive presence of halides in the absence of an electron acceptor adequately facilitated the photocatalyst process below critical levels of anion populations, where beyond the critical point the process was significantly hindered. Below the determined critical point, the performance in some cases near matches that of the facilitation of the photocatalytic process by exclusive oxygen, acting as an electron scavenger. The coupling of halide ions and oxygenation presented significantly improved photo-oxidation of PCP, this was confirmed by the inclusion of formic acid as a comparative electron donor. The Langmuir-Hinshelwood kinetic expression was used to calculate the performance rate kinetics. The probable impact of the halide anions was discussed with regards to the process of electron hole pair recombination prevention.

The role of monovalent cations in the ATPase reaction of DNA gyrase.

Science.gov (United States)

Hearnshaw, Stephen James; Chung, Terence Tsz-Hong; Stevenson, Clare Elizabeth Mary; Maxwell, Anthony; Lawson, David Mark

2015-04-01

Four new crystal structures of the ATPase domain of the GyrB subunit of Escherichia coli DNA gyrase have been determined. One of these, solved in the presence of K(+), is the highest resolution structure reported so far for this domain and, in conjunction with the three other structures, reveals new insights into the function of this domain. Evidence is provided for the existence of two monovalent cation-binding sites: site 1, which preferentially binds a K(+) ion that interacts directly with the α-phosphate of ATP, and site 2, which preferentially binds an Na(+) ion and the functional significance of which is not clear. The crystallographic data are corroborated by ATPase data, and the structures are compared with those of homologues to investigate the broader conservation of these sites.

The effects of halide ions on the radiation-induced decoloration of azo and anthraquinone dyes in N2O-saturated aqueous solutions

International Nuclear Information System (INIS)

Suzuki, Nobutake; Tokunaga, Okihiro; Washino, Masamitsu

1978-01-01

The radiation-induced decoloration of azo and anthraquinone dyes was studied in N 2 O-saturated aqueous solutions containing halide ions. In the N 2 O-saturated solutions, the decoloration yield, G(-Dye), increased markedly upon the addition of Br - and I - , which are efficient scavengers of the OH radical. In the nitrogen-saturated solutions, however, the G(-Dye) decreased upon the addition of Br - and I - . Such an increase in the G(-Dye) upon the addition of Br - and I - in the N 2 O-saturated solutions is mainly attributable to the attacks of the halide radical anions, Br 2 - and I 2 - , on the ring structure of the dyes. On the other hand, the G(-Dye) was not changed upon the addition of Cl - in the N 2 O-saturated solution. This may be attributable to the very slow rate of the formation of Cl 2 - in a neutral solution. (auth.)

Halide salts accelerate degradation of high explosives by zerovalent iron

International Nuclear Information System (INIS)

Kim, Jong Sung; Shea, Patrick J.; Yang, Jae E.; Kim, Jang-Eok

2007-01-01

Zerovalent iron (Fe 0 , ZVI) has drawn great interest as an inexpensive and effective material to promote the degradation of environmental contaminants. A focus of ZVI research is to increase degradation kinetics and overcome passivation for long-term remediation. Halide ions promote corrosion, which can increase and sustain ZVI reactivity. Adding chloride or bromide salts with Fe 0 (1% w/v) greatly enhanced TNT, RDX, and HMX degradation rates in aqueous solution. Adding Cl or Br salts after 24 h also restored ZVI reactivity, resulting in complete degradation within 8 h. These observations may be attributed to removal of the passivating oxide layer and pitting corrosion of the iron. While the relative increase in degradation rate by Cl - and Br - was similar, TNT degraded faster than RDX and HMX. HMX was most difficult to remove using ZVI alone but ZVI remained effective after five HMX reseeding cycles when Br - was present in solution. - The addition of halide ions promotes the degradation of high explosives by zerovalent iron

X-ray yields by low energy heavy ion excitation in alkali halide solid targets

International Nuclear Information System (INIS)

Kurup, M.B.; Prasad, K.G.; Sharma, R.P.

1981-01-01

Solid targets of the alkali halides KCl, NaCl and KBr are bombarded with ion beams of 35 Cl + , 40 Ar + and 63 Cu + in the energy range 165 keV to 320 keV. The MO and characteristic K X-ray yields resulting from the ion-atom collision have been systematically studied. Both MO and Cl K X-ray yields are enhanced by factors 3.5 and 2 respectively in KCl targets as compared to that in NaCl when bombarded with either Cl + or Ar + projectiles. An intercomparison of MO and K X-ray yields for a given projectile-target combination has shown that the latter increases ten times faster than the former as the energy of the projectile is increased from 165 to 320 keV indicating a correspondingly stronger velocity dependence of the K X-ray production process. The X-ray yields observed in the symmetric Cl-Cl collision are identical to those observed in the asymmetric Ar-Cl collision for the same projectile velocities in both KCl and NaCl targets. It is inferred that the multiple ionization of the projectile resulting in an increase in the binding energy of its inner shells offsets the expected enhancement in the X-ray yields in a symmetric collision. The same projectiles, Ar or Cl, incident on KBr targets have produced only Br L X-rays. Using substantially heavier projectiles than the target atoms (Na, K and Cl), like 63 Cu + ions, the inner shell excitation by recoiling atoms is shown. (orig.)

Release of Halide Ions from the Buried Active Site of the Haloalkane Dehalogenase LinB Revealed by Stopped-Flow Fluorescence Analysis and Free Energy Calculations

Czech Academy of Sciences Publication Activity Database

Hladílková, Jana; Prokop, Z.; Chaloupková, R.; Damborský, J.; Jungwirth, Pavel

2013-01-01

Roč. 117, č. 46 (2013), s. 14329-14335 ISSN 1520-6106 R&D Projects: GA ČR GBP208/12/G016 Grant - others:GA ČR(CZ) GAP207/12/0775 Program:GA Institutional support: RVO:61388963 Keywords : access tunnel * buried active site * catalytic activity * enzyme mechanism * haloalkane dehalogenase * halide ions Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.377, year: 2013

Thermodynamics of Small Alkali Metal Halide Cluster Ions: Comparison of Classical Molecular Simulations with Experiment and Quantum Chemistry

Energy Technology Data Exchange (ETDEWEB)

Vlcek, Lukas [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Uhlik, Filip [Charles Univ., Prague (Czech Republic); Moucka, Filip [Purkinje Univ. (Czech Republic); Nezbeda, Ivo [Purkinje Univ. (Czech Republic); Academy of Sciences of the Czech Republic (ASCR), Prague (Czech Republic); Chialvo, Ariel A. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

2015-12-16

We evaluate the ability of selected classical molecular models to describe the thermodynamic and structural aspects of gas-phase hydration of alkali halide ions and the formation of small water clusters. To understand the effect of many-body interactions (polarization) and charge penetration effects on the accuracy of a force field, we perform Monte Carlo simulations with three rigid water models using different functional forms to account for these effects: (i) point charge non-polarizable SPC/E, (ii) Drude point charge polarizable SWM4- DP, and (iii) Drude Gaussian charge polarizable BK3. Model predictions are compared with experimental Gibbs free energies and enthalpies of ion hydration, and with microscopic structural properties obtained from quantum DFT calculations. We find that all three models provide comparable predictions for pure water clusters and cation hydration, but differ significantly in their description of anion hydration. None of the investigated classical force fields can consistently and quantitatively reproduce the experimental gas phase hydration thermodynamics. The outcome of this study highlights the relation between the functional form that describes the effective intermolecular interactions and the accuracy of the resulting ion hydration properties.

Predicting hydration energies for multivalent ions

DEFF Research Database (Denmark)

Andersson, Martin Peter; Stipp, Susan Louise Svane

2014-01-01

We have predicted the free energy of hydration for 40 monovalent and multivalent cations and anions using density functional theory and the implicit solvent model COnductor like Screening MOdel for Real Solvents (COSMO-RS) at the Becke-Perdew (BP)/Triple zeta valence with polarization functions...... (TZVP) level. Agreement with experimental data for monovalent and divalent ions is good and shows no significant systematic errors. Predictions are noticeably better than with standard COSMO. The agreement with experimental data for trivalent and tetravalent ions is slightly worse and shows systematic...... errors. Our results indicate that quantum chemical calculations combined with COSMO-RS solvent treatment is a reliable method for treating multivalent ions in solution, provided one hydration shell of explicit water molecules is included for metal cations. The accuracy is not high enough to allow...

Monovalent Cation Activation of the Radical SAM Enzyme Pyruvate Formate-Lyase Activating Enzyme.

Science.gov (United States)

Shisler, Krista A; Hutcheson, Rachel U; Horitani, Masaki; Duschene, Kaitlin S; Crain, Adam V; Byer, Amanda S; Shepard, Eric M; Rasmussen, Ashley; Yang, Jian; Broderick, William E; Vey, Jessica L; Drennan, Catherine L; Hoffman, Brian M; Broderick, Joan B

2017-08-30

Pyruvate formate-lyase activating enzyme (PFL-AE) is a radical S-adenosyl-l-methionine (SAM) enzyme that installs a catalytically essential glycyl radical on pyruvate formate-lyase. We show that PFL-AE binds a catalytically essential monovalent cation at its active site, yet another parallel with B 12 enzymes, and we characterize this cation site by a combination of structural, biochemical, and spectroscopic approaches. Refinement of the PFL-AE crystal structure reveals Na + as the most likely ion present in the solved structures, and pulsed electron nuclear double resonance (ENDOR) demonstrates that the same cation site is occupied by 23 Na in the solution state of the as-isolated enzyme. A SAM carboxylate-oxygen is an M + ligand, and EPR and circular dichroism spectroscopies reveal that both the site occupancy and the identity of the cation perturb the electronic properties of the SAM-chelated iron-sulfur cluster. ENDOR studies of the PFL-AE/[ 13 C-methyl]-SAM complex show that the target sulfonium positioning varies with the cation, while the observation of an isotropic hyperfine coupling to the cation by ENDOR measurements establishes its intimate, SAM-mediated interaction with the cluster. This monovalent cation site controls enzyme activity: (i) PFL-AE in the absence of any simple monovalent cations has little-no activity; and (ii) among monocations, going down Group 1 of the periodic table from Li + to Cs + , PFL-AE activity sharply maximizes at K + , with NH 4 + closely matching the efficacy of K + . PFL-AE is thus a type I M + -activated enzyme whose M + controls reactivity by interactions with the cosubstrate, SAM, which is bound to the catalytic iron-sulfur cluster.

Monovalent Strep-Tactin for strong and site-specific tethering in nanospectroscopy.

Science.gov (United States)

Baumann, Fabian; Bauer, Magnus S; Milles, Lukas F; Alexandrovich, Alexander; Gaub, Hermann E; Pippig, Diana A

2016-01-01

Strep-Tactin, an engineered form of streptavidin, binds avidly to the genetically encoded peptide Strep-tag II in a manner comparable to streptavidin binding to biotin. These interactions have been used in protein purification and detection applications. However, in single-molecule studies, for example using atomic force microscopy-based single-molecule force spectroscopy (AFM-SMFS), the tetravalency of these systems impedes the measurement of monodispersed data. Here, we introduce a monovalent form of Strep-Tactin that harbours a unique binding site for Strep-tag II and a single cysteine that allows Strep-Tactin to specifically attach to the atomic force microscope cantilever and form a consistent pulling geometry to obtain homogeneous rupture data. Using AFM-SMFS, the mechanical properties of the interaction between Strep-tag II and monovalent Strep-Tactin were characterized. Rupture forces comparable to biotin:streptavidin unbinding were observed. Using titin kinase and green fluorescent protein, we show that monovalent Strep-Tactin is generally applicable to protein unfolding experiments. We expect monovalent Strep-Tactin to be a reliable anchoring tool for a range of single-molecule studies.

Aqueous photochemical reactions of chloride, bromide, and iodide ions in a diode-array spectrophotometer. Autoinhibition in the photolysis of iodide ions.

Science.gov (United States)

Kalmár, József; Dóka, Éva; Lente, Gábor; Fábián, István

2014-03-28

The aqueous photoreactions of three halide ions (chloride, bromide and iodide) were studied using a diode array spectrophotometer to drive and detect the process at the same time. The concentration and pH dependences of the halogen formation rates were studied in detail. The experimental data were interpreted by improving earlier models where the cage complex of a halogen atom and an electron has a central role. The triiodide ion was shown to exert a strong inhibiting effect on the reaction sequence leading to its own formation. An assumed chemical reaction between the triiodide ion and the cage complex interpreted the strong autoinhibition effect. It is shown that there is a real danger of unwanted interference from the photoreactions of halide ions when halide salts are used as supporting electrolytes in spectrophotometric experiments using a relatively high intensity UV light source.

A Simple Halide-to-Anion Exchange Method for Heteroaromatic Salts and Ionic Liquids

Directory of Open Access Journals (Sweden)

Neus Mesquida

2012-04-01

Full Text Available A broad and simple method permitted halide ions in quaternary heteroaromatic and ammonium salts to be exchanged for a variety of anions using an anion exchange resin (A− form in non-aqueous media. The anion loading of the AER (OH− form was examined using two different anion sources, acids or ammonium salts, and changing the polarity of the solvents. The AER (A− form method in organic solvents was then applied to several quaternary heteroaromatic salts and ILs, and the anion exchange proceeded in excellent to quantitative yields, concomitantly removing halide impurities. Relying on the hydrophobicity of the targeted ion pair for the counteranion swap, organic solvents with variable polarity were used, such as CH3OH, CH3CN and the dipolar nonhydroxylic solvent mixture CH3CN:CH2Cl2 (3:7 and the anion exchange was equally successful with both lipophilic cations and anions.

Electrochemical specific adsorption of halides on Cu 111, 100, and 211: A Density Functional Theory study

International Nuclear Information System (INIS)

McCrum, Ian T.; Akhade, Sneha A.; Janik, Michael J.

2015-01-01

The specific adsorption of ions onto electrode surfaces can affect electrocatalytic reactions. Density functional theory is used to investigate the specific adsorption of aqueous F − , Cl − , Br − , and I − onto Cu (111), (100), and (211) surfaces. The adsorption is increasingly favorable in the order of F − < Cl − < Br − < I − . The adsorption has a weak dependence on the surface facet, with adsorption most favorable on Cu (100) and least favorable on Cu (111). Potential ranges where specific adsorption would be expected on each facet are reported. The thermodynamics of bulk copper halide (CuX, CuX 2 ) formation are also investigated as a function of potential. CuX formation occurs at potentials slightly more positive of halide specific adsorption and of copper oxidation in aqueous electrolytes. Specifically adsorbed halides and bulk CuX may be present during a variety of electrochemical reactions carried out over a Cu electrode in halide containing electrolyte solutions

Auger decay mechanism in photon-stimulated desorption of ions from surfaces

International Nuclear Information System (INIS)

Parks, C.C.

1983-11-01

Photon-stimulated desorption (PSD) of positive ions was studied with synchrotron radiation using an angle-integrating time-of-flight mass spectrometer. Ion yields as functions of photon energy near core levels were measured from condensed gases, alkali fluorides, and other alkali and alkaline earth halides. These results are compared to bulk photoabsorption measurements with emphasis on understanding fundamental desorption mechanisms. The applicability of the Auger decay mechanism, in which ion desorption is strictly proportional to surface absorption, is discussed in detail. The Auger decay model is developed in detail to describe Na + and F + desorption from NaF following Na(1s) excitation. The major decay pathways of the Na(1s) hole leading to desorption are described and equations for the energetics of ion desorption are developed. Ion desorption spectra of H + , Li + , and F + are compared to bulk photoabsorption near the F(2s) and Li(1s) edges of LiF. A strong photon beam exposure dependence of ion yields from alkali fluorides is revealed, which may indicate the predominance of metal ion desorption from defect sites. The large role of indirect mechanisms in ion desorption condensed N 2 -O 2 multilayers is demonstrated and discussed. Ion desorption spectra from several alkali halides and alkaline earth halides are compared to bulk photoabsorption spectra. Relative ion yields from BaF 2 and a series of alkali halides are discussed in terms of desorption mechanisms

Monovalent-ion-selective membranes for reserve electrodialysis

NARCIS (Netherlands)

Güler, E.; van Baak, Willem; Saakes, Michel; Nijmeijer, Dorothea C.

2014-01-01

Reverse electrodialysis (RED) is a process that can be used to generate energy from salinity gradients. Since its application in practice requires the use of natural seawater and river water, the presence of multivalent ions is inevitable, but this currently limits RED performance. Membranes with

Strong and Reversible Monovalent Supramolecular Protein Immobilization

NARCIS (Netherlands)

Young, Jacqui F.; Nguyen, Hoang D.; Yang, Lanti; Huskens, Jurriaan; Jonkheijm, Pascal; Brunsveld, Luc

2010-01-01

Proteins with an iron clasp: Site-selective incorporation of a ferrocene molecule into a protein allows for easy, strong, and reversible supramolecular protein immobilization through a selective monovalent interaction of the ferrocene with a cucurbit[7]uril immobilized on a gold surface. The

Improved catalytic properties of halohydrin dehalogenase by modification of the halide-binding site.

Science.gov (United States)

Tang, Lixia; Torres Pazmiño, Daniel E; Fraaije, Marco W; de Jong, René M; Dijkstra, Bauke W; Janssen, Dick B

2005-05-03

Halohydrin dehalogenase (HheC) from Agrobacterium radiobacter AD1 catalyzes the dehalogenation of vicinal haloalcohols by an intramolecular substitution reaction, resulting in the formation of the corresponding epoxide, a halide ion, and a proton. Halide release is rate-limiting during the catalytic cycle of the conversion of (R)-p-nitro-2-bromo-1-phenylethanol by the enzyme. The recent elucidation of the X-ray structure of HheC showed that hydrogen bonds between the OH group of Tyr187 and between the Odelta1 atom of Asn176 and Nepsilon1 atom of Trp249 could play a role in stabilizing the conformation of the halide-binding site. The possibility that these hydrogen bonds are important for halide binding and release was studied using site-directed mutagenesis. Steady-state kinetic studies revealed that mutant Y187F, which has lost both hydrogen bonds, has a higher catalytic activity (k(cat)) with two of the three tested substrates compared to the wild-type enzyme. Mutant W249F also shows an enhanced k(cat) value with these two substrates, as well as a remarkable increase in enantiopreference for (R)-p-nitro-2-bromo-1-phenylethanol. In case of a mutation at position 176 (N176A and N176D), a 1000-fold lower catalytic efficiency (k(cat)/K(m)) was obtained, which is mainly due to an increase of the K(m) value of the enzyme. Pre-steady-state kinetic studies showed that a burst of product formation precedes the steady state, indicating that halide release is still rate-limiting for mutants Y187F and W249F. Stopped-flow fluorescence experiments revealed that the rate of halide release is 5.6-fold higher for the Y187F mutant than for the wild-type enzyme and even higher for the W249F enzyme. Taken together, these results show that the disruption of two hydrogen bonds around the halide-binding site increases the rate of halide release and can enhance the overall catalytic activity of HheC.

Methods for producing single crystal mixed halide perovskites

Science.gov (United States)

Zhu, Kai; Zhao, Yixin

2017-07-11

An aspect of the present invention is a method that includes contacting a metal halide and a first alkylammonium halide in a solvent to form a solution and maintaining the solution at a first temperature, resulting in the formation of at least one alkylammonium halide perovskite crystal, where the metal halide includes a first halogen and a metal, the first alkylammonium halide includes the first halogen, the at least one alkylammonium halide perovskite crystal includes the metal and the first halogen, and the first temperature is above about 21.degree. C.

Photofragmentation of metal halides

International Nuclear Information System (INIS)

Veen, N.J.A. van.

1980-01-01

The author deals with photodissociation of molecules of alkali halides. It is shown that the total absorption cross section consists of two contributions arising from transitions to excited states of total electronic angular momentum Ω=0 + and Ω=1. From the inversion of the absorption continua potential energy curves of the excited states can be constructed in the Franck-Condon region. It is found that for all alkali halides the 0 + state is higher in energy than the Ω=1 state. Extensive studies are reported on three thallium halides, TlI, TlBr and TlCl at various wavelengths covering the near ultraviolet region. (Auth.)

Structure and dynamics of molten salts

International Nuclear Information System (INIS)

Rovere, M.; Tosi, M.P.

1986-02-01

Modern techniques of liquid state physics have been successfully used over the last decade to probe the microscopic structure and dynamics of a variety of multicomponent liquids in which relative ordering of the species is present near freezing. The alkali halides are prototypes for this specific type of short range order in relation to the nature of bonding, but the systems in question include also other monovalent and polyvalent metal-ion halides, alkali-based intermetallic compounds, and chalcogen-based alloys. A viewpoint is taken in this review which gives attention to relations between liquid and solid phase properties across melting for compound systems at stoichiometric composition. In addition, large deviations from stoichiometry can be realized in the liquid phase, to display trends of evolution of structure, bonding and electronic states with composition. (author)

Investigations in anhydrous liquid ammonia. Reaction of group 2, 4, 5, 11 metal and actinoids compounds

International Nuclear Information System (INIS)

Woidy, Patrick

2014-01-01

The solubility and reactivity of metal halides, transition metal halides, and actinoid halides in liquid ammonia can lead to new starting materials for the synthesis of fluorides in low oxidation states or for nitrides via a ''low-temperature route''. In this context the ability of metal and actinoid halides to act as an acceptor for or donor of fluoride ions is also of interest. Four different systems were investigated in this study. In the first section, the synthesis and characterization of new compounds were carried out in the system CuX/NH 3 (X = F, Cl, Br, I, and CN) and lead to a ligand stabilized monovalent copper fluoride as a main result. In the second section, the solubility of uranyl compounds and uranium halides in liquid ammonia was investigated and the products were characterized. In the third section, alkali metal thorates were synthesized. Their solubility in liquid ammonia and their behavior as an acceptor for fluoride ions was investigated. In the last section, the results on the solubility behavior of transition metal halides in liquid ammonia and their coordination behavior are presented. In the first system CuX/NH 3 several new compounds, such as [Cu(NH 3 ) 3 ]X (X = Br, I or CN) were synthesized and characterized. The reactions of this compounds with fluoride ion donors (NH 4 F or Me 4 NF) led unfortunately not to the monovalent copper fluoride CuF. The comproportionation reaction of Cu and CuF 2 in liquid ammonia lead to the compounds [Cu(NH 3 ) 3 ] 2 [Cu 2 (NH 3 ) 2 ] . 4 NH 3 and [Cu(NH 3 ) 2 ]F . NH 3 . For the preparation of binary CuF, various decomposition experiments were executed on the compound [Cu(NH 3 ) 2 ]F . NH 3 which resulted in different decomposition products. In additional studies various complexes of divalent copper was investigated and with the compound [Cu(NH 3 ) 5 ]F 2 . NH 3 the solubility of fluoride containing substances in liquid ammonia could be shown. Studies of six- and tetravalent uranium

Refined potentials for rare gas atom adsorption on rare gas and alkali-halide surfaces

Science.gov (United States)

Wilson, J. W.; Heinbockel, J. H.; Outlaw, R. A.

1985-01-01

The utilization of models of interatomic potential for physical interaction to estimate the long range attractive potential for rare gases and ions is discussed. The long range attractive force is calculated in terms of the atomic dispersion properties. A data base of atomic dispersion parameters for rare gas atoms, alkali ion, and halogen ions is applied to the study of the repulsive core; the procedure for evaluating the repulsive core of ion interactions is described. The interaction of rare gas atoms on ideal rare gas solid and alkali-halide surfaces is analyzed; zero coverage absorption potentials are derived.

Possible configuration of two-knot auto-localized exciton in strainless and deformed alkali halide crystals

International Nuclear Information System (INIS)

Dzhumanov, S.; Tulepbergenov, S.K.; Shunkeev, K.Sh.

2002-01-01

In the paper molecular component of two-knot auto-localized exciton (TALE) occupying centrosymmetric state in alkali halide crystal cubic lattice with local D 2h symmetry is considered. In is suggested that the symmetry lowering of forming small radius auto-localized exciton (ALE) is realizing in order configuration transformation by the scenario: multi-knot continual ALE (with O h symmetry)→six-halide ALE (with O h symmetry)→TALE (with O h symmetry) or by the scenario O h →D 2h . Then for TALE with local D 2h symmetry normal molecular ion shifts are considered as well

Monovalent IgG4 molecules

Science.gov (United States)

Wilkinson, Ian C.; Fowler, Susan B.; Machiesky, LeeAnn; Miller, Kenneth; Hayes, David B.; Adib, Morshed; Her, Cheng; Borrok, M. Jack; Tsui, Ping; Burrell, Matthew; Corkill, Dominic J.; Witt, Susanne; Lowe, David C.; Webster, Carl I.

2013-01-01

Antibodies have become the fastest growing class of biological therapeutics, in part due to their exquisite specificity and ability to modulate protein-protein interactions with a high biological potency. The relatively large size and bivalency of antibodies, however, limits their use as therapeutics in certain circumstances. Antibody fragments, such as single-chain variable fragments and antigen binding-fragments, have emerged as viable alternatives, but without further modifications these monovalent formats have reduced terminal serum half-lives because of their small size and lack of an Fc domain, which is required for FcRn-mediated recycling. Using rational engineering of the IgG4 Fc domain to disrupt key interactions at the CH3-CH3 interface, we identified a number of point mutations that abolish Fc dimerization and created half-antibodies, a novel monovalent antibody format that retains a monomeric Fc domain. Introduction of these mutations into an IgG1 framework also led to the creation of half-antibodies. These half-antibodies were shown to be soluble, thermodynamically stable and monomeric, characteristics that are favorable for use as therapeutic proteins. Despite significantly reduced FcRn binding in vitro, which suggests that avidity gains in a dimeric Fc are critical to optimal FcRn binding, this format demonstrated an increased terminal serum half-life compared with that expected for most alternative antibody fragments. PMID:23567207

Tumour targeting with monovalent fragments of anti-neuroblastoma antibody chCE7

International Nuclear Information System (INIS)

Carrel, F.; Novak-Hofer, I.; Ruch, C.; Zimmermann, K.; Amstutz, H.

1997-01-01

The in vitro and in vivo behaviour of the monovalent single chain (scFv) and Fab-fragments derived from anti-neuroblastoma antibody chCE7 is reported. When comparing tumour uptake and -retention of radioactivity of 67 Cu-labelled monovalent chCE7 with divalent chCE7 F(ab') 2 the advantage of the radiocopper label over the radioiodine label was more pronounced with the divalent (internalising) F(ab') 2 fragments. (author) 1 fig., 1 ref

Relation between the electroforming voltage in alkali halide-polymer diodes and the bandgap of the alkali halide

International Nuclear Information System (INIS)

Bory, Benjamin F.; Wang, Jingxin; Janssen, René A. J.; Meskers, Stefan C. J.; Gomes, Henrique L.; De Leeuw, Dago M.

2014-01-01

Electroforming of indium-tin-oxide/alkali halide/poly(spirofluorene)/Ba/Al diodes has been investigated by bias dependent reflectivity measurements. The threshold voltages for electrocoloration and electroforming are independent of layer thickness and correlate with the bandgap of the alkali halide. We argue that the origin is voltage induced defect formation. Frenkel defect pairs are formed by electron–hole recombination in the alkali halide. This self-accelerating process mitigates injection barriers. The dynamic junction formation is compared to that of a light emitting electrochemical cell. A critical defect density for electroforming is 10 25 /m 3 . The electroformed alkali halide layer can be considered as a highly doped semiconductor with metallic transport characteristics

Diphtheria toxin-induced channels in Vero cells selective for monovalent cations

International Nuclear Information System (INIS)

Sandvig, K.; Olsnes, S.

1988-01-01

Ion fluxes associated with translocation of diphtheria toxin across the surface membrane of Vero cells were studied. When cells with surface-bound toxin were exposed to low pH to induce toxin entry, the cells became permeable to Na+, K+, H+, choline+, and glucosamine+. There was no increased permeability to Cl-, SO4(-2), glucose, or sucrose, whereas the uptake of 45 Ca2+ was slightly increased. The influx of Ca2+, which appears to be different from that of monovalent cations, was reduced by several inhibitors of anion transport and by verapamil, Mn2+, Co2+, and Ca2+, but not by Mg2+. The toxin-induced fluxes of N+, K+, and protons were inhibited by Cd2+. Cd2+ also protected the cells against intoxication by diphtheria toxin, suggesting that the open cation-selective channel is required for toxin translocation. The involvement of the toxin receptor is discussed

Ion distributions at charged aqueous surfaces: Synchrotron X-ray scattering studies

Energy Technology Data Exchange (ETDEWEB)

Bu, Wei [Iowa State Univ., Ames, IA (United States)

2009-01-01

Surface sensitive synchrotron X-ray scattering studies were performed to obtain the distribution of monovalent ions next to a highly charged interface at room temperature. To control surface charge density, lipids, dihexadecyl hydrogen-phosphate (DHDP) and dimysteroyl phosphatidic acid (DMPA), were spread as monolayer materials at the air/water interface, containing CsI at various concentrations. Five decades in bulk concentrations (CsI) are investigated, demonstrating that the interfacial distribution is strongly dependent on bulk concentration. We show that this is due to the strong binding constant of hydronium H3O+ to the phosphate group, leading to proton-transfer back to the phosphate group and to a reduced surface charge. Using anomalous reflectivity off and at the L3 Cs+ resonance, we provide spatial counterion (Cs+) distributions next to the negatively charged interfaces. The experimental ion distributions are in excellent agreement with a renormalized surface charge Poisson-Boltzmann theory for monovalent ions without fitting parameters or additional assumptions. Energy Scans at four fixed momentum transfers under specular reflectivity conditions near the Cs+ L3 resonance were conducted on 10-3 M CsI with DHDP monolayer materials on the surface. The energy scans exhibit a periodic dependence on photon momentum transfer. The ion distributions obtained from the analysis are in excellent agreement with those obtained from anomalous reflectivity measurements, providing further confirmation to the validity of the renormalized surface charge Poisson-Boltzmann theory for monovalent ions. Moreover, the dispersion corrections f0 and f00 for Cs+ around L3 resonance, revealing the local environment of a Cs+ ion in the solution at the interface, were extracted simultaneously with output of ion distributions.

Immunogenic Response of Rabbits to Monovalent and Polyvalent ...

African Journals Online (AJOL)

This work was carried out in University of Surrey UK Department of Microbiology. In this study, the efficacy of monovalent and polyvalent vaccines made from Mannhaemia haemolytica antigens, were evaluated by measuring specific serum antibody titers produced against the bacteria in immunized rabbits. Eleven biotype A ...

Effect of divalent versus monovalent cations on the MS2 retention capacity of amino-functionalized ceramic filters.

Science.gov (United States)

Bartels, J; Hildebrand, N; Nawrocki, M; Kroll, S; Maas, M; Colombi Ciacchi, L; Rezwan, K

2018-04-25

Ceramic capillary membranes conditioned for virus filtration via functionalization with n-(3-trimethoxysilylpropyl)diethylenetriamine (TPDA) are analyzed with respect to their virus retention capacity when using feed solutions based on monovalent and divalent salts (NaCl, MgCl2). The log reduction value (LRV) by operating in dead-end mode using the model bacteriophage MS2 with a diameter of 25 nm and an IEP of 3.9 is as high as 9.6 when using feeds containing MgCl2. In contrast, a lesser LRV of 6.4 is observed for feed solutions based on NaCl. The TPDA functionalized surface is simulated at the atomistic scale using explicit-solvent molecular dynamics in the presence of either Na+ or Mg2+ ions. Computational prediction of the binding free energy reveals that the Mg2+ ions remain preferentially adsorbed at the surface, whereas Na+ ions form a weakly bound dissolved ionic layer. The charge shielding between surface and amino groups by the adsorbed Mg2+ ions leads to an upright orientation of the TPDA molecules as opposed to a more tilted orientation in the presence of Na+ ions. The resulting better accessibility of the TPDA molecules is very likely responsible for the enhanced virus retention capacity using a feed solution with Mg2+ ions.

Halide-Dependent Electronic Structure of Organolead Perovskite Materials

KAUST Repository

Buin, Andrei; Comin, Riccardo; Xu, Jixian; Ip, Alexander H.; Sargent, Edward H.

2015-01-01

-based perovskites, in line with recent experimental data. As a result, the optimal growth conditions are also different for the distinct halide perovskites: growth should be halide-rich for Br and Cl, and halide-poor for I-based perovskites. We discuss stability

Experimental Characterization and Modelization of Ion Exchange Kinetics for a Carboxylic Resin in Infinite Solution Volume Conditions. Application to Monovalent-Trivalent Cations Exchange

Energy Technology Data Exchange (ETDEWEB)

Picart, S.; Mokhtari, H.; Jobelin, I. [CEA Marcoule, Nucl Energy Div, RadioChem and Proc Dept, Actinides Chem and Convers Lab, F-30207 Bagnols Sur Ceze (France); Ramiere, I. [Fuel Simulat Lab, Fuel Study Dept, F-13108 St Paul Les Durance (France)

2010-07-01

This study is devoted to the characterization of ion exchange inside a microsphere of carboxylic resin. It aims at describing the kinetics of this exchange reaction which is known to be controlled by interdiffusion in the particle. The fractional attainment of equilibrium function of time depends on the concentration of the cations in the resin which can be modelled by the Nernst-Planck equation. A powerful approach for the numerical resolution of this equation is introduced in this paper. This modeling is based on the work of Helfferich but involves an implicit numerical scheme which reduces the computational cost. Knowing the diffusion coefficients of the cations in the resin and the radius of the spherical exchanger, the kinetics can be hence completely determined. When those diffusion parameters are missing, they can be deduced by fitting experimental data of fractional attainment of equilibrium. An efficient optimization tool coupled with the implicit resolution has been developed for this purpose. A monovalent/trivalent cation exchange had been experimentally characterized for a carboxylic resin. Diffusion coefficients and concentration profiles in the resin were then deduced through this new model. (authors)

Experimental Characterization and Modelization of Ion Exchange Kinetics for a Carboxylic Resin in Infinite Solution Volume Conditions. Application to Monovalent-Trivalent Cations Exchange

International Nuclear Information System (INIS)

Picart, S.; Mokhtari, H.; Jobelin, I.; Ramiere, I.

2010-01-01

This study is devoted to the characterization of ion exchange inside a microsphere of carboxylic resin. It aims at describing the kinetics of this exchange reaction which is known to be controlled by interdiffusion in the particle. The fractional attainment of equilibrium function of time depends on the concentration of the cations in the resin which can be modelled by the Nernst-Planck equation. A powerful approach for the numerical resolution of this equation is introduced in this paper. This modeling is based on the work of Helfferich but involves an implicit numerical scheme which reduces the computational cost. Knowing the diffusion coefficients of the cations in the resin and the radius of the spherical exchanger, the kinetics can be hence completely determined. When those diffusion parameters are missing, they can be deduced by fitting experimental data of fractional attainment of equilibrium. An efficient optimization tool coupled with the implicit resolution has been developed for this purpose. A monovalent/trivalent cation exchange had been experimentally characterized for a carboxylic resin. Diffusion coefficients and concentration profiles in the resin were then deduced through this new model. (authors)

Inhibition of mild steel corrosion in acidic medium using synthetic and naturally occurring polymers and synergistic halide additives

Energy Technology Data Exchange (ETDEWEB)

Umoren, S.A. [Department of Chemistry, Faculty of Science, University of Uyo, P.M.B 1017 Uyo (Nigeria)], E-mail: saviourumoren@yahoo.com; Ogbobe, O.; Igwe, I.O. [Department of Polymer and Textile Engineering, School of Engineering and Engineering Technology, Federal University of Technology, P.M.B. 1526 Owerri (Nigeria); Ebenso, E.E. [Department of Chemistry and Chemical Technology, National University of Lesotho, P. O. Roma180, Lesotho (South Africa)

2008-07-15

The corrosion inhibition of mild steel in H{sub 2}SO{sub 4} in the presence of gum arabic (GA) (naturally occurring polymer) and polyethylene glycol (PEG) (synthetic polymer) was studied using weight loss, hydrogen evolution and thermometric methods at 30-60 deg. C. PEG was found to be a better inhibitor for mild steel corrosion in acidic medium than GA. The effect of addition of halides (KCl, KBr and KI) was also studied. Results obtained showed that inhibition efficiency (I%) increased with increase in GA and PEG concentration, addition of halides and with increase in temperature. Increase in inhibition efficiency (I%) and degree of surface coverage ({theta}) was found to follow the trend Cl{sup -} < Br{sup -} < I{sup -} which indicates that the radii and electronegativity of the halide ions play a significant role in the adsorption process. GA and PEG alone and in combination with halides were found to obey Temkin adsorption isotherm. Phenomenon of chemical adsorption is proposed from the trend of inhibition efficiency with temperature and values {delta}G{sub ads}{sup 0} obtained. The synergism parameter, S{sub I} evaluated is found to be greater than unity indicating that the enhanced inhibition efficiency caused by the addition of halides is only due to synergism.

Development of Halide and Oxy-Halides for Isotopic Separations

Energy Technology Data Exchange (ETDEWEB)

Martin, Leigh R. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Johnson, Aaron T. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Pfeiffer, Jana [Idaho National Lab. (INL), Idaho Falls, ID (United States); Finck, Martha R. [Idaho National Lab. (INL), Idaho Falls, ID (United States)

2014-10-01

The goal of this project was to synthesize a volatile form of Np for introduction into mass spectrometers at INL. Volatile solids of the 5f elements are typically those of the halides (e.g. UF6), however fluorine is highly corrosive to the sensitive internal components of the mass separator, and the other volatile halides exist as several different stable isotopes in nature. However, iodide is both mono-isotopic and volatile, and as such presents an avenue for creation of a form of Np suitable for introduction into the mass separator. To accomplish this goal, the technical work in the project sought to establish a novel synthetic route for the conversion NpO2+ (dissolved in nitric acid) to NpI3 and NpI4.

Melting and liquid structure of polyvalent metal halides

International Nuclear Information System (INIS)

Tosi, M.P.

1992-08-01

A short review is given of recent progress in determining and understanding liquid structure types and melting mechanisms for halides of polyvalent metals. The nature of the preferred local coordination for the polyvalent metal ion in the melt can usually be ascertained from data on liquid mixtures with halogen-donating alkali halides. The stability of these local coordination states and the connectivity that arises between them in the approach to the pure melt determines the character of its short-range and possible medium-range order. A broad classification of structural and melting behaviours can be given on the basis of measured melting parameters and transport coefficients for many compounds, in combination with the available diffraction data on the liquid structure of several compounds. Correlations have been shown to exist with a simple indicator of the nature of the chemical bond and also with appropriate parameters of ionic models, wherever the latter are usefully applicable for semiquantitative calculations of liquid structure. Consequences on the mechanisms for valence electron localization in solutions of metallic elements into strongly structured molten salts are also briefly discussed. (author). 46 refs, 4 figs, 2 tabs

Study of a new source for positive and negative ions. Final report

International Nuclear Information System (INIS)

Freedman, A.; Davidovits, P.

1985-05-01

This study has focused on the feasibility of a novel ion source based on the technique of photodissociation, which could provide both positive and negative ions at considerably higher intensities (potentially 10 15 cm -3 ) than are currently available. Ions are produced by irradiating a sample of a gaseous thallium halide salt with an argon fluoride excimer laser operating at 193 nm. At this wavelength, both thallium bromide and iodide will produce atomic ion pairs in a single photon process and molecular positive ions and an electron in a two-photon induced process. The potential traits of such an excimer-laser pumped thallium salt ion source include the following: high intensity and pulse rate, good spatial and temporal resolution, low temperature, good focusing properties, and production of heavy ions. This report describes a Phase I effort investigating the efficacy of this approach. A review of the relevant photophysics pertaining to laser excitation of thallium halide salts is presented, followed by a description of both experimental and theoretical efforts involving thallium bromide in particular. The last section will summarize the basic conclusions derived from these studies, as well as discuss potential advantages of an ion source derived from photolyzing thallium halide salts

Multivalent protein assembly using monovalent self-assembling building blocks

NARCIS (Netherlands)

Petkau - Milroy, K.; Sonntag, M.H.; Colditz, A.; Brunsveld, L.

2013-01-01

Discotic molecules, which self-assemble in water into columnar supramolecular polymers, emerged as an alternative platform for the organization of proteins. Here, a monovalent discotic decorated with one single biotin was synthesized to study the self-assembling multivalency of this system in regard

CuI-Catalyzed: One-Pot Synthesis of Diaryl Disulfides from Aryl Halides and Carbon Disulfide

Directory of Open Access Journals (Sweden)

Mohammad Soleiman-Beigi

2013-01-01

Full Text Available A new application of carbon disulfide in the presence of KF/Al2O3 is reported for the synthesis of organic symmetrical diaryl disulfides. These products were synthesized by one-pot reaction of aryl halides with the in situ generated trithiocarbonate ion in the presence of copper under air atmosphere.

The structure of ions and zwitterionic lipids regulates the charge of dipolar membranes.

Science.gov (United States)

Szekely, Or; Steiner, Ariel; Szekely, Pablo; Amit, Einav; Asor, Roi; Tamburu, Carmen; Raviv, Uri

2011-06-21

In pure water, zwitterionic lipids form lamellar phases with an equilibrium water gap on the order of 2 to 3 nm as a result of the dominating van der Waals attraction between dipolar bilayers. Monovalent ions can swell those neutral lamellae by a small amount. Divalent ions can adsorb onto dipolar membranes and charge them. Using solution X-ray scattering, we studied how the structure of ions and zwitterionic lipids regulates the charge of dipolar membranes. We found that unlike monovalent ions that weakly interact with all of the examined dipolar membranes, divalent and trivalent ions adsorb onto membranes containing lipids with saturated tails, with an association constant on the order of ∼10 M(-1). One double bond in the lipid tail is sufficient to prevent divalent ion adsorption. We suggest that this behavior is due to the relatively loose packing of lipids with unsaturated tails that increases the area per lipid headgroup, enabling their free rotation. Divalent ion adsorption links two lipids and limits their free rotation. The ion-dipole interaction gained by the adsorption of the ions onto unsaturated membranes is insufficient to compensate for the loss of headgroup free-rotational entropy. The ion-dipole interaction is stronger for cations with a higher valence. Nevertheless, polyamines behave as monovalent ions near dipolar interfaces in the sense that they interact weakly with the membrane surface, whereas in the bulk their behavior is similar to that of multivalent cations. Advanced data analysis and comparison with theory provide insight into the structure and interactions between ion-induced regulated charged interfaces. This study models biologically relevant interactions between cell membranes and various ions and the manner in which the lipid structure governs those interactions. The ability to monitor these interactions creates a tool for probing systems that are more complex and forms the basis for controlling the interactions between dipolar

Morphology-Controlled Synthesis of Organometal Halide Perovskite Inverse Opals.

Science.gov (United States)

Chen, Kun; Tüysüz, Harun

2015-11-09

The booming development of organometal halide perovskites in recent years has prompted the exploration of morphology-control strategies to improve their performance in photovoltaic, photonic, and optoelectronic applications. However, the preparation of organometal halide perovskites with high hierarchical architecture is still highly challenging and a general morphology-control method for various organometal halide perovskites has not been achieved. A mild and scalable method to prepare organometal halide perovskites in inverse opal morphology is presented that uses a polystyrene-based artificial opal as hard template. Our method is flexible and compatible with different halides and organic ammonium compositions. Thus, the perovskite inverse opal maintains the advantage of straightforward structure and band gap engineering. Furthermore, optoelectronic investigations reveal that morphology exerted influence on the conducting nature of organometal halide perovskites. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Photoluminescence characteristics of sintered silica glass doped with Cu ions using mesoporous SiO{sub 2}-PVA nanocomposite

Energy Technology Data Exchange (ETDEWEB)

Ikeda, Hiroshi [Art, Science and Technology Center for Cooperative Research, Kyushu University, Kasuga, Fukuoka 816-8580 (Japan); Murata, Takahiro [Faculty of Education and Master' s Course in Education, Kumamoto University, 2-40-1 Kurokami, Chuo-ku, Kumamoto 860-8555 (Japan); Fujino, Shigeru, E-mail: fujino@astec.kyushu-u.ac.jp [Art, Science and Technology Center for Cooperative Research, Kyushu University, Kasuga, Fukuoka 816-8580 (Japan)

2015-07-15

Monolithic silica glasses doped with Cu ions were prepared by immersing a mesoporous SiO{sub 2}-polyvinyl alcohol (PVA) nanocomposite in a copper nitrate solution followed by sintering at 1100 °C for 12 h in air. The Cu ions were reduced from divalent to monovalent during the sintering process and consequently Cu{sup +} was doped into the silica glass matrix. The sintered glass possessed blue or yellow photoluminescence (PL) under UV irradiation, depending on the total concentration of Cu ions in the sintered silica glass. At a lower concentration below 30 ppm, the isolated Cu{sup +} existed in the glass matrix resulting in the blue PL. However, above 70 ppm, the Cu{sup +}–Cu{sup +} pairs were present, exhibiting the yellow PL. It was demonstrated that the PL characteristics of the sintered silica glasses doped with monovalent copper ions were affected by the total concentration of Cu ions in the glass, which can be adjusted as a function of the immersion conditions. - Highlights: • Silica glass doped with Cu{sup +} was fabricated by sintering the nanocomposite. • The Cu ions were reduced from divalent to monovalent during the sintering process. • The sintered glass possessed blue or yellow PL under UV irradiation. • The blue and yellow PL are due to isolated Cu{sup +} and Cu{sup +}–Cu{sup +} pairs, respectively. • The PL characteristics depended on the total concentration of Cu ions in the glass.

Making and Breaking of Lead Halide Perovskites

KAUST Repository

Manser, Joseph S.; Saidaminov, Makhsud I.; Christians, Jeffrey A.; Bakr, Osman; Kamat, Prashant V.

2016-01-01

To date, improvements in perovskite solar cell efficiency have resulted primarily from better control over thin film morphology, manipulation of the stoichiometry and chemistry of lead halide and alkylammonium halide precursors, and the choice

TRANSURANIC METAL HALIDES AND A PROCESS FOR THE PRODUCTION THEREOF

Science.gov (United States)

Fried, S.

1951-03-20

Halides of transuranic elements are prepared by contacting with aluminum and a halogen, or with an aluminum halide, a transuranic metal oxide, oxyhalide, halide, or mixture thereof at an elevated temperature.

Halide peroxidase in tissues that interact with bacteria in the host squid Euprymna scolopes.

Science.gov (United States)

Small, A L; McFall-Ngai, M J

1999-03-15

An enzyme with similarities to myeloperoxidase, the antimicrobial halide peroxidase in mammalian neutrophils, occurs abundantly in the light organ tissue of Euprymna scolopes, a squid that maintains a beneficial association with the luminous bacterium Vibrio fischeri. Using three independent assays typically applied to the analysis of halide peroxidase enzymes, we directly compared the activity of the squid enzyme with that of human myeloperoxidase. One of these methods, the diethanolamine assay, confirmed that the squid peroxidase requires halide ions for its activity. The identification of a halide peroxidase in a cooperative bacterial association suggested that this type of enzyme can function not only to control pathogens, but also to modulate the interactions of host animals with their beneficial partners. To determine whether the squid peroxidase functions under both circumstances, we examined its distribution in a variety of host tissues, including those that typically interact with bacteria and those that do not. Tissues interacting with bacteria included those that have specific cooperative associations with bacteria (i.e., the light organ and accessory nidamental gland) and those that have transient nonspecific interactions with bacteria (i.e., the gills, which clear the cephalopod circulatory system of invading microorganisms). These bacteria-associated tissues were compared with the eye, digestive gland, white body, and ink-producing tissues, which do not typically interact directly with bacteria. Peroxidase enzyme assays, immunocytochemical localization, and DNA-RNA hybridizations showed that the halide-dependent peroxidase is consistently expressed in high concentration in tissues that interact bacteria. Elevated levels of the peroxidase were also found in the ink-producing tissues, which are known to have enzymatic pathways associated with antimicrobial activity. Taken together, these data suggest that the host uses a common biochemical response to

Postsynthetic Doping of MnCl2 Molecules into Preformed CsPbBr3 Perovskite Nanocrystals via a Halide Exchange-Driven Cation Exchange.

Science.gov (United States)

Huang, Guangguang; Wang, Chunlei; Xu, Shuhong; Zong, Shenfei; Lu, Ju; Wang, Zhuyuan; Lu, Changgui; Cui, Yiping

2017-08-01

Unlike widely used postsynthetic halide exchange for CsPbX 3 (X is halide) perovskite nanocrystals (NCs), cation exchange of Pb is of a great challenge due to the rigid nature of the Pb cationic sublattice. Actually, cation exchange has more potential for rendering NCs with peculiar properties. Herein, a novel halide exchange-driven cation exchange (HEDCE) strategy is developed to prepare dually emitting Mn-doped CsPb(Cl/Br) 3 NCs via postsynthetic replacement of partial Pb in preformed perovskite NCs. The basic idea for HEDCE is that the partial cation exchange of Pb by Mn has a large probability to occur as a concomitant result for opening the rigid halide octahedron structure around Pb during halide exchange. Compared to traditional ionic exchange, HEDCE is featured by proceeding of halide exchange and cation exchange at the same time and lattice site. The time and space requirements make only MnCl 2 molecules (rather than mixture of Mn and Cl ions) capable of doping into perovskite NCs. This special molecular doping nature results in a series of unusual phenomenon, including long reaction time, core-shell structured mid states with triple emission bands, and dopant molecules composition-dependent doping process. As-prepared dual-emitting Mn-doped CsPb(Cl/Br) 3 NCs are available for ratiometric temperature sensing. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

High-Performance Thin-Film-Nanocomposite Cation Exchange Membranes Containing Hydrophobic Zeolitic Imidazolate Framework for Monovalent Selectivity

Directory of Open Access Journals (Sweden)

Jian Li

2018-05-01

Full Text Available Zeolitic imidazolate framework-8 (ZIF-8 offers good hydrothermal, chemical, and thermal stabilities, and is therefore of interest in membrane synthesis. In this work, an interfacial polymerization (IP method was applied by anchoring ZIF-8 to the skin layer of thin-film nanocomposite (TFN membranes in order to obtain monovalent selectivity in electrodialysis. Organic trimesoyl chloride (TMC, 0.1 wt % solutions and aqueous m-phenyl diamine (MPD, 2% w/v solutions were used during the interfacial polymerization process. A range of polyamine (PA/ZIF-8 based membranes was fabricated by varying the concentration of ZIF-8 in the organic solution. The properties of the primary and modified membrane were characterized by scanning electron microscope (SEM, energy dispersive X-ray analysis (EDAX, atomic force microscopy (AFM, water uptake, ion exchange capacity, and contact angle measurements. No significant changes of the surface structure of the PA/ZIF-8 based membranes were observed. Nevertheless, the presence of ZIF-8 under the PA layer plays a key role in the separation process. For single salt solutions that were applied in electrodialysis (ED, faster transport of Na+ and Mg2+ was obtained after introducing the ZIF-8 nanoparticles, however, the desalination efficiency remained constant. When the hybrid membranes were applied to electrodialysis for binary mixtures containing Na+ as well as Mg2+, it was demonstrated that the monovalent selectivity and Na+ flux were enhanced by a higher ZIF-8 loading.

Muonium centers in the alkali halides

International Nuclear Information System (INIS)

Baumeler, H.; Kiefl, R.F.; Keller, H.; Kuendig, W.; Odermatt, W.; Patterson, B.D.; Schneider, J.W.; Savic, I.M.

1986-01-01

Muonium centers (Mu) in single crystals and powdered alkali halides have been studied using the high-timing-resolution transverse field μSR technique. Mu has been observed and its hyperfine parameter (HF) determined in every alkali halide. For the rocksalt alkali halides, the HF parameter A μ shows a systematic dependence on the host lattice constant. A comparison of the Mu HF parameter with hydrogen ESR data suggests that the Mu center is the muonic analogue of the interstitial hydrogen H i 0 -center. The rate of Mu diffusion can be deduced from the motional narrowing of the nuclear hyperfine interaction. KBr shows two different Mu states, a low-temperature Mu I -state and a high-temperature Mu II -state. (orig.)

The influence of monovalent cations on trimeric G protein Gi1alfa activity in HEK293 cells stably expressing DOR-Gi1alfa (Cys351-Ile351) fusion protein

Czech Academy of Sciences Publication Activity Database

Vošahlíková, Miroslava; Svoboda, Petr

2011-01-01

Roč. 60, č. 3 (2011), s. 541-547 ISSN 0862-8408 R&D Projects: GA AV ČR(CZ) IAA500110606; GA MŠk(CZ) LC554; GA ČR(CZ) GD305/08/H037 Institutional research plan: CEZ:AV0Z50110509 Keywords : delta-opioid receptor (DOR) * monovalent ions * G(i)1alfa protein Subject RIV: CE - Biochemistry Impact factor: 1.555, year: 2011

Investigation of surface halide modification of nitrile butadiene rubber

Science.gov (United States)

Sukhareva, K. V.; Mikhailov, I. A.; Andriasyan, Yu O.; Mastalygina, E. E.; Popov, A. A.

2017-12-01

The investigation is devoted to the novel technology of surface halide modification of rubber samples based on nitrile butadiene rubber (NBR). 1,1,2-trifluoro-1,2,2-trichlorethane was used as halide modifier. The developed technology is characterized by production stages reduction to one by means of treating the rubber compound with a halide modifier. The surface halide modification of compounds based on nitrile butadiene rubber (NBR) was determined to result in increase of resistance to thermal oxidation and aggressive media. The conducted research revealed the influence of modification time on chemical resistance and physical-mechanical properties of rubbers under investigation.

The alkali halide disk technique in infra-red spectrometry : Anomalous behaviour of some samples dispersed in alkali halide disks

NARCIS (Netherlands)

Tolk, A.

1961-01-01

Some difficulties encountered in the application of the alkali halide disk technique in infra-red spectrometry are discussed. Complications due to interaction of the sample with the alkali halide have been studied experimentally. It was found that the anomalous behaviour of benzoic acid, succinic

Abiotic Formation of Methyl Halides in the Terrestrial Environment

Science.gov (United States)

Keppler, F.

2011-12-01

Methyl chloride and methyl bromide are the most abundant chlorine and bromine containing organic compounds in the atmosphere. Since both compounds have relatively long tropospheric lifetimes they can effectively transport halogen atoms from the Earth's surface, where they are released, to the stratosphere and following photolytic oxidation form reactive halogen gases that lead to the chemical destruction of ozone. Methyl chloride and methyl bromide account for more than 20% of the ozone-depleting halogens delivered to the stratosphere and are predicted to grow in importance as the chlorine contribution to the stratosphere from anthropogenic CFCs decline. Today methyl chloride and methyl bromide originate mainly from natural sources with only a minor fraction considered to be of anthropogenic origin. However, until as recently as 2000 most of the methyl chloride and methyl bromide input to the atmosphere was considered to originate from the oceans, but investigations in recent years have clearly demonstrated that terrestrial sources such as biomass burning, wood-rotting fungi, coastal salt marshes, tropical vegetation and organic matter degradation must dominate the atmospheric budgets of these trace gases. However, many uncertainties still exist regarding strengths of both sources and sinks, as well as the mechanisms of formation of these naturally occurring halogenated gases. A better understanding of the atmospheric budget of both methyl chloride and methyl bromide is therefore required for reliable prediction of future ozone depletion. Biotic and abiotic methylation processes of chloride and bromide ion are considered to be the dominant pathways of formation of these methyl halides in nature. In this presentation I will focus on abiotic formation processes in the terrestrial environment and the potential parameters that control their emissions. Recent advances in our understanding of the abiotic formation pathway of methyl halides will be discussed. This will

Energy distributions of atoms sputtered from alkali halides by 540 eV electrons, Ch.1

International Nuclear Information System (INIS)

Overeijnder, H.; Szymonski, M.; Haring, A.; Vries, A.E. de

1978-01-01

The emission of halogen and alkali atoms, occurring under bombardment of alkali halides with electrons has been investigated. The electron energy was 540 eV and the temperature of the target was varied between room temperature and 400 0 C. The energy distribution of the emitted neutral particles was measured with a time of flight method. It was found that either diffusing interstitial halogen atoms or moving holes dominate the sputtering process above 200 0 C. Below 150 0 C alkali halides with lattice parameters s/d >= 0.33 show emission of non-thermal halogen atoms. s is the interionic space between two halogen ions in a direction and d is the diameter of a halogen atom. In general the energy distribution of the alkali and halogen atoms is thermal above 200 0 C, but not Maxwellian. (Auth.)

Treatment of alcaline metals halides for developing crystals

International Nuclear Information System (INIS)

Spurney, R.W.

1974-01-01

A process is described whereby crystals of an alkaline metal halide may be dried and placed in a crucible for development by the Bridgeman-Stockbarger method. Purified alkaline halides from a suspension are dried and formed into dense cakes of transverse section slightly smaller than that of the crucible, where they are packed, melted and grown into crystals according to the Bridgeman-Stockbarger technique. This method applies to the preparation of alkaline halide crystals, particularly sodium iodide for optical elements or scintillation counters [fr

Cation-Dependent Light-Induced Halide Demixing in Hybrid Organic-Inorganic Perovskites.

Science.gov (United States)

Sutter-Fella, Carolin M; Ngo, Quynh P; Cefarin, Nicola; Gardner, Kira L; Tamura, Nobumichi; Stan, Camelia V; Drisdell, Walter S; Javey, Ali; Toma, Francesca M; Sharp, Ian D

2018-06-13

Mixed cation metal halide perovskites with increased power conversion efficiency, negligible hysteresis, and improved long-term stability under illumination, moisture, and thermal stressing have emerged as promising compounds for photovoltaic and optoelectronic applications. Here, we shed light on photoinduced halide demixing using in situ photoluminescence spectroscopy and in situ synchrotron X-ray diffraction (XRD) to directly compare the evolution of composition and phase changes in CH(NH 2 ) 2 CsPb-halide (FACsPb-) and CH 3 NH 3 Pb-halide (MAPb-) perovskites upon illumination, thereby providing insights into why FACs-perovskites are less prone to halide demixing than MA-perovskites. We find that halide demixing occurs in both materials. However, the I-rich domains formed during demixing accumulate strain in FACsPb-perovskites but readily relax in MA-perovskites. The accumulated strain energy is expected to act as a stabilizing force against halide demixing and may explain the higher Br composition threshold for demixing to occur in FACsPb-halides. In addition, we find that while halide demixing leads to a quenching of the high-energy photoluminescence emission from MA-perovskites, the emission is enhanced from FACs-perovskites. This behavior points to a reduction of nonradiative recombination centers in FACs-perovskites arising from the demixing process and buildup of strain. FACsPb-halide perovskites exhibit excellent intrinsic material properties with photoluminescence quantum yields that are comparable to MA-perovskites. Because improved stability is achieved without sacrificing electronic properties, these compositions are better candidates for photovoltaic applications, especially as wide bandgap absorbers in tandem cells.

Formability of ABX3 (X=F,Cl,Br,I) halide perovskites

International Nuclear Information System (INIS)

Li Chonghea; Lu Xionggang; Ding Weizhong; Feng Liming; Gao Yonghui; Guo Ziming

2008-01-01

In this study a total of 186 complex halide systems were collected; the formabilities of ABX 3 (X = F, Cl, Br and I) halide perovskites were investigated using the empirical structure map, which was constructed by Goldschmidt's tolerance factor and the octahedral factor. A model for halide perovskite formability was built up. In this model obtained, for all 186 complex halides systems, only one system (CsF-MnF 2 ) without perovskite structure and six systems (RbF-PbF 2 , CsF- BeF 2 , KCl-FeCl 2 , TlI-MnI 2 , RbI-SnI 2 , TlI-PbI 2 ) with perovskite structure were wrongly classified, so its predicting accuracy reaches 96%. It is also indicated that both the tolerance factor and the octahedral factor are a necessary but not sufficient condition for ABX 3 halide perovskite formability, and a lowest limit of the octahedral factor exists for halide perovskite formation. This result is consistent with our previous report for ABO 3 oxide perovskite, and may be helpful to design novel halide materials with the perovskite structure. (orig.)

Electron transport through monovalent atomic wires

DEFF Research Database (Denmark)

Lee, Y. J.; Brandbyge, Mads; Puska, M. J.

2004-01-01

at the chain determine the conductance. As a result, the conductance for noble-metal chains is close to one quantum of conductance, and it oscillates moderately so that an even number of chain atoms yields a higher value than an odd number. The conductance oscillations are large for alkali-metal chains......Using a first-principles density-functional method we model electron transport through linear chains of monovalent atoms between two bulk electrodes. For noble-metal chains the transport resembles that for free electrons over a potential barrier whereas for alkali-metal chains resonance states...... and their phase is opposite to that of noble-metal chains....

Synthesis, Reactivity and Stability of Aryl Halide Protecting Groups towards Di-Substituted Pyridines

Directory of Open Access Journals (Sweden)

Ptoton Mnangat Brian

2016-03-01

Full Text Available This paper reports the synthesis and reactivity of different Benzyl derivative protecting groups. The synthesis and stability of Benzyl halides, 4-methoxybenzyl halides, 3,5-dimethoxybenzyl halides, 3,4-dimethoxybenzyl halides, 3,4,5-trimethoxybenzyl halide protecting groups and their reactivity towards nitrogen atom of a di-substituted pyridine ring in formation of pyridinium salts is also reported.

Secondary emission of negative ions and electrons resulting from electronic sputtering of cesium salts

International Nuclear Information System (INIS)

Allali, H.; Nsouli, B.; Thomas, J.P.

1993-04-01

Secondary ion emission of negative ions and electrons from alkali salts bombarded with high energy (9 MeV) Ar +++ is discussed. Quite different features are observed according to the nature of the salt investigated (halide or oxygenated). In the case of cesium, the electron emission from halides is characterized by intense electron showers (several hundred electrons) with narrow distributions in intensity and orientation. Conversely, for oxygenated salts, these distributions are broader, much less intense (one order of magnitude), and the ion emission exhibits an dissymmetry, which has never been observed for inorganics. This last result is interpreted in terms of radiolysis of the oxygenated salt, a process well documented for gamma-ray irradiation, but not yet reported in secondary ion emission. (author) 17 refs.; 10 figs

High temperature reactions between molybdenum and metal halides

International Nuclear Information System (INIS)

Boeroeczki, A.; Dobos, G.; Josepovits, V.K.; Hars, Gy.

2006-01-01

Good colour rendering properties, high intensity and efficacy are of vital importance for high-end lighting applications. These requirements can be achieved by high intensity discharge lamps doped with different metal halide additives (metal halide lamps). To improve their reliability, it is very important to understand the different failure processes of the lamps. In this paper, the corrosion reactions between different metal halides and the molybdenum electrical feed-through electrode are discussed. The reactions were studied in the feed-through of real lamps and on model samples too. X-ray photoelectron spectroscopy (XPS) was used to establish the chemical states. In case of the model samples we have also used atomic absorption spectroscopy (AAS) to measure the reaction product amounts. Based on the measurement results we were able to determine the most corrosive metal halide components and to understand the mechanism of the reactions

Halide-Dependent Electronic Structure of Organolead Perovskite Materials

KAUST Repository

Buin, Andrei

2015-06-23

© 2015 American Chemical Society. Organometal halide perovskites have recently attracted tremendous attention both at the experimental and theoretical levels. These materials, in particular methylammonium triiodide, are still limited by poor chemical and structural stability under ambient conditions. Today this represents one of the major challenges for polycrystalline perovskite-based photovoltaic technology. In addition to this, the performance of perovskite-based devices is degraded by deep localized states, or traps. To achieve better-performing devices, it is necessary to understand the nature of these states and the mechanisms that lead to their formation. Here we show that the major sources of deep traps in the different halide systems have different origin and character. Halide vacancies are shallow donors in I-based perovskites, whereas they evolve into a major source of traps in Cl-based perovskites. Lead interstitials, which can form lead dimers, are the dominant source of defects in Br-based perovskites, in line with recent experimental data. As a result, the optimal growth conditions are also different for the distinct halide perovskites: growth should be halide-rich for Br and Cl, and halide-poor for I-based perovskites. We discuss stability in relation to the reaction enthalpies of mixtures of bulk precursors with respect to final perovskite product. Methylammonium lead triiodide is characterized by the lowest reaction enthalpy, explaining its low stability. At the opposite end, the highest stability was found for the methylammonium lead trichloride, also consistent with our experimental findings which show no observable structural variations over an extended period of time.

Probing ion-specific effects on aqueous acetate solutions: Ion pairing versus water structure modifications.

Science.gov (United States)

Petit, Tristan; Lange, Kathrin M; Conrad, Gerrit; Yamamoto, Kenji; Schwanke, Christoph; Hodeck, Kai F; Dantz, Marcus; Brandenburg, Tim; Suljoti, Edlira; Aziz, Emad F

2014-05-01

The effect of monovalent cations (Li(+), K(+), NH4 (+), Na(+)) on the water structure in aqueous chloride and acetate solutions was characterized by oxygen K-edge X-ray absorption spectroscopy (XAS), X-ray emission spectroscopy, and resonant inelastic X-ray scattering (RIXS) of a liquid microjet. We show ion- and counterion dependent effects on the emission spectra of the oxygen K-edge, which we attribute to modifications of the hydrogen bond network of water. For acetates, ion pairing with carboxylates was also probed selectively by XAS and RIXS. We correlate our experimental results to speciation data and to the salting-out properties of the cations.

Probing ion-specific effects on aqueous acetate solutions: Ion pairing versus water structure modifications

Directory of Open Access Journals (Sweden)

Tristan Petit

2014-05-01

Full Text Available The effect of monovalent cations (Li+, K+, NH4+, Na+ on the water structure in aqueous chloride and acetate solutions was characterized by oxygen K-edge X-ray absorption spectroscopy (XAS, X-ray emission spectroscopy, and resonant inelastic X-ray scattering (RIXS of a liquid microjet. We show ion- and counterion dependent effects on the emission spectra of the oxygen K-edge, which we attribute to modifications of the hydrogen bond network of water. For acetates, ion pairing with carboxylates was also probed selectively by XAS and RIXS. We correlate our experimental results to speciation data and to the salting-out properties of the cations.

Entropy in halide perovskites

Science.gov (United States)

Katan, Claudine; Mohite, Aditya D.; Even, Jacky

2018-05-01

Claudine Katan, Aditya D. Mohite and Jacky Even discuss the possible impact of various entropy contributions (stochastic structural fluctuations, anharmonicity and lattice softness) on the optoelectronic properties of halide perovskite materials and devices.

Linear chrono-amperometry using re-dissolution: application to halides

International Nuclear Information System (INIS)

Perchard, J.-P.; Buvet, M.; Molina, R.

1966-06-01

The possibility of applying linear chrono-amperometry to analysis was studied using a falling-drop mercury electrode. Measurements of the cations were carried out by direct reduction or by prior formation of an amalgam, which is then oxidized. Using the first technique, the minimum concentration that can be attained is about 10 -6 M and the reproducibility of the results is of the order of 2%. With the second method the sensitivity is much improved: in the concentration range of 10 -7 to 10 -8 M, the scatter of the results is less than 10% if the agitation and temperature conditions are kept constant. The halides are determined by re-dissolving the mercurous halide deposit formed by electrolysis. From the analytical point of view, the sensitivity is limited in the domain where the phenomena can be interpreted and used. In the case of the chloride ion the lower limit of this zone is close to 10 -5 M; it is 10 -6 M for the bromide and less than 10 -7 M for the iodide. For lower concentrations, simple laws that might be applied in analysis are no longer valid. However, the splitting of the peak observed during the reduction of the mercurous iodide deposit was interpreted as showing that the mono-molecular Hg 2 I 2 layer formed on the drop has particular electrochemical properties. (authors) [fr

MAPbI2.9-xBrxCl0.1 hybrid halide perovskites: Shedding light on the effect of chloride and bromide ions on structural and photoluminescence properties

Science.gov (United States)

Atourki, Lahoucine; Vega, Erika; Marí, Bernabé; Mollar, Miguel; Ait Ahsaine, Hassan; Bouabid, Khalid; Ihlal, Ahmed

2016-12-01

The optical and structural properties of CH3NH3PbI3 can be adjusted by introducing other extrinsic ions such as chloride and bromide. In this work, mixed bromide iodide lead perovskites with a 10% fraction of chloride were prepared from methylamine, lead nitrate and the corresponding hydro acid (X = I, Br, Cl). The effect of bromide and chloride incorporation on different properties of perovskite thin film was investigated. The Pawley fit method indicates the formation of the iodide halide MAPbI3 Pm-3 m cubic phase for x = 0 and the tetragonal P4/mmm phase for x ≥ 0.3. All deposited films showed a strong absorbance in the UV-vis range. The band gap values were estimated from absorbance measurements. It was found that the onset of the absorption edge for MAPbI2.9-xBrxCl0.1 thin film perovskites ranges between 1.60 and 1.80 eV. Moreover, it was found that both Cl and Br affect the PL emission of the mixed halide lead perovskite, the MAPbI2.9-xBrxCl0.1 films displayed intermediate values from 730 nm (MAPbI2.2Br0.7Cl0.1) to 770 nm (MAPbI2.6Br0.3Cl0.1).

Kinetics of ion-ion mutual neutralization: Halide anions with polyatomic cations

Energy Technology Data Exchange (ETDEWEB)

Shuman, Nicholas S.; Wiens, Justin P.; Miller, Thomas M.; Viggiano, Albert A., E-mail: rvborgmailbox@kirtland.af.mil [Space Vehicles Directorate, Air Force Research Laboratory, Kirtland Air Force Base, Albuquerque, New Mexico 87117 (United States)

2014-06-14

The binary mutual neutralization (MN) of a series of 17 cations (O{sub 2}{sup +}, NO{sup +}, NO{sub 2}{sup +}, CO{sup +}, CO{sub 2}{sup +}, Cl{sup +}, Cl{sub 2}{sup +}, SO{sub 2}{sup +}, CF{sub 3}{sup +}, C{sub 2}F{sub 5}{sup +}, NH{sub 3}{sup +}, H{sub 3}{sup +}, D{sub 3}{sup +}, H{sub 2}O{sup +}, H{sub 3}O{sup +}, ArH{sup +}, ArD{sup +}) with 3 halide anions (Cl{sup −}, Br{sup −}, I{sup −}) has been investigated in a flowing afterglow-Langmuir probe apparatus using the variable electron and neutral density attachment mass spectrometry technique. The MN rate constants of atom-atom reactions are dominated by the chemical nature of the system (i.e., the specific locations of curve crossings). As the number of atoms in the system increases, the MN rate constants become dominated instead by the physical nature of the system (e.g., the relative velocity of the reactants). For systems involving 4 or more atoms, the 300 K MN rate constants are well described by 2.7 × 10{sup −7} μ{sup −0.5}, where the reduced mass is in Da and the resulting rate constants in cm{sup 3} s{sup −1}. An upper limit to the MN rate constants appears well described by the complex potential model described by Hickman assuming a cross-section to neutralization of 11 000 Å{sup 2} at 300 K, equivalent to 3.5 × 10{sup −7} μ{sup −0.5}.

Self-assembling multivalency : supramolecular polymers assembled from monovalent mannose-labelled discotic molecules

NARCIS (Netherlands)

Petkau - Milroy, K.; Brunsveld, L.

2013-01-01

Supramolecular synthesis, the "bottom-up" construction of higher-order structures from monomeric building blocks, represents a flexible approach for the generation of multivalent materials. Here, monovalent building blocks decorated with a single bioactive ligand were synthesized. In water, these

UV Photodissociation Action Spectroscopy of Haloanilinium Ions in a Linear Quadrupole Ion Trap Mass Spectrometer

Science.gov (United States)

Hansen, Christopher S.; Kirk, Benjamin B.; Blanksby, Stephen J.; O'Hair, Richard. A. J.; Trevitt, Adam J.

2013-06-01

UV-vis photodissociation action spectroscopy is becoming increasingly prevalent because of advances in, and commercial availability of, ion trapping technologies and tunable laser sources. This study outlines in detail an instrumental arrangement, combining a commercial ion-trap mass spectrometer and tunable nanosecond pulsed laser source, for performing fully automated photodissociation action spectroscopy on gas-phase ions. The components of the instrumentation are outlined, including the optical and electronic interfacing, in addition to the control software for automating the experiment and performing online analysis of the spectra. To demonstrate the utility of this ensemble, the photodissociation action spectra of 4-chloroanilinium, 4-bromoanilinium, and 4-iodoanilinium cations are presented and discussed. Multiple photoproducts are detected in each case and the photoproduct yields are followed as a function of laser wavelength. It is shown that the wavelength-dependent partitioning of the halide loss, H loss, and NH3 loss channels can be broadly rationalized in terms of the relative carbon-halide bond dissociation energies and processes of energy redistribution. The photodissociation action spectrum of (phenyl)Ag2 + is compared with a literature spectrum as a further benchmark.

Quantification of Ionic Diffusion in Lead Halide Perovskite Single Crystals

KAUST Repository

Peng, Wei

2018-05-25

Lead halide perovskites are mixed electronic/ionic semiconductors that have recently revolutionized the photovoltaics field. The physical characterization of the ionic conductivity has been rather elusive due to the highly intermixing of ionic and electronic current. In this work the synthesis of low defect density monocrystalline MAPbBr3 (MA=Methyl ammonium) solar cells free of hole transport layer (HTL) suppresses the effect of electronic current. Impedance spectroscopy reveals the characteristic signature of ionic diffusion (the Warburg element and transmission line equivalent circuit) and ion accumulation at the MAPbBr3/Au interface. Diffusion coefficients are calculated based on a good correlation between thickness of MAPbBr3 and characteristic diffusion transition frequency. In addition, reactive external interfaces are studied by comparison of polycrystalline MAPbBr3 devices prepared either with or without a HTL. The low frequency response in IS measurements is correlated with the chemical reactivity of moving ions with the external interfaces and diffusion into the HTL.

An ion displacement membrame model.

Science.gov (United States)

Hladky, S B; Harris, J D

1967-09-01

The usual assumption in treating the diffusion of ions in an electric field has been that the movement of each ion is independent of the movement of the others. The resulting equation for diffusion by a succession of spontaneous jumps has been well stated by Parlin and Eyring. This paper will consider one simple case in which a different assumption is reasonable. Diffusion of monovalent positive ions is considered as a series of jumps from one fixed negative site to another. The sites are assumed to be full (electrical neutrality). Interaction occurs by the displacement of one ion by another. An ion leaves a site if and only if another ion, not necessarily of the same species, attempts to occupy the same site. Flux ratios and net fluxes are given as functions of the electrical potential, concentration ratios, and number of sites encountered in crossing the membrane. Quantitative comparisons with observations of Hodgkin and Keynes are presented.

Ion exchange purification of scandium

Science.gov (United States)

Herchenroeder, Laurie A.; Burkholder, Harvey R.

1990-10-23

An improvement in purification of scandium through ion exchange chromatography is disclosed in which the oxidation potential of the eluting solution is altered by the addition of potassium chlorate or ammonium chloride so that removal of contaminants is encouraged. The temperature, pH and concentration of the eluent HEDTA are controlled in order to maintain the scandium in the column while minimizing dilution of the scandium band. Recovery of scandium is improved by pumping dilute scandium over the column prior to stripping the scandium and precipitation. This eliminates the HEDTA ion and other monovalent cations contaminating the scandium band. This method maximizes recovery of scandium while maintaining purity.

Monovalent RIVM meningococcal B OMP vesicle F91 vaccines in toddlers

NARCIS (Netherlands)

Lafeber AB; Limpt CJP van; Labadie J; Berbers GAM; Kleijn ED de; Groot R de; Rumke HC; Alphen AJW; Sophia Kinderziekenhuis /; LVO

2001-01-01

This report gives the results of a randomised phase-II clinical study into the safety and immunogenicity of a monovalent MenB OMV vaccine expressing P1.7h,4 PorA (MonoMen) in toddlers. Safety and immunogenicity are compared for two types of vaccine that are differently adjuvated (either

Thermal study of monovalent-divalent phase transition in npBifc-F1TCNQ System

International Nuclear Information System (INIS)

Sato, Michiko; Nishio, Yutaka; Kajita, Koji; Mochida, Tomoyuki

2009-01-01

In a new molecular solid composed of di-neopentyl-biferrocene (npBifc) and fluorotetracyanoquinodimethane (F 1 TCNQ) 3 , Mochida reported the discovery of a reversible valence transfer that can be regarded as an 'ionic(I)-ionic(II)' phase transfer between the monovalent state (D + A - ) and the divalent state (D 2+ A 2- ). We have studied thermo-dynamical properties of this transformation for this complex using the differential thermal analyses (DTA). We observed a broad excess specific heat with multi-peaks attributed to micro-domain structure over the corresponding temperature range (100-150K) accompanied by temperature hysteresis of 7K. The transition entropy (ΔS) was determined to be 22 ± 2 J/mol-K and almost satisfied a Clausius-Clapeyron relation. These experimental results provide an experimental confirmation of the first order phase transition for the monovalent-divalent transfer. At the transition, we observe that the electronic degrees of freedom remained constant values, while large entropy absorbed crossing from low temperature phase to high temperature one is contributed by the lattice one. We finally estimated the internal energy and concluded that delicate energy valance between Madelung, ionization and affinity energies enable this system to exhibit a temperature induce monovalent-divalent phase transition.

Ionic behavior of organic-inorganic metal halide perovskite based metal-oxide-semiconductor capacitors.

Science.gov (United States)

Wang, Yucheng; Zhang, Yuming; Pang, Tiqiang; Xu, Jie; Hu, Ziyang; Zhu, Yuejin; Tang, Xiaoyan; Luan, Suzhen; Jia, Renxu

2017-05-24

Organic-inorganic metal halide perovskites are promising semiconductors for optoelectronic applications. Despite the achievements in device performance, the electrical properties of perovskites have stagnated. Ion migration is speculated to be the main contributing factor for the many unusual electrical phenomena in perovskite-based devices. Here, to understand the intrinsic electrical behavior of perovskites, we constructed metal-oxide-semiconductor (MOS) capacitors based on perovskite films and performed capacitance-voltage (C-V) and current-voltage (I-V) measurements of the capacitors. The results provide direct evidence for the mixed ionic-electronic transport behavior within perovskite films. In the dark, there is electrical hysteresis in both the C-V and I-V curves because the mobile negative ions take part in charge transport despite frequency modulation. However, under illumination, the large amount of photoexcited free carriers screens the influence of the mobile ions with a low concentration, which is responsible for the normal C-V properties. Validation of ion migration for the gate-control ability of MOS capacitors is also helpful for the investigation of perovskite MOS transistors and other gate-control photovoltaic devices.

Coulometric thermometric titration of halides in molten calcium nitrate tetrahydrate.

Science.gov (United States)

Zsigrai, I J; Bartusz, D B

1983-01-01

A method for coulometric thermometric precipitation titrations of chloride, bromide and iodide in molten calcium nitrate tetrahydrate at 55 degrees with coulometrically generated silver ions has been developed. The change in temperature during the titration is followed with the aid of a thermistor bridge coupled to a recorder. To minimize the temperature effect of the passage of current through the melt, two thermistors are connected in opposition in the bridge, with one in the anodic and the other in the cathodic cell compartment. Amounts of 62-80 mumole of halide have been determined with relative error below 0.4% and relative standard deviation less than 2.7%. The relative error in determination of 40 mumole of iodide was + 2%.

Computational screening of mixed metal halide ammines

DEFF Research Database (Denmark)

Jensen, Peter Bjerre; Lysgaard, Steen; Quaade, Ulrich

2013-01-01

Metal halide ammines, e.g. Mg(NH3)6Cl2 and Sr(NH3)8Cl2, can reversibly store ammonia, with high volumetric hydrogen storage capacities. The storage in the halide ammines is very safe, and the salts are therefore highly relevant as a carbon-free energy carrier in future transportation infrastructure...... selection. The GA is evolving from an initial (random) population and selecting those with highest fitness, a function based on e.g. stability, release temperature and storage capacity. The search space includes all alkaline, alkaline earth, 3d and 4d metals and the four lightest halides. In total...... the search spaces consists of millions combinations, which makes a GA ideal, to reduce the number of necessary calculations. We are screening for a one step release from either a hexa or octa ammine, and we have found promising candidates, which will be further investigated ? both computationally...

Catalytic effect of halide additives ball milled with magnesium hydride

Energy Technology Data Exchange (ETDEWEB)

Malka, I.E.; Bystrzycki, J. [Department of Advanced Materials and Technologies, Military University of Technology, Kaliskiego 2, 00-908 Warsaw (Poland); Czujko, T. [Department of Advanced Materials and Technologies, Military University of Technology, Kaliskiego 2, 00-908 Warsaw (Poland); CanmetENERGY, Hydrogen Fuel Cells and Transportation Energy, Natural Resources (Canada)

2010-02-15

The influence of various halide additives milled with magnesium hydride (MgH{sub 2}) on its decomposition temperature was studied. The optimum amount of halide additive and milling conditions were evaluated. The MgH{sub 2} decomposition temperature and energy of activation reduction were measured by temperature programmed desorption (TPD) and differential scanning calorimetry (DSC). The difference in catalytic efficiency between chlorides and fluorides of the various metals studied is presented. The effects of oxidation state, valence and position in the periodic table for selected halides on MgH{sub 2} decomposition temperature were also studied. The best catalysts, from the halides studied, for magnesium hydride decomposition were ZrF{sub 4}, TaF{sub 5}, NbF{sub 5}, VCl{sub 3} and TiCl{sub 3}. (author)

Specificity of the metalloregulator CueR for monovalent metal ions

DEFF Research Database (Denmark)

Szunyogh, Dániel; Szokolai, Hajnalka; Thulstrup, Peter Waaben

2015-01-01

(II) , and Hg(II) binding to model systems encompassing the metal-ion-binding loop of CueR from E. coli and V. cholerae. In the presence of Ag(I) , a conserved cysteine residue displays a pKa value for deprotonation of the thiol that is close to the physiological pH value. This property is only observed...

Monovalent ions control proliferation of Ehrlich Lettre ascites cells

DEFF Research Database (Denmark)

Klausen, Thomas Kjaer; Preisler, Sarah; Pedersen, Stine Helene Falsig

2010-01-01

of Ehrlich Lettre ascites (ELA) cells. We measured the intracellular concentration of each ion in G(0), G(1), and S phases of the cell cycle following synchronization by serum starvation and release. We show that intracellular concentrations and content of Na+ and Cl(-) were reduced in the G(0)-G(1) phase...... effect. Western blots showed reduced chloride intracellular channel CLIC1 and chloride channel ClC-2 expression in the plasma membrane in S compared with G(1). Our results suggest that Na+ regulates ELA cell proliferation by regulating intracellular pH while Cl(-) may regulate proliferation by fine...

Ion-ion correlation, solvent excluded volume and pH effects on physicochemical properties of spherical oxide nanoparticles.

Science.gov (United States)

Ovanesyan, Zaven; Aljzmi, Amal; Almusaynid, Manal; Khan, Asrar; Valderrama, Esteban; Nash, Kelly L; Marucho, Marcelo

2016-01-15

One major source of complexity in the implementation of nanoparticles in aqueous electrolytes arises from the strong influence that biological environments has on their physicochemical properties. A key parameter for understanding the molecular mechanisms governing the physicochemical properties of nanoparticles is the formation of the surface charge density. In this article, we present an efficient and accurate approach that combines a recently introduced classical solvation density functional theory for spherical electrical double layers with a surface complexation model to account for ion-ion correlation and excluded volume effects on the surface titration of spherical nanoparticles. We apply the proposed computational approach to account for the charge-regulated mechanisms on the surface chemistry of spherical silica (SiO2) nanoparticles. We analyze the effects of the nanoparticle size, as well as pH level and electrolyte concentration of the aqueous solution on the nanoparticle's surface charge density and Zeta potential. We validate our predictions for 580Å and 200Å nanoparticles immersed in acid, neutral and alkaline mono-valent aqueous electrolyte solutions against experimental data. Our results on mono-valent electrolyte show that the excluded volume and ion-ion correlations contribute significantly to the surface charge density and Zeta potential of the nanoparticle at high electrolyte concentration and pH levels, where the solvent crowding effects and electrostatic screening have shown a profound influence on the protonation/deprotonation reactions at the liquid/solute interface. The success of this approach in describing physicochemical properties of silica nanoparticles supports its broader application to study other spherical metal oxide nanoparticles. Copyright © 2015 Elsevier Inc. All rights reserved.

Complex fluids with mobile charge-regulating macro-ions

Science.gov (United States)

Markovich, Tomer; Andelman, David; Podgornik, Rudi

2017-10-01

We generalize the concept of charge regulation of ionic solutions, and apply it to complex fluids with mobile macro-ions having internal non-electrostatic degrees of freedom. The suggested framework provides a convenient tool for investigating systems where mobile macro-ions can self-regulate their charge (e.g., proteins). We show that even within a simplified charge-regulation model, the charge dissociation equilibrium results in different and notable properties. Consequences of the charge regulation include a positional dependence of the effective charge of the macro-ions, a non-monotonic dependence of the effective Debye screening length on the concentration of the monovalent salt, a modification of the electric double-layer structure, and buffering by the macro-ions of the background electrolyte.

Inhibition performance of a gemini surfactant and its co-adsorption effect with halides on mild steel in 0.25 M H{sub 2}SO{sub 4} solution

Energy Technology Data Exchange (ETDEWEB)

Wang Xiumei [State Key Laboratory for Corrosion and Protection, Institute of Metal Research Chinese Academy of Sciences, Shenyang 110016 (China); School of Materials Science and Engineering, Shenyang Jianzhu University, Shenyang 110168 (China); Yang Huaiyu, E-mail: hyyang@imr.ac.cn [State Key Laboratory for Corrosion and Protection, Institute of Metal Research Chinese Academy of Sciences, Shenyang 110016 (China); Wang Fuhui [State Key Laboratory for Corrosion and Protection, Institute of Metal Research Chinese Academy of Sciences, Shenyang 110016 (China)

2012-02-15

Highlights: Black-Right-Pointing-Pointer 1,4-Bis (1-chlorobenzyl-benzimidazolyl)-butane has good inhibition effect for mild steel in H{sub 2}SO{sub 4}. Black-Right-Pointing-Pointer The compound acts as a mixed-type inhibitor and obeys Langmuir adsorption isotherm. Black-Right-Pointing-Pointer Halide ions can improve the inhibition property of compound via the co-adsorption effect. Black-Right-Pointing-Pointer The adsorbed halides play an important intermediate bridge role in co-adsorption process. Black-Right-Pointing-Pointer The obtained results can supply the bases for the future using of cationic inhibitor. - Abstract: The inhibition performance of a cationic gemini-surfactant (CBB) and its co-adsorption behavior with halides on mild steel in 0.25 M H{sub 2}SO{sub 4} solution was studied by weight loss and electrochemical techniques. Results showed that the compound could effectively inhibit the mild steel corrosion and acted as a mixed-type inhibitor by suppressing simultaneously anodic and cathodic reactions. Addition of the halides improve the inhibition efficiency of CBB and the synergistic effect increase in the order of I{sup -} > Br{sup -} > Cl{sup -}, revealing that halides radii and their electronegativity may play significant roles in co-adsorption with the cationic inhibitor.

Alkali metal and alkali earth metal gadolinium halide scintillators

Science.gov (United States)

Bourret-Courchesne, Edith; Derenzo, Stephen E.; Parms, Shameka; Porter-Chapman, Yetta D.; Wiggins, Latoria K.

2016-08-02

The present invention provides for a composition comprising an inorganic scintillator comprising a gadolinium halide, optionally cerium-doped, having the formula A.sub.nGdX.sub.m:Ce; wherein A is nothing, an alkali metal, such as Li or Na, or an alkali earth metal, such as Ba; X is F, Br, Cl, or I; n is an integer from 1 to 2; m is an integer from 4 to 7; and the molar percent of cerium is 0% to 100%. The gadolinium halides or alkali earth metal gadolinium halides are scintillators and produce a bright luminescence upon irradiation by a suitable radiation.

Anionic halide···alcohol clusters in the solid state.

Science.gov (United States)

Gushchin, Pavel V; Kuznetsov, Maxim L; Haukka, Matti; Kukushkin, Vadim Yu

2014-10-09

The cationic (1,3,5-triazapentadiene)Pt(II) complexes [1](Cl)2, [2](Cl)2, [3](Br)2, and [4](Cl)2, were crystallized from ROH-containing systems (R = Me, Et) providing alcohol solvates studied by X-ray diffraction. In the crystal structures of [1-4][(Hal)2(ROH)2] (R = Me, Et), the Hal(-) ion interacts with two or three cations [1-4](2+) by means of two or three or four contacts thus uniting stacked arrays of complexes into the layers. The solvated MeOH or EtOH molecules occupy vacant space, giving contacts with [1-4](2+), and connects to the Hal(-) ion through a hydrogen bridge via the H(1O)O(1S) H atom forming, by means of the Hal(-)···HOR (Hal = Cl, Br) contact, the halide-alcohol cluster. Properties of the Cl(-)···HO(Me) H-bond in [1][(Cl)2(MeOH)2] were analyzed using theoretical DFT methods.

A Kirkwood-Buff derived force field for alkaline earth halide salts

Science.gov (United States)

Naleem, Nawavi; Bentenitis, Nikolaos; Smith, Paul E.

2018-06-01

The activity and function of many macromolecules in cellular environments are coupled with the binding of divalent ions such as calcium or magnesium. In principle, computer simulations can be used to understand the molecular level aspects of how many important macromolecules interact with ions. However, most of the force fields currently available often fail to accurately reproduce the properties of divalent ions in aqueous environments. Here we develop classical non-polarizable force fields for the aqueous alkaline earth metal halides (MX2), where M = Mg2+, Ca2+, Sr2+, Ba2+ and X = Cl-, Br-, I-, which can be used in bimolecular simulations and which are compatible with the Simple Point Charge/Extended (SPC/E) water model. The force field parameters are specifically developed to reproduce the experimental Kirkwood-Buff integrals for aqueous solutions and thereby the experimental activity derivatives, partial molar volumes, and excess coordination numbers. This ensures that a reasonable balance between ion-ion, ion-water, and water-water distributions is obtained. However, this requires a scaling of the cation to water oxygen interaction strength in order to accurately reproduce the integrals. The scaling factors developed for chloride salts are successfully transferable to the bromide and iodide salts. Use of these new models leads to reasonable diffusion constants and dielectric decrements. However, the performance of the models decreases with increasing salt concentration (>4m), and simulations of the pure crystals exhibited unstable behavior.

Methyl halide emissions from greenhouse-grown mangroves

Science.gov (United States)

Manley, Steven L.; Wang, Nun-Yii; Walser, Maggie L.; Cicerone, Ralph J.

2007-01-01

Two mangrove species, Avicennia germinans and Rhizophora mangle, were greenhouse grown for nearly 1.5 years from saplings. A single individual of each species was monitored for the emission of methyl halides from aerial tissue. During the first 240 days, salinity was incrementally increased with the addition of seawater, and was maintained between 18 and 28‰ for the duration of the study. Exponential growth occurred after 180 days. Methyl halide emissions normalized to leaf area were measured throughout the study and varied dramatically. Emission rates normalized to land area (mg m-2 y-1), assuming a LAI = 5, yielded 82 and 29 for CH3Cl, 10 and 1.6 for CH3Br, and 26 and 11 for CH3I, for A. germinans and R. mangle, respectively. From these preliminary determinations, only CH3I emissions emerge as being of possible global atmospheric significance. This study emphasizes the need for field studies of methyl halide emissions from mangrove forests.

Lamp-Ballast Compatibility Index for Efficient Ceramic Metal Halide Lamp Operation

OpenAIRE

Sourish Chatterjee

2013-01-01

Development of energy efficient products and exploration of energy saving potential are major challenges for present day’s technology. Ceramic Metal Halide lamp is the latest improved version of metal halide lamp that finds its wide applications in indoor commercial lighting especially in retail shop lighting. This lamp shows better performance in terms of higher lumen per watt and colour constancy in comparison to conventional metal halide lamp. The inherent negative incremental impedance of...

Making and Breaking of Lead Halide Perovskites

KAUST Repository

Manser, Joseph S.

2016-02-16

A new front-runner has emerged in the field of next-generation photovoltaics. A unique class of materials, known as organic metal halide perovskites, bridges the gap between low-cost fabrication and exceptional device performance. These compounds can be processed at low temperature (typically in the range 80–150 °C) and readily self-assemble from the solution phase into high-quality semiconductor thin films. The low energetic barrier for crystal formation has mixed consequences. On one hand, it enables inexpensive processing and both optical and electronic tunability. The caveat, however, is that many as-formed lead halide perovskite thin films lack chemical and structural stability, undergoing rapid degradation in the presence of moisture or heat. To date, improvements in perovskite solar cell efficiency have resulted primarily from better control over thin film morphology, manipulation of the stoichiometry and chemistry of lead halide and alkylammonium halide precursors, and the choice of solvent treatment. Proper characterization and tuning of processing parameters can aid in rational optimization of perovskite devices. Likewise, gaining a comprehensive understanding of the degradation mechanism and identifying components of the perovskite structure that may be particularly susceptible to attack by moisture are vital to mitigate device degradation under operating conditions. This Account provides insight into the lifecycle of organic–inorganic lead halide perovskites, including (i) the nature of the precursor solution, (ii) formation of solid-state perovskite thin films and single crystals, and (iii) transformation of perovskites into hydrated phases upon exposure to moisture. In particular, spectroscopic and structural characterization techniques shed light on the thermally driven evolution of the perovskite structure. By tuning precursor stoichiometry and chemistry, and thus the lead halide charge-transfer complexes present in solution, crystallization

Thermal study of monovalent-divalent phase transition in npBifc-F{sub 1}TCNQ System

Energy Technology Data Exchange (ETDEWEB)

Sato, Michiko; Nishio, Yutaka; Kajita, Koji [Department of Physics, Faculty of Science, Toho University, Miyama 2-2-1, Funabashi, Chiba, 274-8510 (Japan); Mochida, Tomoyuki, E-mail: nishio@ph.sci.toho-u.ac.j [Department of Chemistry, Faculty of Science, Kobe University, Rokkodai, Nada, Kobe 657-8501 (Japan)

2009-03-01

In a new molecular solid composed of di-neopentyl-biferrocene (npBifc) and fluorotetracyanoquinodimethane (F{sub 1}TCNQ){sub 3}, Mochida reported the discovery of a reversible valence transfer that can be regarded as an 'ionic(I)-ionic(II)' phase transfer between the monovalent state (D{sup +}A{sup -}) and the divalent state (D{sup 2+}A{sup 2-}). We have studied thermo-dynamical properties of this transformation for this complex using the differential thermal analyses (DTA). We observed a broad excess specific heat with multi-peaks attributed to micro-domain structure over the corresponding temperature range (100-150K) accompanied by temperature hysteresis of 7K. The transition entropy (DELTAS) was determined to be 22 +- 2 J/mol-K and almost satisfied a Clausius-Clapeyron relation. These experimental results provide an experimental confirmation of the first order phase transition for the monovalent-divalent transfer. At the transition, we observe that the electronic degrees of freedom remained constant values, while large entropy absorbed crossing from low temperature phase to high temperature one is contributed by the lattice one. We finally estimated the internal energy and concluded that delicate energy valance between Madelung, ionization and affinity energies enable this system to exhibit a temperature induce monovalent-divalent phase transition.

Two-phase coexistence in the monovalent-to-divalent phase transition of dineopentylbiferrocene-fluorotetracyanoquinodimethane [npBifc-(F1TCNQ)3], charge-transfer salt

International Nuclear Information System (INIS)

Uruichi, Mikio; Yue, Yue; Yakushi, Kyuya; Mochida, Tomoyuki

2007-01-01

We present experimental findings showing that for npBifc-(F 1 TCNQ) 3 , two phases coexist over a wide temperature interval of 100-150 K near the monovalent-to-divalent phase transition temperature. Macroscopic domains of the high-temperature (monovalent) and low-temperature (divalent) phases were detected in the transition temperature region using X-ray diffraction and micro-Raman spectroscopy techniques. The volume fraction of the two domains continuously varied depending upon the temperature. A considerably large volume difference was found between the monovalent and divalent phases. The effect of volumetric strain due to this volume difference is discussed to understand this inhomogeneous state. (author)

Miscellaneous Lasing Actions in Organo-Lead Halide Perovskite Films.

Science.gov (United States)

Duan, Zonghui; Wang, Shuai; Yi, Ningbo; Gu, Zhiyuan; Gao, Yisheng; Song, Qinghai; Xiao, Shumin

2017-06-21

Lasing actions in organo-lead halide perovskite films have been heavily studied in the past few years. However, due to the disordered nature of synthesized perovskite films, the lasing actions are usually understood as random lasers that are formed by multiple scattering. Herein, we demonstrate the miscellaneous lasing actions in organo-lead halide perovskite films. In addition to the random lasers, we show that a single or a few perovskite microparticles can generate laser emissions with their internal resonances instead of multiple scattering among them. We experimentally observed and numerically confirmed whispering gallery (WG)-like microlasers in polygon shaped and other deformed microparticles. Meanwhile, owing to the nature of total internal reflection and the novel shape of the nanoparticle, the size of the perovskite WG laser can be significantly decreased to a few hundred nanometers. Thus, wavelength-scale lead halide perovskite lasers were realized for the first time. All of these laser behaviors are complementary to typical random lasers in perovskite film and will help the understanding of lasing actions in complex lead halide perovskite systems.

Single Crystals of Organolead Halide Perovskites: Growth, Characterization, and Applications

KAUST Repository

Peng, Wei

2017-04-01

With the soaring advancement of organolead halide perovskite solar cells rising from a power conversion efficiency of merely 3% to more than 22% shortly in five years, researchers’ interests on this big material family have been greatly spurred. So far, both in-depth studies on the fundamental properties of organolead halide perovskites and their extended applications such as photodetectors, light emitting diodes, and lasing have been intensively reported. The great successes have been ascribed to various superior properties of organolead halide hybrid perovskites such as long carrier lifetimes, high carrier mobility, and solution-processable high quality thin films, as will be discussed in Chapter 1. Notably, most of these studies have been limited to their polycrystalline thin films. Single crystals, as a counter form of polycrystals, have no grain boundaries and higher crystallinity, and thus less defects. These characteristics gift single crystals with superior optical, electrical, and mechanical properties, which will be discussed in Chapter 2. For example, organolead halide perovskite single crystals have been reported with much longer carrier lifetimes and higher carrier mobilities, which are especially intriguing for optoelectronic applications. Besides their superior optoelectronic properties, organolead halide perovskites have shown large composition versatility, especially their organic components, which can be controlled to effectively adjust their crystal structures and further fundamental properties. Single crystals are an ideal platform for such composition-structure-property study since a uniform structure with homogeneous compositions and without distraction from grain boundaries as well as excess defects can provide unambiguously information of material properties. As a major part of work of this dissertation, explorative work on the composition-structure-property study of organic-cation-alloyed organolead halide perovskites using their single

Highly reversible open framework nanoscale electrodes for divalent ion batteries.

Science.gov (United States)

Wang, Richard Y; Wessells, Colin D; Huggins, Robert A; Cui, Yi

2013-01-01

The reversible insertion of monovalent ions such as lithium into electrode materials has enabled the development of rechargeable batteries with high energy density. Reversible insertion of divalent ions such as magnesium would allow the creation of new battery chemistries that are potentially safer and cheaper than lithium-based batteries. Here we report that nanomaterials in the Prussian Blue family of open framework materials, such as nickel hexacyanoferrate, allow for the reversible insertion of aqueous alkaline earth divalent ions, including Mg(2+), Ca(2+), Sr(2+), and Ba(2+). We show unprecedented long cycle life and high rate performance for divalent ion insertion. Our results represent a step forward and pave the way for future development in divalent batteries.

Circular Dichroism is Sensitive to Monovalent Cation Binding in Monensin Complexes

Czech Academy of Sciences Publication Activity Database

Nedzhib, A.; Kessler, Jiří; Bouř, Petr; Gyurcsik, B.; Pantcheva, I.

2016-01-01

Roč. 28, č. 5 (2016), s. 420-428 ISSN 0899-0042 R&D Projects: GA ČR GA15-09072S; GA ČR(CZ) GA16-05935S Institutional support: RVO:61388963 Keywords : monovalent polyether ionophore * metal complexes * synchrotron radiation circular dichroism * time-dependent density functional theory Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.956, year: 2016

Effect of halide salts on development of surface browning on fresh-cut 'Granny Smith' (Malus × domestica Borkh) apple slices during storage at low temperature.

Science.gov (United States)

Li, Yongxin; Wills, Ron B H; Golding, John B; Huque, Roksana

2015-03-30

The postharvest life of fresh-cut apple slices is limited by browning on cut surfaces. Dipping in halide salt solutions was examined for their inhibition of surface browning on 'Granny Smith' apple slices and the effects on biochemical factors associated with browning. Delay in browning by salts was greatest with chloride = phosphate > sulfate > nitrate with no difference between sodium, potassium and calcium ions. The effectiveness of sodium halides on browning was fluoride > chloride = bromide > iodide = control. Polyphenol oxidase (PPO) activity of tissue extracted from chloride- and fluoride-treated slices was not different to control but when added into the assay solution, NaF > NaCl both showed lower PPO activity at pH 3-5 compared to control buffer. The level of polyphenols in treated slices was NaF > NaCl > control. Addition of chlorogenic acid to slices enhanced browning but NaCl and NaF counteracted this effect. There was no effect of either halide salt on respiration, ethylene production, ion leakage, and antioxidant activity. Dipping apple slices in NaCl is a low cost treatment with few impediments to commercial use and could be a replacement for other anti-browning additives. The mode of action of NaCl and NaF is through decreasing PPO activity resulting in reduced oxidation of polyphenols. © 2014 Society of Chemical Industry.

Local Polar Fluctuations in Lead Halide Perovskite Crystals

Science.gov (United States)

Yaffe, Omer; Guo, Yinsheng; Tan, Liang Z.; Egger, David A.; Hull, Trevor; Stoumpos, Constantinos C.; Zheng, Fan; Heinz, Tony F.; Kronik, Leeor; Kanatzidis, Mercouri G.; Owen, Jonathan S.; Rappe, Andrew M.; Pimenta, Marcos A.; Brus, Louis E.

2017-03-01

Hybrid lead-halide perovskites have emerged as an excellent class of photovoltaic materials. Recent reports suggest that the organic molecular cation is responsible for local polar fluctuations that inhibit carrier recombination. We combine low-frequency Raman scattering with first-principles molecular dynamics (MD) to study the fundamental nature of these local polar fluctuations. Our observations of a strong central peak in the cubic phase of both hybrid (CH3 NH3 PbBr3 ) and all-inorganic (CsPbBr3 ) lead-halide perovskites show that anharmonic, local polar fluctuations are intrinsic to the general lead-halide perovskite structure, and not unique to the dipolar organic cation. MD simulations indicate that head-to-head Cs motion coupled to Br face expansion, occurring on a few hundred femtosecond time scale, drives the local polar fluctuations in CsPbBr3 .

Experimental and Theoretical Study of the Movement of the Wpd Flexible Loop of Human Protein Tyrosine Phosphatase PTP1B in Complex with Halide Ions

Science.gov (United States)

Katz, Aline; Saenz-Méndez, Patricia; Cousido-Siah, Alexandra; Podjarny, Alberto D.; Ventura, Oscar N.

2012-11-01

Protein tyrosine phosphorylation is a post-translational modification mechanism, crucial for the regulation of nearly all aspects of cell life. This dynamic, reversible process is regulated by the balanced opposing activity of protein tyrosine kinases and protein tyrosine phosphatases. In particular, the protein tyrosine phosphatase 1B (PTP1B) is implicated in the regulation of the insulin-receptor activity, leptin-stimulated signal transduction pathways and other clinically relevant metabolic routes, and it has been found overexpressed or overregulated in human breasts, colon and ovary cancers. The WPD loop of the enzyme presents an inherent flexibility, and it plays a fundamental role in the enzymatic catalysis, turning it into a potential target in the design of new efficient PTP1B inhibitors. In order to determine the interactions that control the spatial conformation adopted by the WPD loop, complexes between the enzyme and halide ions (Br- and I- in particular) were crystallized and their crystallographic structure determined, and the collective movements of the aforementioned complexes were studied through Molecular Dynamics (MD) simulations. Both studies yielded concordant results, indicating the existence of a relationship between the identity of the ion present in the complex and the strength of the interactions it establishes with the surrounding protein residues.

The mechanism of ion exchange on ammonium 12-molybdophosphate (AMP)

International Nuclear Information System (INIS)

Boeyens, J.C.A.; McDougall, G.J.; Smit, J. van R.

1987-01-01

This paper reviews some published and unpublished data on the ion-exchange properties of AMP. The three NH 4 + ions are only partially exchanged for large monovalent ions. In the case of NH 4 + /K + exchange, the energy lost by the breaking of H bonds between the NH 4 + ions and anionic cage oxygen atoms beyond the point of maximum exchange is no longer compensated for by bond strengthening in the anion due to contraction of the cage. With Rb + , Cs + and T1 + , limited convertibility results from the lattice expansion required to accommodate these larger ions. During exchange, part of the cations pass through the anionic cages, thereby causing considerable lattice disorder. The maximum exchange capacity of AMP for the alkali metal ions is not a simple function of cation radius. (author)

The electrochemical reduction rate of colloidal particles of silver halides as a function of the electrolyte composition

International Nuclear Information System (INIS)

Selivanov, V.N.

1997-01-01

Influence of silver halide colloid particles concentration (AgI), electrolyte composition and signs of the electrode and colloids charges on their reduction threshold current densities has been studied. It has been discovered that reduction threshold current densities of positively charged colloid particles exceed by a factor of 3-4 the threshold densities of silver ions diffusion current. It is shown that the threshold density of colloids reduction current is limited by the rates of their electrophoretic transfer and diffusion

Monitoring of heavy/toxic metals and halides in surface/ground water (abstract)

International Nuclear Information System (INIS)

Viqar-un-Nisa; Ahmed, R.; Husain, M.

1999-01-01

Water is essential for maintaining physical and social life. Human and animal consumption is perhaps the most evident essential use of water. Water quality and quantity have become critical issues, affecting all life. The importance of water in our lives, combined with the threats, make water resources use a global problem. Among the different pollutants toxic metals, metalloids and halides have special significance. Industrial effluents and municipal wastewater are normally drained into water streams, rivers and other reservoirs thus polluting these significantly. Quality of our water resources especially is an issue, which continues to arouse the attention of concerned scientists, legislators and the general public. Among various pollutant chemicals, the heavy metals and metalloids are present at trace levels in various compartments of the environment. Some metals become toxic even at trace levels because of the important features that distinguishes metals from other pollutants is that they are not biodegradable. The halides like Cl, Br, and I from different sources can enter easily into water systems and then they make their way directly into the human body. The intake of toxic as wells as essential elements through water and other food items like vegetables, milk wheat flour etc. is significant. The abundance or deficiency of these meals as well as halides results in abnormal metabolic functions. Due to excessive demand for trace analysis in water and other materials a variety of techniques and instrumentation has been developed. Determination of heavy metals ions is of the highest interest in environmental analysis. Among the food materials water is most important because of their large consumption by man. Also toxic metals in water may be in dissolved ionic form, which directly go into human metabolism and start their toxic action. Presence of even small amounts of toxic metals in drinking water can produce serious health hazards. (author)

Ionic conductivity of N-alkyl pyridinium halides mesophases

International Nuclear Information System (INIS)

Meftah, Ahmed

1980-01-01

The quasi anhydrous N-alkyl pyridinium halides undergo at a temperature T c a phase transition from a crystalline isolating state to a conducting mesophase (σ = 3.10 -2 Ω -1 cm -1 ). The transition temperature depends on the nature on counter-ion and on the aliphatic chain length. The present study is devoted to the N-alkyl pyridinium chlorides, bromides and iodides varying the number of carbon atoms in the chain from ten to twenty two. The transition temperatures T c were found to increase from 30 deg. C up to 110 deg. C by a step of 10 deg. C for two added carbon atoms in the chain. The electrical measurements have shown that the conductivity of the mesophases which is ionic in origin is due to a large mobility of counter-ions in hydrophilic parts. At high frequencies (F > 10 3 Hz) ionic conductivity predominates in the bulk and does not depend on frequency. At low frequencies (F 3 Hz) the most important are interface phenomena depending on the square root of inverse frequency (ω -1/2 ) and being due to an electronic exchange limited by diffusion velocity of counter-ions. The electrical conductivity depends weekly on the chain length and the mesophases textures. The most conducting mesophase is the optically isotropic. The conductivity increases with increasing water content of the system and decreases with increasing atomic number of counter-ion. The diffusion measurements by radioactive tracers confirm the ionic character of charge carriers although the diffusion factors obtained by this method are largely higher than the calculated ones from the conductivity values. (author) [fr

Non-hydrolytic metal oxide films for perovskite halide overcoating and stabilization

Science.gov (United States)

Martinson, Alex B.; Kim, In Soo

2017-09-26

A method of protecting a perovskite halide film from moisture and temperature includes positioning the perovskite halide film in a chamber. The chamber is maintained at a temperature of less than 200 degrees Celsius. An organo-metal compound is inserted into the chamber. A non-hydrolytic oxygen source is subsequently inserted into the chamber. The inserting of the organo-metal compound and subsequent inserting of the non-hydrolytic oxygen source into the chamber is repeated for a predetermined number of cycles. The non-hydrolytic oxygen source and the organo-metal compound interact in the chamber to deposit a non-hydrolytic metal oxide film on perovskite halide film. The non-hydrolytic metal oxide film protects the perovskite halide film from relative humidity of greater than 35% and a temperature of greater than 150 degrees Celsius, respectively.

Hybrid lead halide perovskites for light energy conversion: Excited state properties and photovoltaic applications

Science.gov (United States)

Manser, Joseph S.

The burgeoning class of metal halide perovskites constitutes a paradigm shift in the study and application of solution-processed semiconductors. Advancements in thin film processing and our understanding of the underlying structural, photophysical, and electronic properties of these materials over the past five years have led to development of perovskite solar cells with power conversion efficiencies that rival much more mature first and second-generation commercial technologies. It seems only a matter of time before the real-world impact of these compounds is put to the test. Like oxide perovskites, metal halide perovskites have ABX3 stoichiometry, where typically A is a monovalent cation, B a bivalent post-transition metal, and X a halide anion. Characterizing the behavior of photogenerated charges in metal halide perovskites is integral for understanding the operating principles and fundamental limitations of perovskite optoelectronics. The majority of studies outlined in this dissertation involve fundamental study of the prototypical organic-inorganic compound methylammonium lead iodide (CH3NH3PbI 3). Time-resolved pump-probe spectroscopy serves as a principle tool in these investigations. Excitation of a semiconductor can lead to formation of a number different excited state species and electronic complexes. Through analysis of excited state decay kinetics and optical nonlinearities in perovskite thin films, we identify spontaneous formation of a large fraction of free electrons and holes, whose presence is requisite for efficient photovoltaic operation. Following photogeneration of charge carriers in a semiconductor absorber, these species must travel large distances across the thickness of the material to realize large external quantum efficiencies and efficient carrier extraction. Using a powerful technique known as transient absorption microscopy, we directly image long-range carrier diffusion in a CH3NH3PbI 3 thin film. Charges are unambiguously shown to

Methyl halide emission estimates from domestic biomass burning in Africa

Science.gov (United States)

Mead, M. I.; Khan, M. A. H.; White, I. R.; Nickless, G.; Shallcross, D. E.

Inventories of methyl halide emissions from domestic burning of biomass in Africa, from 1950 to the present day and projected to 2030, have been constructed. By combining emission factors from Andreae and Merlet [2001. Emission of trace gases and aerosols from biomass burning. Global Biogeochemical Cycles 15, 955-966], the biomass burning estimates from Yevich and Logan [2003. An assessment of biofuel use and burning of agricultural waste in the developing world. Global Biogeochemical Cycles 17(4), 1095, doi:10.1029/2002GB001952] and the population data from the UN population division, the emission of methyl halides from domestic biomass usage in Africa has been estimated. Data from this study suggest that methyl halide emissions from domestic biomass burning have increased by a factor of 4-5 from 1950 to 2005 and based on the expected population growth could double over the next 25 years. This estimated change has a non-negligible impact on the atmospheric budgets of methyl halides.

Phase space investigation of the lithium amide halides

Energy Technology Data Exchange (ETDEWEB)

Davies, Rosalind A. [Hydrogen Storage Chemistry Group, School of Chemistry, University of Birmingham, Edgbaston, Birmingham B15 2TT (United Kingdom); Hydrogen and Fuel Cell Group, School of Chemical Engineering, University of Birmingham, Edgbaston B15 2TT (United Kingdom); Hewett, David R.; Korkiakoski, Emma [Hydrogen Storage Chemistry Group, School of Chemistry, University of Birmingham, Edgbaston, Birmingham B15 2TT (United Kingdom); Thompson, Stephen P. [Diamond Light Source, Harwell Science and Innovation Campus, Didcot, Oxfordshire OX11 0QX (United Kingdom); Anderson, Paul A., E-mail: p.a.anderson@bham.ac.uk [Hydrogen Storage Chemistry Group, School of Chemistry, University of Birmingham, Edgbaston, Birmingham B15 2TT (United Kingdom)

2015-10-05

Highlights: • The lower limits of halide incorporation in lithium amide have been investigated. • The only amide iodide stoichiometry observed was Li{sub 3}(NH{sub 2}){sub 2}I. • Solid solutions were observed in both the amide chloride and amide bromide systems. • A 46% reduction in chloride content resulted in a new phase: Li{sub 7}(NH{sub 2}){sub 6}Cl. • New low-chloride phase maintained improved H{sub 2} desorption properties of Li{sub 4}(NH{sub 2}){sub 3}Cl. - Abstract: An investigation has been carried out into the lower limits of halide incorporation in lithium amide (LiNH{sub 2}). It was found that the lithium amide iodide Li{sub 3}(NH{sub 2}){sub 2}I was unable to accommodate any variation in stoichiometry. In contrast, some variation in stoichiometry was accommodated in Li{sub 7}(NH{sub 2}){sub 6}Br, as shown by a decrease in unit cell volume when the bromide content was reduced. The amide chloride Li{sub 4}(NH{sub 2}){sub 3}Cl was found to adopt either a rhombohedral or a cubic structure depending on the reaction conditions. Reduction in chloride content generally resulted in a mixture of phases, but a new rhombohedral phase with the stoichiometry Li{sub 7}(NH{sub 2}){sub 6}Cl was observed. In comparison to LiNH{sub 2}, this new low-chloride phase exhibited similar improved hydrogen desorption properties as Li{sub 4}(NH{sub 2}){sub 3}Cl but with a much reduced weight penalty through addition of chloride. Attempts to dope lithium amide with fluoride ions have so far proved unsuccessful.

Halide based MBE of crystalline metals and oxides

Energy Technology Data Exchange (ETDEWEB)

Greenlee, Jordan D.; Calley, W. Laws; Henderson, Walter; Doolittle, W. Alan [Georgia Institute of Technology, School of Electrical and Computer Engineering, Atlanta, Georgia (United States)

2012-02-15

A halide based growth chemistry has been demonstrated which can deliver a range of transition metals using low to moderate effusion cell temperatures (30-700 C) even for high melting point metals. Previously, growth with transition metal species required difficult to control electron beam or impurity inducing metal organic sources. Both crystalline oxide and metal films exhibiting excellent crystal quality are grown using this halide-based growth chemistry. Films are grown using a plasma assisted Molecular Beam Epitaxy (MBE) system with metal-chloride precursors. Crystalline niobium, cobalt, iron, and nickel were grown using this chemistry but the technology can be generalized to almost any metal for which a chloride precursor is available. Additionally, the oxides LiNbO{sub 3} and LiNbO{sub 2} were grown with films exhibiting X-ray diffraction (XRD) rocking curve full-widths at half maximum of 150 and 190 arcseconds respectively. LiNbO{sub 2} films demonstrate a memristive response due to the rapid movement of lithium in the layered crystal structure. The rapid movement of lithium ions in LiNbO{sub 2} memristors is characterized using impedance spectroscopy measurements. The impedance spectroscopy measurements suggest an ionic current of.1 mA for a small drive voltage of 5 mV AC or equivalently an ionic current density of {proportional_to}87 A/cm{sup 2}. This high ionic current density coupled with low charge transfer resistance of {proportional_to}16.5 {omega} and a high relaxation frequency (6.6 MHz) makes this single crystal material appealing for battery applications in addition to memristors. (copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

A three-scale model for ionic solute transport in swelling clays incorporating ion-ion correlation effects

Science.gov (United States)

Le, Tien Dung; Moyne, Christian; Murad, Marcio A.

2015-01-01

A new three-scale model is proposed to describe the movement of ionic species of different valences in swelling clays characterized by three separate length scales (nano, micro, and macro) and two levels of porosity (nano- and micropores). At the finest (nano) scale the medium is treated as charged clay particles saturated by aqueous electrolyte solution containing monovalent and divalent ions forming the electrical double layer. A new constitutive law is constructed for the disjoining pressure based on the numerical resolution of non-local problem at the nanoscale which, in contrast to the Poisson-Boltzmann theory for point charge ions, is capable of capturing the short-range interactions between the ions due to their finite size. At the intermediate scale (microscale), the two-phase homogenized particle/electrolyte solution system is represented by swollen clay clusters (or aggregates) with the nanoscale disjoining pressure incorporated in a modified form of Terzaghi's effective principle. At the macroscale, the electro-chemical-mechanical couplings within clay clusters is homogenized with the ion transport in the bulk fluid lying in the micro pores. The resultant macroscopic picture is governed by a three-scale model wherein ion transport takes place in the bulk solution strongly coupled with the mechanics of the clay clusters which play the role of sources/sinks of mass to the bulk fluid associated with ion adsorption/desorption in the electrical double layer at the nanoscale. Within the context of the quasi-steady version of the multiscale model, wherein the electrolyte solution in the nanopores is assumed at instantaneous thermodynamic equilibrium with the bulk fluid in the micropores, we build-up numerically the ion-adsorption isotherms along with the constitutive law of the retardation coefficients of monovalent and divalent ions. In addition, the constitutive law for the macroscopic swelling pressure is reconstructed numerically showing patterns of

Electrically driven ion separations and nanofiltration through membranes coated with polyelectrolyte multilayers

Science.gov (United States)

White, Nicholas

Polyelectrolyte multilayer (PEM) films deposited using the layer-by-layer (LBL) method are attractive for their simple deposition, tailorable nature, scalability, and charge or size-based selectivity for solutes. This dissertation explores ion separations in electrodialysis (ED) and solute removal through nanofiltration with PEMs deposited on polymer membranes. ED membranes typically exhibit modest selectivities between monovalent and divalent ions. In contrast, this work shows that K+/Mg 2+ ED selectivities reach values >1000 when using Nafion 115 cation-exchange membranes coated with multilayer poly(4-styrenesulfonate) (PSS)/protonated poly(allylamine) (PAH) films. For comparison, the corresponding K+ /Mg2+ selectivity of bare Nafion 115 is salt concentrations, the K+ transference number approaches unity and the K+/Mg2+ selectivity is >20,000, presumably because the applied current is below the limiting value for K+ and H+ transport is negligible at this high K+ concentration. The high selectivities of these membranes may enable electrodialysis applications such as purification of salts that contain divalent or trivalent ions. The high ED selectivities of (PAH/PSS)5PAH-coated Nafion membranes translate to separations with Li+/Co2+ and K +/La3+. Even with adsorption of only 3 polyelectrolyte layers, Nafion membranes exhibit a Li+/Co2+ selectivity >23. However, the resistance to monovalent-ion passage does not decrease significantly with fewer polyelectrolyte layers. At overlimiting currents, hydroxides from water splitting form insoluble metal hydroxides to foul the membrane. With 0.1 M source-phase salt concentrations, transference numbers for monovalent cations approach unity and selectivities are >5000 because the diffusion-limited K+ or Li+ currents exceed the applied current. However, ED selectivities gradually decline with time. Thus, future research should aim to increase membrane stability and limiting currents to fully exploit the remarkable selectivity

Solar cells, structures including organometallic halide perovskite monocrystalline films, and methods of preparation thereof

KAUST Repository

Bakr, Osman M.

2017-03-02

Embodiments of the present disclosure provide for solar cells including an organometallic halide perovskite monocrystalline film (see fig. 1.1B), other devices including the organometallic halide perovskite monocrystalline film, methods of making organometallic halide perovskite monocrystalline film, and the like.

Definition of a high intensity metal halide discharge reference lamp

NARCIS (Netherlands)

Stoffels, W.W.; Baede, A.H.F.M.; Mullen, van der J.J.A.M.; Haverlag, M.; Zissis, G.

2006-01-01

The design of a ref. metal halide discharge lamp is presented. This lamp is meant as a common study object for researchers working on metal halide discharge lamps, who by using the same design will be able to compare results between research groups, diagnostic techniques and numerical models. The

Inhibitory action of quaternary ammonium bromide on mild steel and synergistic effect with other halide ions in 0.5 M H2SO4

Directory of Open Access Journals (Sweden)

A. Khamis

2014-11-01

Full Text Available The corrosion inhibition of mild steel in 0.5 M H2SO4 solution has been investigated using electrochemical methods, X-ray diffraction (XRD and scanning electron microscope (SEM. The adsorption and inhibition action of acid corrosion of mild steel using cetyltrimethylammonium bromide (CTABr and different halides (NaCl, NaBr and NaI has shown synergetic effect. The results showed that the protection efficiency (P% has high values at considerable high concentration of CTABr. However, in the presence of the different halides, the P increases dramatically at low concentration of CTABr. Physisorption was proposed from the the values of ΔGads0. The synergism parameter (Sθ is found to be greater than unity indicating that the enhanced P% caused by the addition of the halides to the CTABr is due to a co-operative adsorption of both species. Corrosion products phases and surface morphology were studied using X-ray diffraction (XRD and scanning electron microscopy (SEM, respectively.

The apparent monovalency of human IgG4 is due to bispecificity

NARCIS (Netherlands)

Aalberse, R. C.; Schuurman, J.; van Ree, R.

1999-01-01

A hypothesis is put forward to explain the apparent monovalency of human IgG4. It is based upon the known instability of the IgG4 hinge. IgG4 is secreted as a regular bivalent antibody, but after secretion interacts with another IgG4 molecule. This interaction results in the exchange of half

78 FR 51463 - Energy Conservation Program: Energy Conservation Standards for Metal Halide Lamp Fixtures

Science.gov (United States)

2013-08-20

... merging the metal halide lamp fixture and the high-intensity discharge (HID) lamp rulemakings. This NOPR... Conservation Program: Energy Conservation Standards for Metal Halide Lamp Fixtures; Proposed Rule #0;#0;Federal...: Energy Conservation Standards for Metal Halide Lamp Fixtures AGENCY: Office of Energy Efficiency and...

Energetics of the ruthenium-halide bond in olefin metathesis (pre)catalysts

KAUST Repository

Falivene, Laura; Poater, Albert; Cazin, Catherine S J; Slugovc, Christian; Cavallo, Luigi

2013-01-01

A DFT analysis of the strength of the Ru-halide bond in a series of typical olefin metathesis (pre)catalysts is presented. The calculated Ru-halide bond energies span the rather broad window of 25-43 kcal mol-1. This indicates that in many systems dissociation of the Ru-halide bond is possible and is actually competitive with dissociation of the labile ligand generating the 14e active species. Consequently, formation of cationic Ru species in solution should be considered as a possible event. © 2013 The Royal Society of Chemistry.

Development of halide copper vapor laser (the characteristics of using Cul)

International Nuclear Information System (INIS)

Oouti, Kazumi; Wada, Yukio; Sasao, Nobuyuki

1990-01-01

We are developing halide copper vapor laser that is high efficiency and high reputation rate visible laser. Halide copper vapor laser uses halide copper of copper vapor source. It melts low temperature in comporison with metal copper, because laser tube structure is very simple and it can operate easy. This time, we experiment to use Cul for copper vapor source. We resulted maximum output energy 17.8 (W) and maximum efficiency 0.78 (%) when operate condition was reputation rate 30 (kHz), gas pressure 90 (Torr), charging voltage 13 (kV). (author)

Broadly tunable metal halide perovskites for solid-state light-emission applications

NARCIS (Netherlands)

Adjokatse, Sampson; Fang, Hong-Hua; Loi, Maria Antonietta

2017-01-01

The past two years have witnessed heightened interest in metal-halide perovskites as promising optoelectronic materials for solid-state light emitting applications beyond photovoltaics. Metal-halide perovskites are low-cost solution-processable materials with excellent intrinsic properties such as

Two-Dimensional Halide Perovskites for Emerging New- Generation Photodetectors

DEFF Research Database (Denmark)

Tang, Yingying; Cao, Xianyi; Chi, Qijin

2018-01-01

Compared to their conventional three-dimensional (3D) counterparts, two-dimensional (2D) halide perovskites have attracted more interests recently in a variety of areas related to optoelectronics because of their unique structural characteristics and enhanced performances. In general, there are two...... distinct types of 2D halide perovskites. One represents those perovskites with an intrinsic layered crystal structure (i.e. MX6 layers, M = metal and X = Cl, Br, I), the other defines the perovskites with a 2D nanostructured morphology such as nanoplatelets and nanosheets. Recent studies have shown that 2D...... halide perovskites hold promising potential for the development of new-generation photodetectors, mainly arising from their highly efficient photoluminescence and absorbance, color tunability in the visible-light range and relatively high stability. In this chapter, we present the summary and highlights...

Tunable Crystal-to-Crystal Phase Transition in a Cadmium Halide Chain Polymer

Directory of Open Access Journals (Sweden)

Ulli Englert

2011-07-01

Full Text Available The chain polymer [{Cd(μ-X2py2}1∞] (X = Cl, Br; py = pyridine undergoes a fully reversible phase transition between a monoclinic low-temperature and an orthorhombic high-temperature phase. The transformation can be directly monitored in single crystals and can be confirmed for the bulk by powder diffraction. The transition temperature can be adjusted by tuning the composition of the mixed-halide phase: Transition temperatures between 175 K up to the decomposition of the material at ca. 350 K are accessible. Elemental analysis, ion chromatography and site occupancy refinements from single-crystal X-ray diffraction agree with respect to the stoichiometric composition of the samples.

Repulsive energy and the Grueneisen parameter of alkali halides calculated on the basis of a quantum-statistical ab initio theory

International Nuclear Information System (INIS)

Kucharczyk, M.; Olszewski, S.

1982-01-01

The Grueneisen parameter of alkali halides is calculated by an ab initio quantum-statistical method and then compared with the experimental data. The crystal model applied assumes the crystal ions to be compressible but impenetrable spheres. The ions are described with the aid of a modified Thomas-Fermi theory with exchange. At the next step it is possible to calculate the energy needed to transform the system of the non-interacting ions into the ionic system represented by the crystal lattice. This calculation allows for an ab initio estimate of the parameters entering the Born, or the Born-Mayer, repulsive part of the crystal energy. The parameters are then used in the calculation of the Grueneisen parameter and its dependence on the crystal compression. (author)

Modeling ion sensing in molecular electronics

International Nuclear Information System (INIS)

Chen, Caroline J.; Smeu, Manuel; Ratner, Mark A.

2014-01-01

We examine the ability of molecules to sense ions by measuring the change in molecular conductance in the presence of such charged species. The detection of protons (H + ), alkali metal cations (M + ), calcium ions (Ca 2+ ), and hydronium ions (H 3 O + ) is considered. Density functional theory (DFT) is used within the Keldysh non-equilibrium Green's function framework (NEGF) to model electron transport properties of quinolinedithiol (QDT, C 9 H 7 NS 2 ), bridging Al electrodes. The geometry of the transport region is relaxed with DFT. The transport properties of the device are modeled with NEGF-DFT to determine if this device can distinguish among the M + + QDT species containing monovalent cations, where M + = H + , Li + , Na + , or K + . Because of the asymmetry of QDT in between the two electrodes, both positive and negative biases are considered. The electron transmission function and conductance properties are simulated for electrode biases in the range from −0.5 V to 0.5 V at increments of 0.1 V. Scattering state analysis is used to determine the molecular orbitals that are the main contributors to the peaks in the transmission function near the Fermi level of the electrodes, and current-voltage relationships are obtained. The results show that QDT can be used as a proton detector by measuring transport through it and can conceivably act as a pH sensor in solutions. In addition, QDT may be able to distinguish among different monovalent species. This work suggests an approach to design modern molecular electronic conductance sensors with high sensitivity and specificity using well-established quantum chemistry

Electrochemistry of plutonium in molten halides

International Nuclear Information System (INIS)

McCurry, L.E.; Moy, G.M.M.; Bowersox, D.F.

1987-01-01

The electrochemistry of plutonium in molten halides is of technological importance as a method of purification of plutonium. Previous authors have reported that plutonium can be purified by electrorefining impure plutonium in various molten haldies. Work to eluciate the mechanism of the plutonium reduction in molten halides has been limited to a chronopotentiometric study in LiCl-KCl. Potentiometric studies have been carried out to determine the standard reduction potential for the plutonium (III) couple in various molten alkali metal halides. Initial cyclic voltammetric experiments were performed in molten KCL at 1100 K. A silver/silver chloride (10 mole %) in equimolar NaCl-KCl was used as a reference electrode. Working and counter electrodes were tungsten. The cell components and melt were contained in a quartz crucible. Background cyclic voltammograms of the KCl melt at the tungsten electrode showed no evidence of electroactive impurities in the melt. Plutonium was added to the melt as PuCl/sub 3/, which was prepared by chlorination of the oxide. At low concentrations of PuCl/sub 3/ in the melt (0.01-0.03 molar), no reduction wave due to the reduction of Pu(III) was observed in the voltammograms up to the potassium reduction limit of the melt. However on scan reversal after scanning into the potassium reduction limit a new oxidation wave was observed

Structural, dynamical, and transport properties of the hydrated halides: How do At{sup −} bulk properties compare with those of the other halides, from F{sup −} to I{sup −}?

Energy Technology Data Exchange (ETDEWEB)

Réal, Florent, E-mail: florent.real@univ-lille1.fr; Severo Pereira Gomes, André; Guerrero Martínez, Yansel Omar; Vallet, Valérie [Université de Lille, CNRS, UMR 8523–PhLAM–Physique des Lasers Atomes et Molécules, F-59000 Lille (France); Ayed, Tahra; Galland, Nicolas [CEISAM UMR CNRS 6230, Université de Nantes, 2 Rue de la Houssinière, BP 92208 F-44322 Nantes Cedex 3 (France); Masella, Michel [Laboratoire de Biologie Structurale et Radiobiologie, Service de Bioénergétique, Biologie Structurale et Mécanismes, Institut de Biologie et de Technologies de Saclay, CEA Saclay, F-91191 Gif sur Yvette Cedex (France)

2016-03-28

The properties of halides from the lightest, fluoride (F{sup −}), to the heaviest, astatide (At{sup −}), have been studied in water using a polarizable force-field approach based on molecular dynamics (MD) simulations at the 10 ns scale. The selected force-field explicitly treats the cooperativity within the halide-water hydrogen bond networks. The force-field parameters have been adjusted to ab initio data on anion/water clusters computed at the relativistic Möller-Plesset second-order perturbation theory level of theory. The anion static polarizabilities of the two heaviest halides, I{sup −} and At{sup −}, were computed in the gas phase using large and diffuse atomic basis sets, and taking into account both electron correlation and spin-orbit coupling within a four-component framework. Our MD simulation results show the solvation properties of I{sup −} and At{sup −} in aqueous phase to be very close. For instance, their first hydration shells are structured and encompass 9.2 and 9.1 water molecules at about 3.70 ± 0.05 Å, respectively. These values have to be compared to the F{sup −}, Cl{sup −}, and Br{sup −} ones, i.e., 6.3, 8.4, and 9.0 water molecules at 2.74, 3.38, and 3.55 Å, respectively. Moreover our computations predict the solvation free energy of At{sup −} in liquid water at ambient conditions to be 68 kcal mol{sup −1}, a value also close the I{sup −} one, about 70 kcal mol{sup −1}. In all, our simulation results for I{sup −} are in excellent agreement with the latest neutron- and X-ray diffraction studies. Those for the At{sup −} ion are predictive, as no theoretical or experimental data are available to date.

Impact of the organic halide salt on final perovskite composition for photovoltaic applications

KAUST Repository

Moore, David T.

2014-08-01

The methylammonium lead halide perovskites have shown significant promise as a low-cost, second generation, photovoltaic material.Despite recent advances, however, there are still a number of fundamental aspects of their formation as well as their physical and electronic behavior that are not well understood. In this letter we explore the mechanism by which these materials crystallize by testing the outcome of each of the reagent halide salts. We find that components of both salts, lead halide and methylammonium halide, are relatively mobile and can be readily exchanged during the crystallization process when the reaction is carried out in solution or in the solid state. We exploit this fact by showing that the perovskite structure is formed even when the lead salt\\'s anion is a non-halide, leading to lower annealing temperature and time requirements for film formation. Studies into these behaviors may ultimately lead to improved processing conditions for photovoltaic films. © 2014 Author(s).

Impact of the organic halide salt on final perovskite composition for photovoltaic applications

Directory of Open Access Journals (Sweden)

David T. Moore

2014-08-01

Full Text Available The methylammonium lead halide perovskites have shown significant promise as a low-cost, second generation, photovoltaic material. Despite recent advances, however, there are still a number of fundamental aspects of their formation as well as their physical and electronic behavior that are not well understood. In this letter we explore the mechanism by which these materials crystallize by testing the outcome of each of the reagent halide salts. We find that components of both salts, lead halide and methylammonium halide, are relatively mobile and can be readily exchanged during the crystallization process when the reaction is carried out in solution or in the solid state. We exploit this fact by showing that the perovskite structure is formed even when the lead salt's anion is a non-halide, leading to lower annealing temperature and time requirements for film formation. Studies into these behaviors may ultimately lead to improved processing conditions for photovoltaic films.

Observation of vapor pressure enhancement of rare-earth metal-halide salts in the temperature range relevant to metal-halide lamps

Energy Technology Data Exchange (ETDEWEB)

Curry, J. J.; Henins, A.; Hardis, J. E. [National Institute of Standards and Technology, Gaithersburg, Maryland 20899 (United States); Estupinan, E. G. [Osram Sylvania Inc., Beverly, Massachusetts 01915 (United States); Lapatovich, W. P. [Independent Consultant, 51 Pye Brook Lane, Boxford, Massachusetts 01921 (United States); Shastri, S. D. [Advanced Photon Source, Argonne National Laboratory, Argonne, Illinois 60439 (United States)

2012-02-20

Total vapor-phase densities of Dy in equilibrium with a DyI{sub 3}/InI condensate and Tm in equilibrium with a TmI{sub 3}/TlI condensate have been measured for temperatures between 900 K and 1400 K. The measurements show strong enhancements in rare-earth vapor densities compared to vapors in equilibrium with the pure rare-earth metal-halides. The measurements were made with x-ray induced fluorescence on the sector 1-ID beam line at the Advanced Photon Source. The temperature range and salt mixtures are relevant to the operation of metal-halide high-intensity discharge lamps.

Ultrafast time-resolved spectroscopy of lead halide perovskite films

Science.gov (United States)

Idowu, Mopelola A.; Yau, Sung H.; Varnavski, Oleg; Goodson, Theodore

2015-09-01

Recently, lead halide perovskites which are organic-inorganic hybrid structures, have been discovered to be highly efficient as light absorbers. Herein, we show the investigation of the excited state dynamics and emission properties of non-stoichiometric precursor formed lead halide perovskites grown by interdiffusion method using steady-state and time-resolved spectroscopic measurements. The influence of the different ratios of the non-stoichiometric precursor solution was examined. The observed photoluminescence properties were correlated with the femtosecond transient absorption measurements.

Epidemiological and Economic Impact of Monovalent and Pentavalent Rotavirus Vaccines in Low and Middle Income Countries: A Cost-effectiveness Modeling Analysis.

Science.gov (United States)

Paternina-Caicedo, Angel; De la Hoz-Restrepo, Fernando; Alvis-Guzmán, Nelson

2015-07-01

The competing choices of vaccination with either RV1 or RV5, the potential budget impact of vaccines on the EPI with different prices and new evidence make important an updated analysis for health decision makers in each country. The objective of this study is to assess cost-effectiveness of the monovalent and pentavalent rotavirus vaccines and impact on children deaths, inpatient and outpatient visits in 116 low and middle income countries that represent approximately 99% of rotavirus mortality. A decision tree model followed hypothetical cohorts of children from birth up to 5 years of age for each country in 2010. Inputs were gathered from international databases and previous research on incidence and effectiveness of monovalent and pentavalent vaccines. Costs were expressed in 2010 international dollars. Outcomes were reported in terms of cost per disability-adjusted life-year averted, comparing no vaccination with either monovalent or pentavalent mass introduction. Vaccine price was assumed fixed for all world low-income and middle-income countries. Around 292,000 deaths, 3.34 million inpatient cases and 23.09 million outpatient cases would occur with no vaccination. In the base-case scenario, monovalent vaccination would prevent 54.7% of inpatient cases and 45.4% of deaths. Pentavalent vaccination would prevent 51.4% of inpatient cases and 41.1% of deaths. The vaccine was cost-effective in all world countries in the base-case scenario for both vaccines. Cost per disability-adjusted life-year averted in all selected countries was I$372 for monovalent, and I$453 for pentavalent vaccination. Rotavirus vaccine is cost-effective in most analyzed countries. Despite cost-effectiveness analysis is a useful tool for decision making in middle-income countries, for low-income countries health decision makers should also assess the impact of introducing either vaccine on local resources and budget impact analysis of vaccination.

Standard Gibbs free energies for transfer of actinyl ions at the aqueous/organic solution interface

International Nuclear Information System (INIS)

Kitatsuji, Yoshihiro; Okugaki, Tomohiko; Kasuno, Megumi; Kubota, Hiroki; Maeda, Kohji; Kimura, Takaumi; Yoshida, Zenko; Kihara, Sorin

2011-01-01

Research highlights: → Standard Gibbs free energies for ion-transfer of tri- to hexavalent actinide ions. → Determination is based on distribution method combined with ion-transfer voltammetry. → Organic solvents examined are nitrobenzene, DCE, benzonitrile, acetophenone and NPOE. → Gibbs free energies of U(VI), Np(VI) and Pu(VI) are similar to each other. → Gibbs free energies of Np(V) is very large, comparing with ordinary monovalent cations. - Abstract: Standard Gibbs free energies for transfer (ΔG tr 0 ) of actinyl ions (AnO 2 z+ ; z = 2 or 1; An: U, Np, or Pu) between an aqueous solution and an organic solution were determined based on distribution method combined with voltammetry for ion transfer at the interface of two immiscible electrolyte solutions. The organic solutions examined were nitrobenzene, 1,2-dichloroethane, benzonitrile, acetophenone, and 2-nitrophenyl octyl ether. Irrespective of the type of organic solutions, ΔG tr 0 of UO 2 2+ ,NpO 2 2+ , and PuO 2 2+ were nearly equal to each other and slightly larger than that of Mg 2+ . The ΔG tr 0 of NpO 2 + was extraordinary large compared with those of ordinary monovalent cations. The dependence of ΔG tr 0 of AnO 2 z+ on the type of organic solutions was similar to that of H + or Mg 2+ . The ΔG tr 0 of An 3+ and An 4+ were also discussed briefly.

Gaseous odd- and even-electron ions

International Nuclear Information System (INIS)

Wagner, W.; Heimbach, H.; Levsen, K.

1980-01-01

The principal collision-induced fragmentations of simple protonated ketones, aldehydes, ethers, amines, sulphides, alcohols, acids, nitriles and halides are discussed. These protonated molecules decompose mainly by loss of alkane, alkene and RX (R = alkyl, H; X = OH, SH, NH 2 , Br, I). Substantial radical losses are only observed for small protonated molecules. Deuterium-labelling demonstrates that the X-H bond is particularly strong. The fragmentation of (MH) + ions is compared with that of the corresponding (M) + sup(.) ions is compared with that of the corresponding (M) + sup(.) ions. The spectra of the (M) + sup(.) ions are dominated by direct bond cleavages, in particular α-cleavages, as a result of both the stability of the ionic fragment and the loose transition state. In (MH) + ions direct bond cleavages lead to energetically less favourable products. Thus rearrangement reactions play a more important role in the decomposition of these ions. (MH) + ions are more stable relative to fragmentation than (M) + sup(.) ions. (orig.)

Origins and mechanisms of hysteresis in organometal halide perovskites

Science.gov (United States)

Li, Cheng; Guerrero, Antonio; Zhong, Yu; Huettner, Sven

2017-05-01

Inorganic-organic halide organometal perovskites, such as CH3NH3PbI3 and CsPbI3, etc, have been an unprecedented rising star in the field of photovoltaics since 2009, owing to their exceptionally high power conversion efficiency and simple fabrication processability. Despite its relatively short history of development, intensive investigations have been concentrating on this material; these have ranged from crystal structure analysis and photophysical characterization to performance optimization and device integration, etc. Yet, when applied in photovoltaic devices, this material suffers from hysteresis, that is, the difference of the current-voltage (I-V) curve during sweeping in two directions (from short-circuit towards open-circuit and vice versa). This behavior may significantly impede its large-scale commercial application. This Review will focus on the recent theoretical and experimental efforts to reveal the origin and mechanism of hysteresis. The proposed origins include (1) ferroelectric polarization, (2) charge trapping/detrapping, and (3) ion migration. Among them, recent evidence consistently supports the idea that ion migration plays a key role for the hysteretic behavior in perovskite solar cells (PSCs). Hence, this Review will summarize the recent results on ion migration such as the migrating ion species, activation energy measurement, capacitive characterization, and internal electrical field modulation, etc. In addition, this Review will also present the devices with alleviation/elimination of hysteresis by incorporating either large-size grains or phenyl-C61-butyric acid methyl ester molecules. In a different application, the hysteretic property has been utilized in photovoltaic and memristive switching devices. In sum, by examining these three possible mechanisms, it is concluded that the origin of hysteresis in PSCs is associated with a combination of effects, but mainly limited by ion/defect migration. This strong interaction between ion

Lanthanide doped strontium-barium cesium halide scintillators

Science.gov (United States)

Bizarri, Gregory; Bourret-Courchesne, Edith; Derenzo, Stephen E.; Borade, Ramesh B.; Gundiah, Gautam; Yan, Zewu; Hanrahan, Stephen M.; Chaudhry, Anurag; Canning, Andrew

2015-06-09

The present invention provides for a composition comprising an inorganic scintillator comprising an optionally lanthanide-doped strontium-barium, optionally cesium, halide, useful for detecting nuclear material.

Open-Structured V ₂ O ₅ · n H ₂ O Nanoflakes as Highly Reversible Cathode Material for Monovalent and Multivalent Intercalation Batteries

Energy Technology Data Exchange (ETDEWEB)

Wang, Huali [Beijing Key Laboratory of Environmental Science and Engineering, School of Materials Science and Engineering, Beijing Institute of Technology, Beijing 100081 China; Bi, Xuanxuan [Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 South Cass Avenue Lemont IL 60439 USA; Department of Chemistry and Biochemistry, Ohio State University, 100 West 18th Avenue Columbus OH 43210 USA; Bai, Ying [Beijing Key Laboratory of Environmental Science and Engineering, School of Materials Science and Engineering, Beijing Institute of Technology, Beijing 100081 China; Wu, Chuan [Beijing Key Laboratory of Environmental Science and Engineering, School of Materials Science and Engineering, Beijing Institute of Technology, Beijing 100081 China; Collaborative Innovation Center of Electric Vehicles in Beijing, Beijing 100081 China; Gu, Sichen [Beijing Key Laboratory of Environmental Science and Engineering, School of Materials Science and Engineering, Beijing Institute of Technology, Beijing 100081 China; Chen, Shi [Beijing Key Laboratory of Environmental Science and Engineering, School of Materials Science and Engineering, Beijing Institute of Technology, Beijing 100081 China; Collaborative Innovation Center of Electric Vehicles in Beijing, Beijing 100081 China; Wu, Feng [Beijing Key Laboratory of Environmental Science and Engineering, School of Materials Science and Engineering, Beijing Institute of Technology, Beijing 100081 China; Collaborative Innovation Center of Electric Vehicles in Beijing, Beijing 100081 China; Amine, Khalil [Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 South Cass Avenue Lemont IL 60439 USA; Lu, Jun [Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 South Cass Avenue Lemont IL 60439 USA

2017-04-21

The high-capacity cathode material V2O5·nH2O has attracted considerable attention for metal ion batteries due to the multielectron redox reaction during electrochemical processes. It has an expanded layer structure, which can host large ions or multivalent ions. However, structural instability and poor electronic and ionic conductivities greatly handicap its application. Here, in cell tests, self-assembly V2O5·nH2O nanoflakes shows excellent electrochemical performance with either monovalent or multivalent cation intercalation. They are directly grown on a 3D conductive stainless steel mesh substrate via a simple and green hydrothermal method. Well-layered nanoflakes are obtained after heat treatment at 300 °C (V2O5·0.3H2O). Nanoflakes with ultrathin flower petals deliver a stable capacity of 250 mA h g-1 in a Li-ion cell, 110 mA h g-1 in a Na-ion cell, and 80 mA h g-1 in an Al-ion cell in their respective potential ranges (2.0–4.0 V for Li and Na-ion batteries and 0.1–2.5 V for Al-ion battery) after 100 cycles.

Atomic forces between noble gas atoms, alkali ions, and halogen ions for surface interactions

Science.gov (United States)

Wilson, J. W.; Outlaw, R. A.; Heinbockel, J. H.

1988-01-01

The components of the physical forces between noble gas atoms, alkali ions, and halogen ions are analyzed and a data base developed from analysis of the two-body potential data, the alkali-halide molecular data, and the noble gas crystal and salt crystal data. A satisfactory global fit to this molecular and crystal data is then reproduced by the model to within several percent. Surface potentials are evaluated for noble gas atoms on noble gas surfaces and salt crystal surfaces with surface tension neglected. Within this context, the noble gas surface potentials on noble gas and salt crystals are considered to be accurate to within several percent.

A metal-ion NMR investigation of the antibiotic facilitated transport of monovalent cations through the walls of phospholipid vesicles. II. Sulfur-33 NMR

International Nuclear Information System (INIS)

Buster, D.C.

1988-01-01

A technique has been developed to investigate the antibiotic facilitated transmembrane transport of monovalent cations using 23 Na and 7 Li Nuclear Magnetic Resonance spectroscopy. The initial portion of this thesis outlines the production and characterization of a model lipid system amenable to the NMR detection of cation transport. Large unilamellar vesicles (LUV) have been prepared from a 4:1 mixture of phosphatidylcholine and phosphatidylglycerol. The presence of the anionic chemical shift reagent dysprosium (III) tripolyphosphate, either inside or outside of the vesicles, allows for the spectroscopic separation of the NMR resonances arising from the inter- and extravesicular cation pools. The cation transporting properties of the channel-forming pentadecapeptide, gramicidin D, have been studied using the NMR technique

Luminescence of Er3+ doped double lead halide crystals under X-ray, UV, VIS and IR excitation

Science.gov (United States)

Serazetdinov, A. R.; Smirnov, A. A.; Pustovarov, V. A.; Isaenko, L. I.

2017-09-01

Er3+ doped double lead halide crystals incorporate a number of properties making them interesting for practical use in light conducting materials. X-ray excited luminescence (XRL) spectra, photoluminescence (PL) spectra in region of 1.5-3.5 eV, photoluminescence excitation (PLE) spectra (2.75-5 eV) and anti-stokes luminescence (ASL) spectra were measured at room temperature in KPb2Cl5 (KPC) and RbPb2Br5 (RPB) matrices doped with Er3+ (1%) ions and in KPC doped with Er3++ Yb3+ ions(1:3 ratio concentration). Intraconfigurational f→f transitions are observed in Er3+ ions in most of the cases. The concrete spectrum form is strongly dependent on the excitation energy. Under 980 nm excitation upper Er3+ levels are excited, showing upconversional processes. In case of 313 nm (UV) and 365 nm (VIS) excitation self trapped exciton luminescence was detected in RPB crystal. Additional Yb3+ doping ions strongly increase quantum yield under 980 nm excitation and this doping cause insignificant influence on quantum yield under VIS or UV excitation.

luminescence in coloured alkali halide crystals

Indian Academy of Sciences (India)

have studied the effect of annealing in chlorine gas on the ML of X-rayed KCl crystals. ..... high temperature because of the thermal bleaching of the coloration in alkali halide ..... [31] J Hawkins, Ph.D. Thesis (University of Reading, 1976).

Ultraviolet optical absorption of alkali cyanides and alkali halide cyanides

International Nuclear Information System (INIS)

Souza Camargo Junior, S.A. de.

1982-09-01

The ultraviolet absorption spectra of alkali cyanide and mixed alkali halide cyanide crystals were measured at temperatures ranging from 300K down to 4.2K. A set of small absorption peaks was observed at energies near 6 eV and assigned to parity forbidden X 1 Σ + →a' 3 Σ + transitions of the CN - molecular ions. It was observed that the peak position depends on the alkali atom while the absorption cross section strongly depends on the halogen and on the CN - concentration of the mixed crystals. These effects are explained in terms of an interaction between the triplet molecular excitons and charge transfer excitons. The experimental data were fit with a coupling energy of a few meV. The coupling mechanism is discussed and it is found to be due to the overlap between the wave functions of the two excitations. (Author) [pt

Purcell effect in an organic-inorganic halide perovskite semiconductor microcavity system

International Nuclear Information System (INIS)

Wang, Jun; Wang, Yafeng; Hu, Tao; Wu, Lin; Shen, Xuechu; Chen, Zhanghai; Cao, Runan; Xu, Fei; Da, Peimei; Zheng, Gengfeng; Lu, Jian

2016-01-01

Organic-inorganic halide perovskite semiconductors with the attractive physics properties, including strong photoluminescence (PL), huge oscillator strengths, and low nonradiative recombination losses, are ideal candidates for studying the light-matter interaction in nanostructures. Here, we demonstrate the coupling of the exciton state and the cavity mode in the lead halide perovskite microcavity system at room temperature. The Purcell effect in the coupling system is clearly observed by using angle-resolved photoluminescence spectra. Kinetic analysis based on time-resolved PL reveals that the spontaneous emission rate of the halide perovskite semiconductor is significantly enhanced at resonance of the exciton energy and the cavity mode. Our results provide the way for developing electrically driven organic polariton lasers, optical devices, and on-chip coherent quantum light sources

In vitro neutralisation of rotavirus infection by two broadly specific recombinant monovalent llama-derived antibody fragments

NARCIS (Netherlands)

F. Aladin (Farah); A.W.C. Einerhand (Sandra); J. Bouma (Janneke); S. Bezemer (Sandra); P. Hermans (Pim); D. Wolvers (Danielle); K. Bellamy (Kate); L.G.J. Frenken (Leon); J. Gray (Jim); M. Iturriza-Gómara (Miren)

2012-01-01

textabstractRotavirus is the main cause of viral gastroenteritis in young children. Therefore, the development of inexpensive antiviral products for the prevention and/or treatment of rotavirus disease remains a priority. Previously we have shown that a recombinant monovalent antibody fragment

10 CFR 431.322 - Definitions concerning metal halide lamp ballasts and fixtures.

Science.gov (United States)

2010-01-01

... high intensity discharge fixture, the efficiency of a lamp and ballast combination, expressed as a... lamps. Metal halide lamp means a high intensity discharge lamp in which the major portion of the light... 10 Energy 3 2010-01-01 2010-01-01 false Definitions concerning metal halide lamp ballasts and...

Complexes of alkylphenols with aluminium halides

International Nuclear Information System (INIS)

Golounin, A.V.

1997-01-01

Interaction of aluminium halides with alkylphenols is studied through the NMR method. The peculiarity of complex formation of pentamethylphenol with AlI 3 is revealed. By AlI 3 action on the pentamethylphenol the complexes are formed both of keto- and oxy form [ru

Raman microspectroscopic study of effects of Na(I) and Mg(II) ions on low pH induced DNA structural changes.

Science.gov (United States)

Muntean, C M; Segers-Nolten, G M J

2003-01-01

In this work a confocal Raman microspectrometer is used to investigate the influence of Na(+) and Mg(2+) ions on the DNA structural changes induced by low pH. Measurements are carried out on calf thymus DNA at neutral pH (7) and pH 3 in the presence of low and high concentrations of Na(+) and Mg(2+) ions, respectively. It is found that low concentrations of Na(+) ions do not protect DNA against binding of H(+). High concentrations of monovalent ions can prevent protonation of the DNA double helix. Our Raman spectra show that low concentrations of Mg(2+) ions partly protect DNA against protonation of cytosine (line at 1262 cm(-1)) but do not protect adenine and guanine N(7) against binding of H(+) (characteristic lines at 1304 and 1488 cm(-1), respectively). High concentrations of Mg(2+) can prevent protonation of cytosine and protonation of adenine (disruption of AT pairs). By analyzing the line at 1488 cm(-1), which obtains most of its intensity from a guanine vibration, high magnesium salt protect the N(7) of guanine against protonation. A high salt concentration can prevent protonation of guanine, cytosine, and adenine in DNA. Higher salt concentrations cause less DNA protonation than lower salt concentrations. Magnesium ions are found to be more effective in protecting DNA against binding of H(+) as compared with calcium ions presented in a previous study. Divalent metal cations (Mg(2+), Ca(2+)) are more effective in protecting DNA against protonation than monovalent ions (Na(+)). Copyright 2003 Wiley Periodicals, Inc. Biopolymers (Biospectroscopy) 72: 000-000, 2003

Broadly tunable metal halide perovskites for solid-state light-emission applications

OpenAIRE

Adjokatse, Sampson; Fang, Hong-Hua; Loi, Maria Antonietta

2017-01-01

The past two years have witnessed heightened interest in metal-halide perovskites as promising optoelectronic materials for solid-state light emitting applications beyond photovoltaics. Metal-halide perovskites are low-cost solution-processable materials with excellent intrinsic properties such as broad tunability of bandgap, defect tolerance, high photoluminescence quantum efficiency and high emission color purity (narrow full-width at half maximum). In this review, the photophysical propert...

Cation-Dependent Light-Induced Halide Demixing in Hybrid Organic-Inorganic Perovskites

OpenAIRE

Sutter-Fella, CM; Ngo, QP; Cefarin, N; Gardener, K; Tamura, N; Stan, CV; Drisdell, WS; Javey, A; Toma, FM; Sharp, ID

2018-01-01

© 2018 American Chemical Society. Mixed cation metal halide perovskites with increased power conversion efficiency, negligible hysteresis, and improved long term stability under illumination, moisture, and thermal stressing have emerged as promising compounds for photovoltaic and optoelectronic applications. Here, we shed light on photo-induced halide demixing using in-situ photoluminescence spectroscopy and in-situ synchrotron X-ray diffraction (XRD) to directly compare the evolution of comp...

Refined global methyl halide budgets with respect to rapeseed (Brassica napus) by life-cycle measurements

Science.gov (United States)

Jiao, Y.; Acdan, J.; Xu, R.; Deventer, M. J.; Rhew, R. C.

2017-12-01

A precise quantification of global methyl halide budgets is needed to evaluate the ozone depletion potential of these compounds and to predict future changes of stratospheric ozone. However, the global budgets of methyl halides are not balanced between currently identified and quantified sources and sinks. Our study re-evaluated the methyl bromide budget from global cultivated rapeseed (Brassica napus) through life-cycle flux measurements both in the greenhouse and in the field, yielding a methyl bromide emission rate that scales globally to 1.0 - 1.2 Gg yr-1. While this indicates a globally significant source, it is much smaller than the previously widely cited value of 5 - 6 Gg yr-1(Mead et al., 2008), even taking into account the near tripling of annual global yield of rapeseed since the previous evaluation was conducted. Our study also evaluated the methyl chloride and methyl iodide emission levels from rapeseed, yielding emission rates that scale to 5.4 Gg yr-1 for methyl chloride and 1.8 Gg yr-1 of methyl iodide. The concentrations of the methyl donor SAM (S-adenosyl methionine) and the resultant product SAH (S-Adenosyl-L-homocysteine) were also analyzed to explore their role in biogenic methyl halide formation. Halide gradient incubations showed that the magnitude of methyl halide emissions from rapeseed is highly correlated to soil halide levels, thus raising the concern that the heterogeneity of soil halide contents geographically should be considered when extrapolating to global budget.

Solar cells, structures including organometallic halide perovskite monocrystalline films, and methods of preparation thereof

KAUST Repository

Bakr, Osman; Peng, Wei; Wang, Lingfei

2017-01-01

Embodiments of the present disclosure provide for solar cells including an organometallic halide perovskite monocrystalline film (see fig. 1.1B), other devices including the organometallic halide perovskite monocrystalline film, methods of making

Behaviour of zirconium oxidation and is oxide films in alkali halide solutions as studied by electrochemical techniques

International Nuclear Information System (INIS)

Saleh, H.E.M.

1996-01-01

Study of the properties of Zr electrode and the oxide films that cover the metal surface is of extreme importance due to their wide applications in chemical and nuclear industry. In this thesis the electrochemical behaviour of Zr electrode in alkali halide solutions and with various surface conditions was studied, Also the galvanostatic oxidation of the metal in addition to the open circuit and impedance measurements were employed. Chapter I is a literature survey of the electrochemistry of Zr metal with particular emphasis on the stability and growth process of Zr in different media. Chapter II contains the experimental part, including details of the electrochemical techniques used in the measurements. The electrode impedance was always balanced as a series capacitance Cs and resistance Rs.Chapter III includes the experimental results and discussion. It is divide into sections, A and B. Section A includes the results of some experimental parameters which affect the reactivity of the oxide growth process on the zirconium surface, such as surface pre - treatment, electrolyte composition, the effect of different alkali halide anions, as well as the triiodide ion. 9 tabs.,26 figs.,67 refs

EVALUATION OF REACTOGENICITY, SAFETY AND IMMUNOGENICITY OF INACTIVATED MONOVALENT VACCINE IN CHILDREN

OpenAIRE

A.N. Mironov; A.A. Romanova; R.Ya. Meshkova; I.V. Fel’dblyum; N.V. Kupina; D.S. Bushmenkov; A.A. Tsaan

2010-01-01

NPO «Microgen» developed vaccine «PANDEFLU» — influenza inactivated subunit adsorbed monovalent vaccine, strain A/California/7/2009 (H1N1), for specific prophylaxis of pandemic influenza in different age groups of citizens. Reactogenicity, safety and immunogenicity were analyzed in a study of volunteers 18–60 years old. The article presents results of administration of vaccine «PANDEFLU» in children. The study performed in two clinical centers proves good tolerability, reactogenicity, safety ...

Heterofacial alkylation of alkylenediamines by higher alkyl halides

International Nuclear Information System (INIS)

Semenov, V.A.; Kryshko, G.M.; Sokal'skaya, L.I.; Zhukova, N.G.

1985-01-01

A study of the physiochemical properties of alkylenediamines substituted by lower alkyls, showed that they possess increased complex-forming ability with respect to salts of different metals as titanium, niobium, zirconium, molybdenum, and zinc. To create a simpler method of synthesis of higher tetraaklyalkylalklyenediamines, based on the use of the accessible domestic raw material, the authors investigated the reaction of alkylenediamines with various alkyl halides. It was established that the best reagents can be obtained using alkyl bromides. It is concluded that the procedure of alkylation of alkylenediamines by higher alkyl halides in the presence of water developed permits the production of terraalkylalkylenediamines in one step with good yield and with purity acceptable for use as extraction reagents

Lasing in robust cesium lead halide perovskite nanowires

Science.gov (United States)

Eaton, Samuel W.; Lai, Minliang; Gibson, Natalie A.; Wong, Andrew B.; Dou, Letian; Ma, Jie; Wang, Lin-Wang; Leone, Stephen R.; Yang, Peidong

2016-01-01

The rapidly growing field of nanoscale lasers can be advanced through the discovery of new, tunable light sources. The emission wavelength tunability demonstrated in perovskite materials is an attractive property for nanoscale lasers. Whereas organic–inorganic lead halide perovskite materials are known for their instability, cesium lead halides offer a robust alternative without sacrificing emission tunability or ease of synthesis. Here, we report the low-temperature, solution-phase growth of cesium lead halide nanowires exhibiting low-threshold lasing and high stability. The as-grown nanowires are single crystalline with well-formed facets, and act as high-quality laser cavities. The nanowires display excellent stability while stored and handled under ambient conditions over the course of weeks. Upon optical excitation, Fabry–Pérot lasing occurs in CsPbBr3 nanowires with an onset of 5 μJ cm−2 with the nanowire cavity displaying a maximum quality factor of 1,009 ± 5. Lasing under constant, pulsed excitation can be maintained for over 1 h, the equivalent of 109 excitation cycles, and lasing persists upon exposure to ambient atmosphere. Wavelength tunability in the green and blue regions of the spectrum in conjunction with excellent stability makes these nanowire lasers attractive for device fabrication. PMID:26862172

Quantum confinement effect of two-dimensional all-inorganic halide perovskites

KAUST Repository

Cai, Bo; Li, Xiaoming; Gu, Yu; Harb, Moussab; Li, Jianhai; Xie, Meiqiu; Cao, Fei; Song, Jizhong; Zhang, Shengli; Cavallo, Luigi; Zeng, Haibo

2017-01-01

Quantum confinement effect (QCE), an essential physical phenomenon of semiconductors when the size becomes comparable to the exciton Bohr radius, typically results in quite different physical properties of low-dimensional materials from their bulk counterparts and can be exploited to enhance the device performance in various optoelectronic applications. Here, taking CsPbBr3 as an example, we reported QCE in all-inorganic halide perovskite in two-dimensional (2D) nanoplates. Blue shifts in optical absorption and photoluminescence spectra were found to be stronger in thinner nanoplates than that in thicker nanoplates, whose thickness lowered below ∼7 nm. The exciton binding energy results showed similar trend as that obtained for the optical absorption and photoluminescence. Meanwile, the function of integrated intensity and full width at half maximum and temperature also showed similar results, further supporting our conclusions. The results displayed the QCE in all-inorganic halide perovskite nanoplates and helped to design the all-inorganic halide perovskites with desired optical properties.

Quaternary oxide halides of group 15 with zinc and cadmium

International Nuclear Information System (INIS)

Rueck, Nadia

2014-01-01

The present thesis ''Quaternary oxide halides of group 15 with zinc and cadmium'' deals with the chemical class of oxide halides, which contain d-block element cations and pnicogens. Over the past few years compounds containing pnicogene cations are intensively investigated. The reason for this is the free electron pair of the Pn"3"+ cation, which is responsible for some interesting properties. Free electron pairs do not only impact the spatial structure of molecules but also the properties of materials. The object of this work was the synthesis and characterization of compounds containing Pn"3"+ cations with free electron pairs. Due to the structure-determining effect of these free electron pairs and in combination with halides it is possible to synthesize compounds with low-dimensional structures like chains and layers. In these compounds the structure is separated into halophilic and chalcophilic sub-structures, which are held together only by weak Van der Waals forces.

Quantum confinement effect of two-dimensional all-inorganic halide perovskites

KAUST Repository

Cai, Bo

2017-09-07

Quantum confinement effect (QCE), an essential physical phenomenon of semiconductors when the size becomes comparable to the exciton Bohr radius, typically results in quite different physical properties of low-dimensional materials from their bulk counterparts and can be exploited to enhance the device performance in various optoelectronic applications. Here, taking CsPbBr3 as an example, we reported QCE in all-inorganic halide perovskite in two-dimensional (2D) nanoplates. Blue shifts in optical absorption and photoluminescence spectra were found to be stronger in thinner nanoplates than that in thicker nanoplates, whose thickness lowered below ∼7 nm. The exciton binding energy results showed similar trend as that obtained for the optical absorption and photoluminescence. Meanwile, the function of integrated intensity and full width at half maximum and temperature also showed similar results, further supporting our conclusions. The results displayed the QCE in all-inorganic halide perovskite nanoplates and helped to design the all-inorganic halide perovskites with desired optical properties.

Electrochemical behavior of Ti and Ti6Al4V in aqueous solutions of citric acid containing halides

Directory of Open Access Journals (Sweden)

Anelise Marlene Schmidt

2006-12-01

Full Text Available This paper reports on an investigation of the electrochemical behavior of Ti grade 2 and Ti6Al4V alloy in aqueous citric acid solutions with pH 2.0 containing halide ions. Voltammetric studies of Ti and the alloy in citric acid, with and without chloride ions, indicate that the Ti and Ti alloy presented a passive behavior in the test solutions used. Pitting was observed at 3.0 and 2.5 V/SCE for Ti and Ti6Al4V, respectively, when bromide ions were added to the solution. In solutions containing fluoride ions, dissolution of the film occurred at potentials close to - 1.0 V/SCE in both electrodes. The iodide ions oxidized on the passive oxide film at potentials close to 1.0 V/SCE. EIS results of the materials in citric acid solutions containing chloride ions revealed that the film's resistance increased as the applied potential rose from 0 to 1.0 V. In bromide-containing solutions, breakdown of the film was confirmed at potentials above 2.0 V/SCE in both electrodes. These results suggest film reformation for Ti and the alloy in solutions containing fluoride at potentials within the passive region.

Radiation damages on superionic conductors

International Nuclear Information System (INIS)

Awano, T.; Ikezawa, M.; Matsuyama, T.

1995-01-01

Irradiation coloration on superionic conductors of MA 4 X 5 (M=K, Rb, NH 4 ; A=Ag, Cu; X=Cl, I) was observed. Five absorption bands were observed at 1.4, 1.8, 2.1, 2.3 and 2.9 eV in RbAg 4 I 5 . In these crystals, stable coloration was observed at lower temperature than in alkali halides. The absorption bands due to electronic centers and hole one were classified from the results of optical breaching and electron or hole doping. Growth rate and induced spectra by irradiation changed drastically at the temperatures just above the superionic phase transition. The growth rate increased drastically also at 40 K. ESR signal of γ-irradiated RbCu 4 Cl 3 I 2 showed that one of the induced defects is a hole trapped by a monovalent copper ion (Cu 2+ ). (author)

Crucial role of dynamic linker histone binding and divalent ions for DNA accessibility and gene regulation revealed by mesoscale modeling of oligonucleosomes

Science.gov (United States)

Collepardo-Guevara, Rosana; Schlick, Tamar

2012-01-01

Monte Carlo simulations of a mesoscale model of oligonucleosomes are analyzed to examine the role of dynamic-linker histone (LH) binding/unbinding in high monovalent salt with divalent ions, and to further interpret noted chromatin fiber softening by dynamic LH in monovalent salt conditions. We find that divalent ions produce a fiber stiffening effect that competes with, but does not overshadow, the dramatic softening triggered by dynamic-LH behavior. Indeed, we find that in typical in vivo conditions, dynamic-LH binding/unbinding reduces fiber stiffening dramatically (by a factor of almost 5, as measured by the elasticity modulus) compared with rigidly fixed LH, and also the force needed to initiate chromatin unfolding, making it consistent with those of molecular motors. Our data also show that, during unfolding, divalent ions together with LHs induce linker-DNA bending and DNA–DNA repulsion screening, which guarantee formation of heteromorphic superbeads-on-a-string structures that combine regions of loose and compact fiber independently of the characteristics of the LH–core bond. These structures might be important for gene regulation as they expose regions of the DNA selectively. Dynamic control of LH binding/unbinding, either globally or locally, in the presence of divalent ions, might constitute a mechanism for regulation of gene expression. PMID:22790986

Thorium valency in molten alkali halides in equilibrium with metallic thorium

International Nuclear Information System (INIS)

Smirnov, M.V.; Kudyakov, V.Ya.

1983-01-01

Metallic thorium is shown to corrode in molten alkali halides even in the absence of external oxidizing agents, alkali cations acting as oxidizing agents. Its corrosion rate grows in the series of alkali chlorides from LiCl to CsCl at constant temperature. Substituting halide anions for one another exerts a smaller influence, the rate rising slightly in going from chlorides to bromides and iodides, having the same alkali cations. Thorium valency is determined coulometrically, the metal being dissolved anodically in molten alkali halides and their mixtures. In fluoride melts it is equal to 4 but in chloride, bromide and iodide ones, as a rule, it has non-integral values between 4 and 2 which diminish as the temperature is raised, as the thorium concentration is lowered, as the radii of alkali cations decrease and those of halide anions increase. The emf of cells Th/N ThHlsub(n) + (1-N) MHl/MHl/C, Hlsub(2(g)) where Hl is Cl, Br or I, M is Li, Na, K, Cs or Na + K, and N < 0.05, is measured as a function of concentration at several temperatures. Expressions are obtained for its concentration dependence. The emf grows in the series of alkali chlorides from LiCl to CsCl, other conditions being equal. (author)

Ion Permeation and Mechanotransduction Mechanisms of Mechanosensitive Piezo Channels.

Science.gov (United States)

Zhao, Qiancheng; Wu, Kun; Geng, Jie; Chi, Shaopeng; Wang, Yanfeng; Zhi, Peng; Zhang, Mingmin; Xiao, Bailong

2016-03-16

Piezo proteins have been proposed as the long-sought-after mechanosensitive cation channels in mammals that play critical roles in various mechanotransduction processes. However, the molecular bases that underlie their ion permeation and mechanotransduction have remained functionally undefined. Here we report our finding of the miniature pore-forming module of Piezo1 that resembles the pore architecture of other trimeric channels and encodes the essential pore properties. We further identified specific residues within the pore module that determine unitary conductance, pore blockage and ion selectivity for divalent and monovalent cations and anions. The non-pore-containing region of Piezo1 confers mechanosensitivity to mechano-insensitive trimeric acid-sensing ion channels, demonstrating that Piezo1 channels possess intrinsic mechanotransduction modules separate from their pore modules. In conclusion, this is the first report on the bona fide pore module and mechanotransduction components of Piezo channels, which define their ion-conducting properties and gating by mechanical stimuli, respectively. Copyright © 2016 Elsevier Inc. All rights reserved.

Transfer Hydro-dehalogenation of Organic Halides Catalyzed by Ruthenium(II) Complex.

Science.gov (United States)

You, Tingjie; Wang, Zhenrong; Chen, Jiajia; Xia, Yuanzhi

2017-02-03

A simple and efficient Ru(II)-catalyzed transfer hydro-dehalogenation of organic halides using 2-propanol solvent as the hydride source was reported. This methodology is applicable for hydro-dehalogenation of a variety of aromatic halides and α-haloesters and amides without additional ligand, and quantitative yields were achieved in many cases. The potential synthetic application of this method was demonstrated by efficient gram-scale transformation with catalyst loading as low as 0.5 mol %.

Does an electronic continuum correction improve effective short-range ion-ion interactions in aqueous solution?

Science.gov (United States)

Bruce, Ellen E.; van der Vegt, Nico F. A.

2018-06-01

Non-polarizable force fields for hydrated ions not always accurately describe short-range ion-ion interactions, frequently leading to artificial ion clustering in bulk aqueous solutions. This can be avoided by adjusting the nonbonded anion-cation or cation-water Lennard-Jones parameters. This approach has been successfully applied to different systems, but the parameterization is demanding owing to the necessity of separate investigations of each ion pair. Alternatively, polarization effects may effectively be accounted for using the electronic continuum correction (ECC) of Leontyev et al. [J. Chem. Phys. 119, 8024 (2003)], which involves scaling the ionic charges with the inverse square-root of the water high-frequency dielectric permittivity. ECC has proven to perform well for monovalent salts as well as for divalent salts in water. Its performance, however, for multivalent salts with higher valency remains unexplored. The present work illustrates the applicability of the ECC model to trivalent K3PO4 and divalent K2HPO4 in water. We demonstrate that the ECC models, without additional tuning of force field parameters, provide an accurate description of water-mediated interactions between salt ions. This results in predictions of the osmotic coefficients of aqueous K3PO4 and K2HPO4 solutions in good agreement with experimental data. Analysis of ion pairing thermodynamics in terms of contact ion pair (CIP), solvent-separated ion pair, and double solvent-separated ion pair contributions shows that potassium-phosphate CIP formation is stronger with trivalent than with divalent phosphate ions.

Structure and energetics of trivalent metal halides

International Nuclear Information System (INIS)

Hutchinson, F.

1999-01-01

Metal trihalide (MX 3 ) systems represent a stern challenge in terms of constructing transferable potential models. Starting from a previously published set of potentials, 'extended' ionic models are developed which, at the outset, include only anion polarization. Deficiencies in these models, particularly for smaller (highly polarizing) cations, axe shown to be significant. For example, crystal structures different to those observed experimentally axe adopted. The potentials axe improved upon by reference to ab initio information available for alkali halides with the 'constraint' that the parameters transfer systematically in a physically transparent manner, for example, in terms of ion radii. The possible influence of anion compression ('breathing') and the relative abundance of anion-anion interactions are considered. Simulation techniques axe developed to allow for the effective simulation of any system symmetry and for the study of transitions between different crystals (constant stress). The developed models are fully tested for a large range of metal trichloride (MCl 3 ) systems. Particular attention is paid to the comparison with recent neutron and X-ray diffraction data on the liquid state. Polarization effects axe shown to be vital in reproducing strong experimental features. The excellent agreement between simulation and experiment allows for differences in experimental procedures to be highlighted. The transferability is further tested by modelling mixtures of the lanthanides with alkali halides with potentials unchanged from the pure systems. The complex evolution of the melt structure is highlighted as the concentration of MCl 3 increases. The effectiveness of the models is tested by reference to dynamical properties. Particular attention is paid to the comparison with Raman scattering data available for a wide range of systems and mixture concentrations. The simulated spectra are generated both by a simple molecular picture of the underlying

Low-Temperature Electron Beam-Induced Transformations of Cesium Lead Halide Perovskite Nanocrystals

Science.gov (United States)

2017-01-01

Cesium lead halide perovskite (CsPbX3, with X = Br, Cl, I) nanocrystals have been found to undergo severe modifications under the high-energy electron beam irradiation of a transmission electron microscope (80/200 keV). In particular, in our previous work, together with halogen desorption, Pb2+ ions were found to be reduced to Pb0 and then diffused to form lead nanoparticles at temperatures above −40 °C. Here, we present a detailed irradiation study of CsPbBr3 nanocrystals at temperatures below −40 °C, a range in which the diffusion of Pb0 atoms/clusters is drastically suppressed. Under these conditions, the irradiation instead induces the nucleation of randomly oriented CsBr, CsPb, and PbBr2 crystalline domains. In addition to the Br desorption, which accompanies Pb2+ reduction at all the temperatures, Br is also desorbed from the CsBr and PbBr2 domains at low temperatures, leading to a more pronounced Br loss, thus the final products are mainly composed of Cs and Pb. The overall transformation involves the creation of voids, which coalesce upon further exposure, as demonstrated in both nanosheets and nanocuboids. Our results show that although low temperatures hinder the formation of Pb nanoparticles in CsPbBr3 nanocrystals when irradiated, the nanocrystals are nevertheless unstable. Consequently, we suggest that an optimum combination of temperature range, electron energy, and dose rate needs to be carefully chosen for the characterization of halide perovskite nanocrystals to minimize both the Pb nanoparticle formation and the structural decomposition. PMID:28983524

Environmental Effects on the Photophysics of Organic-Inorganic Halide Perovskites.

Science.gov (United States)

Galisteo-López, Juan F; Anaya, M; Calvo, M E; Míguez, H

2015-06-18

The photophysical properties of films of organic-inorganic lead halide perovskites under different ambient conditions are herein reported. We demonstrate that their luminescent properties are determined by the interplay between photoinduced activation and darkening processes, which strongly depend on the atmosphere surrounding the samples. We have isolated oxygen and moisture as the key elements in each process, activation and darkening, both of which involve the interaction with photogenerated carriers. These findings show that environmental factors play a key role in the performance of lead halide perovskites as efficient luminescent materials.

Advancement on Lead-Free Organic-Inorganic Halide Perovskite Solar Cells: A Review.

Science.gov (United States)

Sani, Faruk; Shafie, Suhaidi; Lim, Hong Ngee; Musa, Abubakar Ohinoyi

2018-06-14

Remarkable attention has been committed to the recently discovered cost effective and solution processable lead-free organic-inorganic halide perovskite solar cells. Recent studies have reported that, within five years, the reported efficiency has reached 9.0%, which makes them an extremely promising and fast developing candidate to compete with conventional lead-based perovskite solar cells. The major challenge associated with the conventional perovskite solar cells is the toxic nature of lead (Pb) used in the active layer of perovskite material. If lead continues to be used in fabricating solar cells, negative health impacts will result in the environment due to the toxicity of lead. Alternatively, lead free perovskite solar cells could give a safe way by substituting low-cost, abundant and non toxic material. This review focuses on formability of lead-free organic-inorganic halide perovskite, alternative metal cations candidates to replace lead (Pb), and possible substitutions of organic cations, as well as halide anions in the lead-free organic-inorganic halide perovskite architecture. Furthermore, the review gives highlights on the impact of organic cations, metal cations and inorganic anions on stability and the overall performance of lead free perovskite solar cells.

Metal induced gap states at alkali halide/metal interface

International Nuclear Information System (INIS)

Kiguchi, Manabu; Yoshikawa, Genki; Ikeda, Susumu; Saiki, Koichiro

2004-01-01

The electronic state of a KCl/Cu(0 0 1) interface was investigated using the Cl K-edge near-edge X-ray absorption fine structure (NEXAFS). A pre-peak observed on the bulk edge onset of thin KCl films has a similar feature to the peak at a LiCl/Cu(0 0 1) interface, which originates from the metal induced gap state (MIGS). The present result indicates that the MIGS is formed universally at alkali halide/metal interfaces. The decay length of MIGS to an insulator differs from each other, mainly due to the difference in the band gap energy of alkali halide

Examination of Organic Vapor Adsorption onto Alkali Metal and Halide Atomic Ions by using Ion Mobility Mass Spectrometry.

Science.gov (United States)

Maiβer, Anne; Hogan, Christopher J

2017-11-03

We utilize ion mobility mass spectrometry with an atmospheric pressure differential mobility analyzer coupled to a time-of-flight mass spectrometer (DMA-MS) to examine the formation of ion-vapor molecule complexes with seed ions of K + , Rb + , Cs + , Br - , and I - exposed to n-butanol and n-nonane vapor under subsaturated conditions. Ion-vapor molecule complex formation is indicated by a shift in the apparent mobility of each ion. Measurement results are compared to predicted mobility shifts based upon the Kelvin-Thomson equation, which is commonly used in predicting rates of ion-induced nucleation. We find that n-butanol at saturation ratios as low as 0.03 readily binds to all seed ions, leading to mobility shifts in excess of 35 %. Conversely, the binding of n-nonane is not detectable for any ion for saturation ratios in the 0-0.27 range. An inverse correlation between the ionic radius of the initial seed and the extent of n-butanol uptake is observed, such that at elevated n-butanol concentrations, the smallest ion (K + ) has the smallest apparent mobility and the largest (I - ) has the largest apparent mobility. Though the differences in behavior of the two vapor molecules types examined and the observed effect of ionic seed radius are not accounted for by the Kelvin-Thomson equation, its predictions are in good agreement with measured mobility shifts for Rb + , Cs + , and Br - in the presence of n-butanol (typically within 10 % of measurements). © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Metal halides vapor lasers with inner reactor and small active volume.

Science.gov (United States)

Shiyanov, D. V.; Sukhanov, V. B.; Evtushenko, G. S.

2018-04-01

Investigation of the energy characteristics of copper, manganese, lead halide vapor lasers with inner reactor and small active volume 90 cm3 was made. The optimal operating pulse repetition rates, temperatures, and buffer gas pressure for gas discharge tubes with internal and external electrodes are determined. Under identical pump conditions, such systems are not inferior in their characteristics to standard metal halide vapor lasers. It is shown that the use of a zeolite halogen generator provides lifetime laser operation.

Silver halide photographic material providing an image and an unsharp mask

International Nuclear Information System (INIS)

Broadhead, P.; Farnell, G.C.

1981-01-01

Desirable edge effects are produced by normal imagewise exposure and processing of a sensitive radiographic film comprising a transparent film support bearing a layer of a direct-positive silver halide emulsion and a layer of a negative silver halide emulsion and wherein the film comprises means to reduce crossover between the two emulsion layers, one of said emulsion layers being adapted to record a primary image and the other being adapted to record an unsharp mask image. (author)

Monocrystalline halide perovskite nanostructures for optoelectronic applications

NARCIS (Netherlands)

Khoram, P.

2018-01-01

Halide perovskites are a promising class of materials for incorporation in optoelectronics with higher efficiency and lower cost. The solution processability of these materials provides unique opportunities for simple nanostructure fabrication. In the first half of the thesis (chapter 2 and 3) we

Electrochemically reduced titanocene dichloride as a catalyst of reductive dehalogenation of organic halides

International Nuclear Information System (INIS)

Magdesieva, Tatiana V.; Graczyk, Magdalena; Vallat, Alain; Nikitin, Oleg M.; Demyanov, Petr I.; Butin, Kim P.; Vorotyntsev, Mikhail A.

2006-01-01

We have studied a reaction between the reduced form of titanocene dichloride (Cp 2 TiCl 2 ) and a group of organic halides: benzyl derivatives (4-X-C 6 H 4 CH 2 Cl, X = H, NO 2 , CH 3 ; 4-X-C 6 H 4 CH 2 Br, X = H, NO 2 , PhC(O); 4-X-C 6 H 4 CH 2 SCN, X = H, NO 2 ) as well as three aryl halides (4-NO 2 C 6 H 4 Hal, Hal = Cl, Br; 4-CH 3 O-C 6 H 4 Cl). It has been shown that the electrochemical reduction of Cp 2 TiCl 2 in the presence of these benzyl halides leads to a catalytic cycle resulting in the reductive dehalogenation of these organic substrates to yield mostly corresponding toluene derivatives as the main product. No dehalogenation has been observed for aryl derivatives. Based on electrochemical data and digital simulation, possible schemes of the catalytic process have been outlined. For non-substituted benzyl halides halogen atom abstraction is a key step. For the reaction of nitrobenzyl halides the complexation of Ti(III) species with the nitro group takes place, with the electron transfer from Ti(III) to this group (owing to its highest coefficient in LUMO of the nitro benzyl halide) followed by an intramolecular dissociative electron redistribution in the course of the heterolytic C-Hal bond cleavage. The results for reduced titanocene dichloride centers immobilized inside a polymer film showed that the catalytic reductive dehalogenation of the p-nitrobenzyl chloride does occur but with a low efficiency because of the partial deactivation of the film due to the blocking of the electron charge transport between the electrode and catalytic centers

Electrochemically reduced titanocene dichloride as a catalyst of reductive dehalogenation of organic halides

Energy Technology Data Exchange (ETDEWEB)

Magdesieva, Tatiana V. [Department Chemistry, M.V. Lomonosov Moscow State University, Moscow 119992 (Russian Federation)]. E-mail: tvm@org.chem.msu.ru; Graczyk, Magdalena [LSEO-UMR 5188 CNRS, Universite de Bourgogne, Dijon (France); Vallat, Alain [LSEO-UMR 5188 CNRS, Universite de Bourgogne, Dijon (France); Nikitin, Oleg M. [Department Chemistry, M.V. Lomonosov Moscow State University, Moscow 119992 (Russian Federation); Demyanov, Petr I. [Department Chemistry, M.V. Lomonosov Moscow State University, Moscow 119992 (Russian Federation); Butin, Kim P. [Department Chemistry, M.V. Lomonosov Moscow State University, Moscow 119992 (Russian Federation); Vorotyntsev, Mikhail A. [LSEO-UMR 5188 CNRS, Universite de Bourgogne, Dijon (France)]. E-mail: MV@u-bourgogne.fr

2006-11-12

We have studied a reaction between the reduced form of titanocene dichloride (Cp{sub 2}TiCl{sub 2}) and a group of organic halides: benzyl derivatives (4-X-C{sub 6}H{sub 4}CH{sub 2}Cl, X = H, NO{sub 2}, CH{sub 3}; 4-X-C{sub 6}H{sub 4}CH{sub 2}Br, X = H, NO{sub 2}, PhC(O); 4-X-C{sub 6}H{sub 4}CH{sub 2}SCN, X = H, NO{sub 2}) as well as three aryl halides (4-NO{sub 2}C{sub 6}H{sub 4}Hal, Hal = Cl, Br; 4-CH{sub 3}O-C{sub 6}H{sub 4}Cl). It has been shown that the electrochemical reduction of Cp{sub 2}TiCl{sub 2} in the presence of these benzyl halides leads to a catalytic cycle resulting in the reductive dehalogenation of these organic substrates to yield mostly corresponding toluene derivatives as the main product. No dehalogenation has been observed for aryl derivatives. Based on electrochemical data and digital simulation, possible schemes of the catalytic process have been outlined. For non-substituted benzyl halides halogen atom abstraction is a key step. For the reaction of nitrobenzyl halides the complexation of Ti(III) species with the nitro group takes place, with the electron transfer from Ti(III) to this group (owing to its highest coefficient in LUMO of the nitro benzyl halide) followed by an intramolecular dissociative electron redistribution in the course of the heterolytic C-Hal bond cleavage. The results for reduced titanocene dichloride centers immobilized inside a polymer film showed that the catalytic reductive dehalogenation of the p-nitrobenzyl chloride does occur but with a low efficiency because of the partial deactivation of the film due to the blocking of the electron charge transport between the electrode and catalytic centers.

Radiation damage in the alkali halide crystals

International Nuclear Information System (INIS)

Diller, K.M.

1975-10-01

A general review is given of the experimental data on radiation damage in the alkali halide crystals. A report is presented of an experimental investigation of irradiation produced interstitial dislocation loops in NaCl. These loops are found to exhibit the usual growth and coarsening behaviour during thermal annealing which operates by a glide and self-climb mechanism. It is shown that the recombination of defects in these crystals is a two stage process, and that the loss of interstitials stabilized at the loops is caused by extrinsic vacancies. The theoretical techniques used in simulating point defects in ionic crystals are described. Shell model potentials are derived for all the alkali halide crystals by fitting to bulk crystal data. The fitting is supplemented by calculations of the repulsive second neighbour interactions using methods based on the simple electron gas model. The properties of intrinsic and substitutional impurity defects are calculated. The HADES computer program is used in all the defect calculations. Finally the report returns to the problems of irradiation produced interstitial defects. The properties of H centres are discussed; their structure, formation energies, trapping at impurities and dimerization. The structure, formation energies and mobility of the intermediate and final molecular defects are then discussed. The thermodynamics of interstitial loop formation is considered for all the alklai halide crystals. The nucleation of interstitial loops in NaCl and NaBr is discussed, and the recombination of interstitial and vacancy defects. The models are found to account for all the main features of the experimental data. (author)

A deep cavitand with a fluorescent wall functions as an ion sensor.

Science.gov (United States)

Berryman, Orion B; Sather, Aaron C; Rebek, Julius

2011-10-07

The synthesis and characterization of a deep cavitand bearing a fluorescent benzoquinoxaline wall is reported. Noncovalent host-guest recognition events are exploited to sense small charged molecules including acetylcholine. The cavitand also exhibits an anion dependent change in fluorescence that is used to differentiate halide ions in solution. © 2011 American Chemical Society

Thallous and cesium halide materials for use in cryogenic applications

International Nuclear Information System (INIS)

Lawless, W.N.

1983-01-01

Certain thallous and cesium halides, either used alone or in combination with other ceramic materials, are provided in cryogenic applications such as heat exchange material for the regenerator section of a closed-cycle cryogenic refrigeration section, as stabilizing coatings for superconducting wires, and as dielectric insulating materials. The thallous and cesium halides possess unusually large specific heats at low temperatures, have large thermal conductivities, are nonmagnetic, and are nonconductors of electricity. They can be formed into a variety of shapes such as spheres, bars, rods, or the like and can be coated or extruded onto substrates or wires. (author)

Development and melt growth of novel scintillating halide crystals

Science.gov (United States)

Yoshikawa, Akira; Yokota, Yuui; Shoji, Yasuhiro; Kral, Robert; Kamada, Kei; Kurosawa, Shunsuke; Ohashi, Yuji; Arakawa, Mototaka; Chani, Valery I.; Kochurikhin, Vladimir V.; Yamaji, Akihiro; Andrey, Medvedev; Nikl, Martin

2017-12-01

Melt growth of scintillating halide crystals is reviewed. The vertical Bridgman growth technique is still considered as very popular method that enables production of relatively large and commercially attractive crystals. On the other hand, the micro-pulling-down method is preferable when fabrication of small samples, sufficient for preliminary characterization of their optical and/or scintillation performance, is required. Moreover, bulk crystal growth is also available using the micro-pulling-down furnace. The examples of growths of various halide crystals by industrially friendly melt growth techniques including Czochralski and edge-defined film-fed growth methods are also discussed. Finally, traveling molten zone growth that in some degree corresponds to horizontal zone melting is briefly overviewed.

Alkali Halide Microstructured Optical Fiber for X-Ray Detection

Science.gov (United States)

DeHaven, S. L.; Wincheski, R. A.; Albin, S.

2014-01-01

Microstructured optical fibers containing alkali halide scintillation materials of CsI(Na), CsI(Tl), and NaI(Tl) are presented. The scintillation materials are grown inside the microstructured fibers using a modified Bridgman-Stockbarger technique. The x-ray photon counts of these fibers, with and without an aluminum film coating are compared to the output of a collimated CdTe solid state detector over an energy range from 10 to 40 keV. The photon count results show significant variations in the fiber output based on the materials. The alkali halide fiber output can exceed that of the CdTe detector, dependent upon photon counter efficiency and fiber configuration. The results and associated materials difference are discussed.

Formation of structured nanophases in halide crystals

Czech Academy of Sciences Publication Activity Database

Kulveit, Jan; Demo, Pavel; Polák, Karel; Sveshnikov, Alexey; Kožíšek, Zdeněk

2013-01-01

Roč. 5, č. 6 (2013), s. 561-564 ISSN 2164-6627 R&D Projects: GA ČR GAP108/12/0891 Institutional support: RVO:68378271 Keywords : halide crystals * nucleation Subject RIV: BM - Solid Matter Physics ; Magnetism http://www.aspbs.com/asem.html#v5n6

Determination of the structural phase and octahedral rotation angle in halide perovskites

Science.gov (United States)

dos Reis, Roberto; Yang, Hao; Ophus, Colin; Ercius, Peter; Bizarri, Gregory; Perrodin, Didier; Shalapska, Tetiana; Bourret, Edith; Ciston, Jim; Dahmen, Ulrich

2018-02-01

A key to the unique combination of electronic and optical properties in halide perovskite materials lies in their rich structural complexity. However, their radiation sensitive nature limits nanoscale structural characterization requiring dose efficient microscopic techniques in order to determine their structures precisely. In this work, we determine the space-group and directly image the Br halide sites of CsPbBr3, a promising material for optoelectronic applications. Based on the symmetry of high-order Laue zone reflections of convergent-beam electron diffraction, we identify the tetragonal (I4/mcm) structural phase of CsPbBr3 at cryogenic temperature. Electron ptychography provides a highly sensitive phase contrast measurement of the halide positions under low electron-dose conditions, enabling imaging of the elongated Br sites originating from the out-of-phase octahedral rotation viewed along the [001] direction of I4/mcm persisting at room temperature. The measurement of these features and comparison with simulations yield an octahedral rotation angle of 6.5°(±1.5°). The approach demonstrated here opens up opportunities for understanding the atomic scale structural phenomena applying advanced characterization tools on a wide range of radiation sensitive halide-based all-inorganic and hybrid organic-inorganic perovskites.

NMRON on a mixed halide antiferromagnet, (54Mn)Mn(Cl0.6Br0.4)2.4H2O

International Nuclear Information System (INIS)

Chaplin, D.H.; Harker, S.J.; Hutchison, W.D.; Bowden, G.J.

2000-01-01

Full text: Recently we reported on the significant gains that can be made in Low Temperature Nuclear Orientation (LTNO) of the magnetically dominant species in an antiferromagnetic single crystal by heterogeneous mixing of the halide ligands. This new approach relies on enhanced nuclear spin lattice relaxation (NSLR) at the magnetic ion, in this case Mn, through broadbanded electronic magnons, in the cooled, single crystal host. Whereas the isomorphous terminal compounds ( 54 Mn)MnCI 2 .4H 2 O and ( 54 Mn)MnBr 2 .4H 2 O, have yielded zero field directional anisotropies of only 5% and 14%, respectively, from the daughter gamma from the long-lived parent 54 Mn, the mixed halides have yielded up to 40% zero field gamma anisotropy at the same base temperature of about 7-8 millikelvin. This improved zero field LTNO provides sufficient sensitivity to enable meaningful NMRON studies of the details of the hyperfine parameters at the Mn site in these mixed halide systems. In this paper we provide the NMRON results for single crystal ( 54 Mn)Mn(CI 0.6 Br 0.4 ) 2 .4H 2 O and compare them with the two terminal compounds which possess surprisingly different NMR responses due to different ratios of magnetic exchange to magnetic anisotropy fields. It is shown that whereas the static magnetic hyperfine field at the Mn nucleus is largely unchanged, and the spin flop field nicely interpolates when compared with the terminal compounds, there are significant differences in the pseudoquadrupolar splittings and sub-resonance linewidths

The effects of monovalent and divalent cations on the stability of silver nanoparticles formed from direct reduction of silver ions by Suwannee River humic acid/natural organic matter

Energy Technology Data Exchange (ETDEWEB)

Akaighe, Nelson [Chemistry Department, Florida Institute of Technology, 150 West University Boulevard, Melbourne, FL 32901 (United States); Depner, Sean W.; Banerjee, Sarbajit [Department of Chemistry, 410 Natural Sciences Complex, University at Buffalo, The State University of New York, Buffalo, NY 14260-3000 (United States); Sharma, Virender K. [Chemistry Department, Florida Institute of Technology, 150 West University Boulevard, Melbourne, FL 32901 (United States); Sohn, Mary, E-mail: msohn@fit.edu [Chemistry Department, Florida Institute of Technology, 150 West University Boulevard, Melbourne, FL 32901 (United States)

2012-12-15

The formation and characterization of AgNPs (silver nanoparticles) formed from the reduction of Ag{sup +} by SRNOM (Suwannee River natural organic matter) is reported. The images of SRNOM-formed AgNPs and the selected area electron diffraction (SAED) were captured by high resolution transmission electron microscopy (HRTEM). The colloidal and chemical stability of SRNOM- and SRHA (Suwannee River humic acid)-formed AgNPs in different ionic strength solutions of NaCl, KCl, CaCl{sub 2} and MgCl{sub 2} was investigated in an effort to evaluate the key fate and transport processes of these nanoparticles in natural aqueous environments. The aggregation state, stability and sedimentation rate of the AgNPs were monitored by Dynamic Light Scattering (DLS), zeta potential, and UV-vis measurements. The results indicate that both types of AgNPs are very unstable in high ionic strength solutions. Interestingly, the nanoparticles appeared more unstable in divalent cation solutions than in monovalent cation solutions at similar concentrations. Furthermore, the presence of SRNOM and SRHA contributed to the nanoparticle instability at high ionic strength in divalent metallic cation solutions, most likely due to intermolecular bridging with the organic matter. The results clearly suggest that changes in solution chemistry greatly affect nanoparticle long term stability and transport in natural aqueous environments. Highlights: Black-Right-Pointing-Pointer Formation of SRNOM-AgNPs under environmentally relevant conditions Black-Right-Pointing-Pointer Influence of monovalent versus divalent cations on SRHA- and SRNOM-AgNP stability Black-Right-Pointing-Pointer Effect of AgNPs on organic matter removal from water columns.

Europium ion as a probe for binding sites to carrageenans

International Nuclear Information System (INIS)

Ramos, Ana P.; Goncalves, Rogeria R.; Serra, Osvaldo A.; Zaniquelli, Maria Elisabete D.; Wong, Kenneth

2007-01-01

Carrageenans, sulfated polysaccharides extracted from red algae, present a coil-helix transition and helix aggregation dependence on the type and concentration of counterions. In this study, we focus attention on a mixed valence counterion system: Eu 3+ /Na + or K + with different gel-forming carrageenans: kappa, iota, and kappa-2. Results of stationary and time-dependent luminescence showed to be a suitable tool to probe ion binding to both the negatively charged sulfate group and the hydroxyl groups present in the biopolymer. For lower europium ion concentrations, a single longer decay emission lifetime was detected, which was attributed to the binding of europium ion to the carrageenan sulfate groups. An additional decay ascribed to europium binding to hydroxyl groups was observed above a threshold concentration, and this decay was dependent on the carrageenan charge density. Symmetry of the europium ion microenvironment was estimated by the ratio between the intensities of its emission bands, which has been shown to depend on the concentration of europium ions and on the specificity of the monovalent counterion bound to the carrageenan

Europium ion as a probe for binding sites to carrageenans

Energy Technology Data Exchange (ETDEWEB)

Ramos, Ana P.; Goncalves, Rogeria R.; Serra, Osvaldo A. [Departamento de Quimica, Faculdade de Filosofia, Ciencias e Letras de Ribeirao Preto, Universidade de Sao Paulo, Ribeirao Preto, Sao Paulo 14040-901 (Brazil); Zaniquelli, Maria Elisabete D. [Departamento de Quimica, Faculdade de Filosofia, Ciencias e Letras de Ribeirao Preto, Universidade de Sao Paulo, Ribeirao Preto, Sao Paulo 14040-901 (Brazil)], E-mail: medzaniquelli@ffclrp.usp.br; Wong, Kenneth [Laboratorio de Fisico-Quimica, Centro de Pesquisas de Paulinia, Rhodia Brasil, Paulinia, Sao Paulo (Brazil)

2007-12-15

Carrageenans, sulfated polysaccharides extracted from red algae, present a coil-helix transition and helix aggregation dependence on the type and concentration of counterions. In this study, we focus attention on a mixed valence counterion system: Eu{sup 3+}/Na{sup +} or K{sup +} with different gel-forming carrageenans: kappa, iota, and kappa-2. Results of stationary and time-dependent luminescence showed to be a suitable tool to probe ion binding to both the negatively charged sulfate group and the hydroxyl groups present in the biopolymer. For lower europium ion concentrations, a single longer decay emission lifetime was detected, which was attributed to the binding of europium ion to the carrageenan sulfate groups. An additional decay ascribed to europium binding to hydroxyl groups was observed above a threshold concentration, and this decay was dependent on the carrageenan charge density. Symmetry of the europium ion microenvironment was estimated by the ratio between the intensities of its emission bands, which has been shown to depend on the concentration of europium ions and on the specificity of the monovalent counterion bound to the carrageenan.

Electron detachment energies in high-symmetry alkali halide solvated-electron anions

Science.gov (United States)

Anusiewicz, Iwona; Berdys, Joanna; Simons, Jack; Skurski, Piotr

2003-07-01

We decompose the vertical electron detachment energies (VDEs) in solvated-electron clusters of alkali halides in terms of (i) an electrostatic contribution that correlates with the dipole moment (μ) of the individual alkali halide molecule and (ii) a relaxation component that is related to the polarizability (α) of the alkali halide molecule. Detailed numerical ab initio results for twelve species (MX)n- (M=Li,Na; X=F,Cl,Br; n=2,3) are used to construct an interpolation model that relates the clusters' VDEs to their μ and α values as well as a cluster size parameter r that we show is closely related to the alkali cation's ionic radius. The interpolation formula is then tested by applying it to predict the VDEs of four systems [i.e., (KF)2-, (KF)3-, (KCl)2-, and (KCl)3-] that were not used in determining the parameters of the model. The average difference between the model's predicted VDEs and the ab initio calculated electron binding energies is less than 4% (for the twelve species studied). It is concluded that one can easily estimate the VDE of a given high-symmetry solvated electron system by employing the model put forth here if the α, μ and cation ionic radii are known. Alternatively, if VDEs are measured for an alkali halide cluster and the α and μ values are known, one can estimate the r parameter, which, in turn, determines the "size" of the cluster anion.

Local Polar Fluctuations in Lead Halide Perovskite Crystals

Energy Technology Data Exchange (ETDEWEB)

Yaffe, Omer; Guo, Yinsheng; Tan, Liang Z.; Egger, David A.; Hull, Trevor; Stoumpos, Constantinos C.; Zheng, Fan; Heinz, Tony F.; Kronik, Leeor; Kanatzidis, Mercouri G.; Owen, Jonathan S.; Rappe, Andrew M.; Pimenta, Marcos A.; Brus, Louis E.

2017-03-01

Hybrid lead-halide perovskites have emerged as an excellent class of photovoltaic materials. Recent reports suggest that the organic molecular cation is responsible for local polar fluctuations that inhibit carrier recombination. We combine low-frequency Raman scattering with first-principles molecular dynamics (MD) to study the fundamental nature of these local polar fluctuations. Our observations of a strong central peak in the cubic phase of both hybrid (CH3NH3PbBr3) and all-inorganic (CsPbBr3) leadhalide perovskites show that anharmonic, local polar fluctuations are intrinsic to the general lead-halide perovskite structure, and not unique to the dipolar organic cation. MD simulations indicate that head-tohead Cs motion coupled to Br face expansion, occurring on a few hundred femtosecond time scale, drives the local polar fluctuations in CsPbBr3.

Methyl halide fluxes from tropical plants under controlled radiation and temperature regimes

Science.gov (United States)

Blei, Emanuel; Yokouchi, Yoko; Saito, Takuya; Nozoe, Susumu

2015-04-01

Methyl halides (CH3Cl, CH3Br, CH3I) contribute significantly to the halogen burden of the atmosphere and have the potential to influence the stratospheric ozone layer through their catalytic effect in the Chapman cycle. As such they have been studied over the years, and many plants and biota have been examined for their potential to act as a source of these gases. One of the potentially largest terrestrial sources identified was tropical vegetation such as tropical ferns and Dipterocarp trees. Most of these studies concentrated on the identification and quantification of such fluxes rather than their characteristics and often the chambers used in these studies were either opaque or only partially transparent to the full solar spectrum. Therefore it is not certain to which degree emissions of methyl halides are innate to the plants and how much they might vary due to radiation or temperature conditions inside the enclosures. In a separate development it had been proposed that UV-radiation could cause live plant materials to be become emitters of methane even under non-anoxic conditions. As methane is chemically very similar to methyl halides and had been proposed to be produced from methyl-groups ubiquitously found in plant cell material there is a relatively good chance that such a production mechanism would also apply to methyl halides. To test whether radiation can affect elevated emissions of methyl halides from plant materials and to distinguish this from temperature effects caused by heat build-up in chambers a set of controlled laboratory chamber enclosures under various radiation and temperature regimes was conducted on four different tropical plant species (Magnolia grandiflora, Cinnamonum camphora, Cyathea lepifera, Angiopteris lygodiifolia), the latter two of which had previously been identified as strong methyl halide emitters. Abscised leaf samples of these species were subjected to radiation treatments such UV-B, UV-A and broad spectrum radiation

Study of the pitting and repassiv,tion corrosion potential of zicaloy-4 halides solutions at 250C and several pH

International Nuclear Information System (INIS)

Gardiazabal, J.I.; Cordova, R.; Gomez, H.; Layana, G.; Schrebler, R.

1987-01-01

The electrochemical behaviour of Zircaloy-4 electrode in chloride, bromide and iodide acid solution was investigated at 25 0 C employing stationary, quasi-stationary and potentiodynamic techniques. The results show that the pitting and repassivation potentials are independent on pH but both are dependent on halice concentration, following linear relation ships in these cases. It is also possible to correlate the pitting potential with the ionic radius of the anions, allowing thus to establish an order in their agressive properties. This order was extrapolated for fluoride ion and further experimental measurements show that the corrosion potential of Zircaloy-4 in acid or neutra solution of this ion (which undergoes active dissolution) is coincident with that predicted from the Ep v/s ionic radius determined for the other halides. (Author) [pt

Thermal battery. [solid metal halide electrolytes with enhanced electrical conductance after a phase transition

Science.gov (United States)

Carlsten, R.W.; Nissen, D.A.

1973-03-06

The patent describes an improved thermal battery whose novel design eliminates various disadvantages of previous such devices. Its major features include a halide cathode, a solid metal halide electrolyte which has a substantially greater electrical conductance after a phase transition at some temperature, and a means for heating its electrochemical cells to activation temperature.

Analysis and modeling of alkali halide aqueous solutions

DEFF Research Database (Denmark)

Kim, Sun Hyung; Anantpinijwatna, Amata; Kang, Jeong Won

2016-01-01

on calculations for various electrolyte properties of alkali halide aqueous solutions such as mean ionic activity coefficients, osmotic coefficients, and salt solubilities. The model covers highly nonideal electrolyte systems such as lithium chloride, lithium bromide and lithium iodide, that is, systems...

Adsorption of molecular additive onto lead halide perovskite surfaces: A computational study on Lewis base thiophene additive passivation

Science.gov (United States)

Zhang, Lei; Yu, Fengxi; Chen, Lihong; Li, Jingfa

2018-06-01

Organic additives, such as the Lewis base thiophene, have been successfully applied to passivate halide perovskite surfaces, improving the stability and properties of perovskite devices based on CH3NH3PbI3. Yet, the detailed nanostructure of the perovskite surface passivated by additives and the mechanisms of such passivation are not well understood. This study presents a nanoscopic view on the interfacial structure of an additive/perovskite interface, consisting of a Lewis base thiophene molecular additive and a lead halide perovskite surface substrate, providing insights on the mechanisms that molecular additives can passivate the halide perovskite surfaces and enhance the perovskite-based device performance. Molecular dynamics study on the interactions between water molecules and the perovskite surfaces passivated by the investigated additive reveal the effectiveness of employing the molecular additives to improve the stability of the halide perovskite materials. The additive/perovskite surface system is further probed via molecular engineering the perovskite surfaces. This study reveals the nanoscopic structure-property relationships of the halide perovskite surface passivated by molecular additives, which helps the fundamental understanding of the surface/interface engineering strategies for the development of halide perovskite based devices.

2D halide perovskite-based van der Waals heterostructures: contact evaluation and performance modulation

Science.gov (United States)

Guo, Yaguang; Saidi, Wissam A.; Wang, Qian

2017-09-01

Halide perovskites and van der Waals (vdW) heterostructures are both of current interest owing to their novel properties and potential applications in nano-devices. Here, we show the great potential of 2D halide perovskite sheets (C4H9NH3)2PbX4 (X  =  Cl, Br and I) that were synthesized recently (Dou et al 2015 Science 349 1518-21) as the channel materials contacting with graphene and other 2D metallic sheets to form van der Waals heterostructures for field effect transistor (FET). Based on state-of-the-art theoretical simulations, we show that the intrinsic properties of the 2D halide perovskites are preserved in the heterojunction, which is different from the conventional contact with metal surfaces. The 2D halide perovskites form a p-type Schottky barrier (Φh) contact with graphene, where tunneling barrier exists, and a negative band bending occurs at the lateral interface. We demonstrate that the Schottky barrier can be turned from p-type to n-type by doping graphene with nitrogen atoms, and a low-Φh or an Ohmic contact can be realized by doping graphene with boron atoms or replacing graphene with other high-work-function 2D metallic sheets such as ZT-MoS2, ZT-MoSe2 and H-NbS2. This study not only predicts a 2D halide perovskite-based FETs, but also enhances the understanding of tuning Schottky barrier height in device applications.

Atomistic Modeling of Ion Conduction through the Voltage-Sensing Domain of the Shaker K+ Ion Channel.

Science.gov (United States)

Wood, Mona L; Freites, J Alfredo; Tombola, Francesco; Tobias, Douglas J

2017-04-20

Voltage-sensing domains (VSDs) sense changes in the membrane electrostatic potential and, through conformational changes, regulate a specific function. The VSDs of wild-type voltage-dependent K + , Na + , and Ca 2+ channels do not conduct ions, but they can become ion-permeable through pathological mutations in the VSD. Relatively little is known about the underlying mechanisms of conduction through VSDs. The most detailed studies have been performed on Shaker K + channel variants in which ion conduction through the VSD is manifested in electrophysiology experiments as a voltage-dependent inward current, the so-called omega current, which appears when the VSDs are in their resting state conformation. Only monovalent cations appear to permeate the Shaker VSD via a pathway that is believed to be, at least in part, the same as that followed by the S4 basic side chains during voltage-dependent activation. We performed μs-time scale atomistic molecular dynamics simulations of a cation-conducting variant of the Shaker VSD under applied electric fields in an experimentally validated resting-state conformation, embedded in a lipid bilayer surrounded by solutions containing guanidinium chloride or potassium chloride. Our simulations provide insights into the Shaker VSD permeation pathway, the protein-ion interactions that control permeation kinetics, and the mechanism of voltage-dependent activation of voltage-gated ion channels.

Dipole-dipole van der Waals interaction in alkali halides

International Nuclear Information System (INIS)

Thakur, B.N.; Thakur, K.P.

1978-01-01

Values of van der Waals dipole-dipole constants and interaction energetics of alkali halides are reported using the recent data. The values obtained are somewhat larger than those of earlier workers. (orig.) [de

Lead Halide Perovskite Nanocrystals in the Research Spotlight: Stability and Defect Tolerance

Science.gov (United States)

2017-01-01

This Perspective outlines basic structural and optical properties of lead halide perovskite colloidal nanocrystals, highlighting differences and similarities between them and conventional II–VI and III–V semiconductor quantum dots. A detailed insight into two important issues inherent to lead halide perovskite nanocrystals then follows, namely, the advantages of defect tolerance and the necessity to improve their stability in environmental conditions. The defect tolerance of lead halide perovskites offers an impetus to search for similar attributes in other related heavy metal-free compounds. We discuss the origins of the significantly blue-shifted emission from CsPbBr3 nanocrystals and the synthetic strategies toward fabrication of stable perovskite nanocrystal materials with emission in the red and infrared parts of the optical spectrum, which are related to fabrication of mixed cation compounds guided by Goldschmidt tolerance factor considerations. We conclude with the view on perspectives of use of the colloidal perovskite nanocrystals for applications in backlighting of liquid-crystal TV displays. PMID:28920080

Calcium phosphate cements with strontium halides as radiopacifiers.

Science.gov (United States)

López, Alejandro; Montazerolghaem, Maryam; Engqvist, Håkan; Ott, Marjam Karlsson; Persson, Cecilia

2014-02-01

High radiopacity is required to monitor the delivery and positioning of injectable implants. Inorganic nonsoluble radiopacifiers are typically used in nondegradable bone cements; however, their usefulness in resorbable cements is limited due to their low solubility. Strontium halides, except strontium fluoride, are ionic water-soluble compounds that possess potential as radiopacifiers. In this study, we compare the radiopacity, mechanical properties, composition, and cytotoxicity of radiopaque brushite cements prepared with strontium fluoride (SrF2 ), strontium chloride (SrCl2 ·6H2 O), strontium bromide (SrBr2 ), or strontium iodide (SrI2 ). Brushite cements containing 10 wt % SrCl2 ·6H2 O, SrBr2 , or SrI2 exhibited equal to or higher radiopacity than commercial radiopaque cements. Furthermore, the brushite crystal lattice in cements that contained the ionic radiopacifiers was larger than in unmodified cements and in cements that contained SrF2 , indicating strontium substitution. Despite the fact that the strontium halides increased the solubility of the cements and affected their mechanical properties, calcium phosphate cements containing SrCl2 ·6H2 O, SrBr2 , and SrI2 showed no significant differences in Saos-2 cell viability and proliferation with respect to the control. Strontium halides: SrCl2 ·6H2 O, SrBr2 , and SrI2 may be potential candidates as radiopacifiers in resorbable biomaterials although their in vivo biocompatibility, when incorporated into injectable implants, is yet to be assessed. Copyright © 2013 Wiley Periodicals, Inc.

Local polar fluctuations in lead halide perovskites

Science.gov (United States)

Tan, Liang; Yaffe, Omer; Guo, Yinsheng; Brus, Louis; Rappe, Andrew; Egger, David; Kronik, Leeor

The lead halide perovskites have recently attracted much attention because of their large and growing photovoltaic power conversion efficiencies. However, questions remain regarding the temporal and spatial correlations of the structural fluctuations, their atomistic nature, and how they affect electronic and photovoltaic properties. To address these questions, we have performed a combined ab initio molecular dynamics (MD) and density functional theory (DFT) study on CsPbBr3. We have observed prevalent anharmonic motion in our MD trajectories, with local polar fluctuations involving head-to-head motion of A-site Cs cations coupled with Br window opening. We calculate Raman spectra from the polarizability auto-correlation functions obtained from these trajectories and show that anharmonic A-site cation motion manifests as a broad central peak in the Raman spectrum, which increases in intensity with temperature. A comparison of the experimental Raman spectrum of hybrid organometallic MAPbBr3 and fully inorganic CsPbBr3 suggests that structural fluctuations in lead-halide perovskites is more general than rotation of polar organic cations and is intimately coupled to the inorganic framework.

Atmospheric pressure ionization of chlorinated ethanes in ion mobility spectrometry and mass spectrometry

Energy Technology Data Exchange (ETDEWEB)

Ewing, Robert G.; Atkinson, David A.; Benson, Michael T.

2015-05-16

This study investigates the APCI mechanisms associated with chlorinated ethanes in an attempt to define conditions under which unique pseudo-molecular adducts, in addition to chloride ion, can be produced for analytical measurements using IMS and MS. The ionization chemistry of chlorinated compounds typically leads to the detection of only the halide ions. Using molecular modeling, which provides insights into the ion formation and relative binding energies, predictions for the formation of pseudo-molecular adducts are postulated. Predicted structures of the chloride ion with multiple hydrogens on the ethane backbone was supported by the observation of specific pseudo-molecular adducts in IMS and MS spectra. With the proper instrumental conditions, such as short reaction times and low temp.

Solution-Phase Synthesis of Cesium Lead Halide Perovskite Nanowires.

Science.gov (United States)

Zhang, Dandan; Eaton, Samuel W; Yu, Yi; Dou, Letian; Yang, Peidong

2015-07-29

Halide perovskites have attracted much attention over the past 5 years as a promising class of materials for optoelectronic applications. However, compared to hybrid organic-inorganic perovskites, the study of their pure inorganic counterparts, like cesium lead halides (CsPbX3), lags far behind. Here, a catalyst-free, solution-phase synthesis of CsPbX3 nanowires (NWs) is reported. These NWs are single-crystalline, with uniform growth direction, and crystallize in the orthorhombic phase. Both CsPbBr3 and CsPbI3 are photoluminescence active, with composition-dependent temperature and self-trapping behavior. These NWs with a well-defined morphology could serve as an ideal platform for the investigation of fundamental properties and the development of future applications in nanoscale optoelectronic devices based on all-inorganic perovskites.

Development of alkali halide-optics for high power-IR laser

International Nuclear Information System (INIS)

Pohl, L.

1989-01-01

In this work 'Development of Alkali Halide-Optics for High Power-IR Laser' we investigated the purification of sodiumchloride-, potassiumchloride- and potassiumbromide-raw materials. We succeeded to reduce the content of impurities like Cu, Pb, V, Cr, Mn, Fe, Co and Ni in these raw materials to the lower of ppb's by a Complex-Adsorption-Method (CAM). Crystals were grown from purified substances by 'Kyropoulos' method'. Windows were cur thereof, polished and measured by FTIR-spectroscopy. Analytical data showed, that the resulting crystals were of lower quality than the raw materials. Because of this fact crystal-growing-conditions have to undergo a special improvement. Alkali halide windows from other sources on the market had been tested. (orig.) [de

Spectroscopic investigation of indium halides as substitudes of mercury in low pressure discharges for lighting applications

Energy Technology Data Exchange (ETDEWEB)

Briefi, Stefan

2012-05-22

Low pressure discharges with indium halides as radiator are discussed as substitutes for hazardous mercury in conventional fluorescent lamps. In this work, the applicability of InBr and InCl in a low pressure discharge light source is investigated. The aim is to identify and understand the physical processes which determine the discharge characteristics and the efficiency of the generated near-UV emission of the indium halide molecule and of the indium atom which is created due to dissociation processes in the plasma. As discharge vessels sealed cylindrical quartz glass tubes which contain a defined amount of indium halide and a rare gas are used. Preliminary investigations showed that for a controlled variation of the indium halide density a well-defined cold spot setup is mandatory. This was realized in the utilized experimental setup. The use of metal halides raises the issue, that power coupling by internal electrodes is not possible as the electrodes would quickly be eroded by the halides. The comparison of inductive and capacitive RF-coupling with external electrodes revealed that inductively coupled discharges provide higher light output and much better long term stability. Therefore, all investigations are carried out using inductive RF-coupling. The diagnostic methods optical emission and white light absorption spectroscopy are applied. As the effects of absorption-signal saturation and reabsorption of emitted radiation within the plasma volume could lead to an underestimation of the determined population densities by orders of magnitude, these effects are considered in the data evaluation. In order to determine the electron temperature and the electron density from spectroscopic measurements, an extended corona model as population model of the indium atom has been set up. A simulation of the molecular emission spectra has been implemented to investigate the rovibrational population processes of the indium halide molecules. The impact of the cold spot

Thermomechanical measurements of lead halide single crystals

Czech Academy of Sciences Publication Activity Database

Nitsch, Karel; Rodová, Miroslava

2002-01-01

Roč. 234, č. 2 (2002), s. 701-709 ISSN 0370-1972 R&D Projects: GA AV ČR IAA2010926 Institutional research plan: CEZ:AV0Z1010914 Keywords : PbX 2 (X=Cl, Br, I) * coefficients of linear thermal expansion * polymorphism in lead halides Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 0.930, year: 2002

Dislocation unpinning model of acoustic emission from alkali halide ...

Indian Academy of Sciences (India)

The present paper reports the dislocation unpinning model of acoustic emis- sion (AE) from ... Acoustic emission; dislocation; alkali halide crystals; plastic deformation. ..... [5] T Nishimura, A Tahara and T Kolama, Jpn. Metal Inst. 64, 339 (2000).

Competitive separation of di- vs. mono-valent cations in electrodialysis: effects of the boundary layer properties.

Science.gov (United States)

Kim, Younggy; Walker, W Shane; Lawler, Desmond F

2012-05-01

In electrodialysis desalination, the boundary layer near ion-exchange membranes is the limiting region for the overall rate of ionic separation due to concentration polarization over tens of micrometers in that layer. Under high current conditions, this sharp concentration gradient, creating substantial ionic diffusion, can drive a preferential separation for certain ions depending on their concentration and diffusivity in the solution. Thus, this study tested a hypothesis that the boundary layer affects the competitive transport between di- and mono-valent cations, which is known to be governed primarily by the partitioning with cation-exchange membranes. A laboratory-scale electrodialyzer was operated at steady state with a mixture of 10mM KCl and 10mM CaCl(2) at various flow rates. Increased flows increased the relative calcium transport. A two-dimensional model was built with analytical solutions of the Nernst-Planck equation. In the model, the boundary layer thickness was considered as a random variable defined with three statistical parameters: mean, standard deviation, and correlation coefficient between the thicknesses of the two boundary layers facing across a spacer. Model simulations with the Monte Carlo method found that a greater calcium separation was achieved with a smaller mean, greater standard deviation, or more negative correlation coefficient. The model and experimental results were compared for the cationic transport number as well as the current and potential relationship. The mean boundary layer thickness was found to decrease from 40 to less than 10 μm as the superficial water velocity increased from 1.06 to 4.24 cm/s. The standard deviation was greater than the mean thickness at slower water velocities and smaller at faster water velocities. Copyright © 2012 Elsevier Ltd. All rights reserved.

Alternative route to metal halide free ionic liquids

International Nuclear Information System (INIS)

Takao, Koichiro; Ikeda, Yasuhisa

2008-01-01

An alternative synthetic route to metal halide free ionic liquids using trialkyloxonium salt is proposed. Utility of this synthetic route has been demonstrated by preparing 1-ethyl-3-methylimidazolium tetrafluoroborate ionic liquid through the reaction between 1-methylimidazole and triethyloxonium tetra-fluoroborate in anhydrous ether. (author)

The thermo-elastic instability model of melting of alkali halides in the Debye approximation

Science.gov (United States)

Owens, Frank J.

2018-05-01

The Debye model of lattice vibrations of alkali halides is used to show that there is a temperature below the melting temperature where the vibrational pressure exceeds the electrostatic pressure. The onset temperature of this thermo-elastic instability scales as the melting temperature of NaCl, KCl, and KBr, suggesting its role in the melting of the alkali halides in agreement with a previous more rigorous model.

Large polarons in lead halide perovskites

Science.gov (United States)

Miyata, Kiyoshi; Meggiolaro, Daniele; Trinh, M. Tuan; Joshi, Prakriti P.; Mosconi, Edoardo; Jones, Skyler C.; De Angelis, Filippo; Zhu, X.-Y.

2017-01-01

Lead halide perovskites show marked defect tolerance responsible for their excellent optoelectronic properties. These properties might be explained by the formation of large polarons, but how they are formed and whether organic cations are essential remain open questions. We provide a direct time domain view of large polaron formation in single-crystal lead bromide perovskites CH3NH3PbBr3 and CsPbBr3. We found that large polaron forms predominantly from the deformation of the PbBr3− frameworks, irrespective of the cation type. The difference lies in the polaron formation time, which, in CH3NH3PbBr3 (0.3 ps), is less than half of that in CsPbBr3 (0.7 ps). First-principles calculations confirm large polaron formation, identify the Pb-Br-Pb deformation modes as responsible, and explain quantitatively the rate difference between CH3NH3PbBr3 and CsPbBr3. The findings reveal the general advantage of the soft [PbX3]− sublattice in charge carrier protection and suggest that there is likely no mechanistic limitations in using all-inorganic or mixed-cation lead halide perovskites to overcome instability problems and to tune the balance between charge carrier protection and mobility. PMID:28819647

Nanostructure of propylammonium nitrate in the presence of poly(ethylene oxide) and halide salts

Science.gov (United States)

Stefanovic, Ryan; Webber, Grant B.; Page, Alister J.

2018-05-01

Nanoscale structure of protic ionic liquids is critical to their utility as molecular electrochemical solvents since it determines the capacity to dissolve salts and polymers such as poly(ethylene oxide) (PEO). Here we use quantum chemical molecular dynamics simulations to investigate the impact of dissolved halide anions on the nanostructure of an archetypal nanostructured protic ionic liquid, propylammonium nitrate (PAN), and how this impacts the solvation of a model PEO polymer. At the molecular level, PAN is nanostructured, consisting of charged/polar and uncharged/nonpolar domains. The charged domain consists of the cation/anion charge groups, and is formed by their electrostatic interaction. This domain solvophobically excludes the propyl chains on the cation, which form a distinct, self-assembled nonpolar domain within the liquid. Our simulations demonstrate that the addition of Cl- and Br- anions to PAN disrupts the structure within the PAN charged domain due to competition between nitrate and halide anions for the ammonium charge centre. This disruption increases with halide concentration (up to 10 mol. %). However, at these concentrations, halide addition has little effect on the structure of the PAN nonpolar domain. Addition of PEO to pure PAN also disrupts the structure within the charged domain of the liquid due to hydrogen bonding between the charge groups and the terminal PEO hydroxyl groups. There is little other association between the PEO structure and the surrounding ionic liquid solvent, with strong PEO self-interaction yielding a compact, coiled polymer morphology. Halide addition results in greater association between the ionic liquid charge centres and the ethylene oxide components of the PEO structure, resulting in reduced conformational flexibility, compared to that observed in pure PAN. Similarly, PEO self-interactions increase in the presence of Cl- and Br- anions, compared to PAN, indicating that the addition of halide salts to PAN

Resonant halide perovskite nanoparticles

Science.gov (United States)

Tiguntseva, Ekaterina Y.; Ishteev, Arthur R.; Komissarenko, Filipp E.; Zuev, Dmitry A.; Ushakova, Elena V.; Milichko, Valentin A.; Nesterov-Mueller, Alexander; Makarov, Sergey V.; Zakhidov, Anvar A.

2017-09-01

The hybrid halide perovskites is a prospective material for fabrication of cost-effective optical devices. Unique perovskites properties are used for solar cells and different photonic applications. Recently, perovskite-based nanophotonics has emerged. Here, we consider perovskite like a high-refractive index dielectric material, which can be considered to be a basis for nanoparticles fabrication with Mie resonances. As a result, we fabricate and study resonant perovskite nanoparticles with different sizes. We reveal, that spherical nanoparticles show enhanced photoluminescence signal. The achieved results lay a cornerstone in the field of novel types of organic-inorganic nanophotonics devices with optical properties improved by Mie resonances.

A Cluster-Bethe lattice treatment for the F-center in alkali-halides

International Nuclear Information System (INIS)

Queiroz, S.L.A. de; Koiller, B.; Maffeo, B.; Brandi, H.S.

1977-01-01

The electronic structure of the F-center in alkali-halides with the NaCl structure has been studied using the Cluster-Bethe lattice method. The central cluster has been taken as constituted by the vacancy and the nearest- and second- neighbors to it, respectively, cations and anions. The optical transitions have been calculated and compared to experimental data on the location of the peak of the F-absorption band. The agreement obtained indicates that this method may be used to study properties of this defect in alkali halides [pt

First-principles study of γ-ray detector materials in perovskite halides

Science.gov (United States)

Im, Jino; Jin, Hosub; Stoumpos, Constantinos; Chung, Duck; Liu, Zhifu; Peters, John; Wessels, Bruce; Kanatzidis, Mercouri; Freeman, Arthur

2013-03-01

In an effort to search for good γ-ray detector materials, perovskite halide compounds containing heavy elements were investigated. Despite the three-dimensional network of the corner shared octahedra and the extended nature of the outermost shell, its strong ionic character leads to a large band gap, which is one of the essential criteria for γ-ray detector materials. Thus, considering high density and high atomic number, these pervoskite halides are possible candidate for γ-ray detector materials. We performed first-principles calculations to investigate electronic structures and thermodynamic properties of intrinsic defects in the selected perovskite halide, CsPbBr3. The screened-exchange local density approximation scheme was employed to correct the underestimation of the band gap in the LDA method. As a result, the calculated band gap of CsPbBr3 is found to be suitable for γ-ray detection. Furthermore, defect formation energy calculations allow us to predict thermodynamic and electronic properties of possible intrinsic defects, which affect detector efficiency and energy resolution. Supported by the office of Nonproliferation and Verification R &D under Contract No. DE-AC02-06CH11357

Single Crystals of Organolead Halide Perovskites: Growth, Characterization, and Applications

KAUST Repository

Peng, Wei

2017-01-01

Despite their outstanding charge transport characteristics, organolead halide perovskite single crystals grown by hitherto reported crystallization methods are not suitable for most optoelectronic devices due to their small aspect ratios

Highly Efficient Broadband Yellow Phosphor Based on Zero-Dimensional Tin Mixed-Halide Perovskite.

Science.gov (United States)

Zhou, Chenkun; Tian, Yu; Yuan, Zhao; Lin, Haoran; Chen, Banghao; Clark, Ronald; Dilbeck, Tristan; Zhou, Yan; Hurley, Joseph; Neu, Jennifer; Besara, Tiglet; Siegrist, Theo; Djurovich, Peter; Ma, Biwu

2017-12-27

Organic-inorganic hybrid metal halide perovskites have emerged as a highly promising class of light emitters, which can be used as phosphors for optically pumped white light-emitting diodes (WLEDs). By controlling the structural dimensionality, metal halide perovskites can exhibit tunable narrow and broadband emissions from the free-exciton and self-trapped excited states, respectively. Here, we report a highly efficient broadband yellow light emitter based on zero-dimensional tin mixed-halide perovskite (C 4 N 2 H 14 Br) 4 SnBr x I 6-x (x = 3). This rare-earth-free ionically bonded crystalline material possesses a perfect host-dopant structure, in which the light-emitting metal halide species (SnBr x I 6-x 4- , x = 3) are completely isolated from each other and embedded in the wide band gap organic matrix composed of C 4 N 2 H 14 Br - . The strongly Stokes-shifted broadband yellow emission that peaked at 582 nm from this phosphor, which is a result of excited state structural reorganization, has an extremely large full width at half-maximum of 126 nm and a high photoluminescence quantum efficiency of ∼85% at room temperature. UV-pumped WLEDs fabricated using this yellow emitter together with a commercial europium-doped barium magnesium aluminate blue phosphor (BaMgAl 10 O 17 :Eu 2+ ) can exhibit high color rendering indexes of up to 85.

Cation–Anion Interactions within the Nucleic Acid Ion Atmosphere Revealed by Ion Counting

Science.gov (United States)

Gebala, Magdalena; Giambasu, George M.; Lipfert, Jan; Bisaria, Namita; Bonilla, Steve; Li, Guangchao; York, Darrin M.; Herschlag, Daniel

2016-01-01

The ion atmosphere is a critical structural, dynamic, and energetic component of nucleic acids that profoundly affects their interactions with proteins and ligands. Experimental methods that “count” the number of ions thermodynamically associated with the ion atmosphere allow dissection of energetic properties of the ion atmosphere, and thus provide direct comparison to theoretical results. Previous experiments have focused primarily on the cations that are attracted to nucleic acid polyanions, but have also showed that anions are excluded from the ion atmosphere. Herein, we have systematically explored the properties of anion exclusion, testing the zeroth-order model that anions of different identity are equally excluded due to electrostatic repulsion. Using a series of monovalent salts, we find, surprisingly, that the extent of anion exclusion and cation inclusion significantly depends on salt identity. The differences are prominent at higher concentrations and mirror trends in mean activity coefficients of the electrolyte solutions. Salts with lower activity coefficients exhibit greater accumulation of both cations and anions within the ion atmosphere, strongly suggesting that cation–anion correlation effects are present in the ion atmosphere and need to be accounted for to understand electrostatic interactions of nucleic acids. To test whether the effects of cation–anion correlations extend to nucleic acid kinetics and thermodynamics, we followed the folding of P4–P6, a domain of the Tetrahymena group I ribozyme, via single-molecule fluorescence resonance energy transfer in solutions with different salts. Solutions of identical concentration but lower activity gave slower and less favorable folding. Our results reveal hitherto unknown properties of the ion atmosphere and suggest possible roles of oriented ion pairs or anion-bridged cations in the ion atmosphere for electrolyte solutions of salts with reduced activity. Consideration of these new

Monovalent cation and amiloride analog modulation of adrenergic ligand binding to the unglycosylated alpha 2B-adrenergic receptor subtype

International Nuclear Information System (INIS)

Wilson, A.L.; Seibert, K.; Brandon, S.; Cragoe, E.J. Jr.; Limbird, L.E.

1991-01-01

The unglycosylated alpha 2B subtype of the alpha 2-adrenergic receptor found in NG-108-15 cells possesses allosteric regulation of adrenergic ligand binding by monovalent cations and 5-amino-substituted amiloride analogs. These findings demonstrate that allosteric modulation of adrenergic ligand binding is not a property unique to the alpha 2A subtype. The observation that amiloride analogs as well as monovalent cations can modulate adrenergic ligand binding to the nonglycosylated alpha 2B subtype indicates that charge shielding due to carbohydrate moieties does not play a role in this allosteric modulation but, rather, these regulatory effects result from interactions of cations and amiloride analogs with the protein moiety of the receptor. Furthermore, the observation that both alpha 2A and alpha 2B receptor subtypes are modulated by amiloride analogs suggests that structural domains that are conserved between the two are likely to be involved in this allosteric modulation

Influence of electrode, buffer gas and control gear on metal halide lamp performance

International Nuclear Information System (INIS)

Lamouri, A; Naruka, A; Sulcs, J; Varanasi, C V; Brumleve, T R

2005-01-01

In this paper the influence of electrode composition, buffer gas fill pressure and control gear on the performance of metal halide lamps is investigated. It is shown that pure tungsten electrodes improve lumen maintenance and reduce voltage rise over lamp life. An optimum buffer gas fill pressure condition is discovered which allows for reduced electrode erosion during lamp starting as well as under normal operating conditions. Use of electronic control gear is shown to improve the performance of metal halide lamps

Reversible photo-induced trap formation in mixed-halide hybrid perovskites for photovoltaics.

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Hoke, Eric T; Slotcavage, Daniel J; Dohner, Emma R; Bowring, Andrea R; Karunadasa, Hemamala I; McGehee, Michael D

2015-01-01

We report on reversible, light-induced transformations in (CH 3 NH 3 )Pb(Br x I 1- x ) 3 . Photoluminescence (PL) spectra of these perovskites develop a new, red-shifted peak at 1.68 eV that grows in intensity under constant, 1-sun illumination in less than a minute. This is accompanied by an increase in sub-bandgap absorption at ∼1.7 eV, indicating the formation of luminescent trap states. Light soaking causes a splitting of X-ray diffraction (XRD) peaks, suggesting segregation into two crystalline phases. Surprisingly, these photo-induced changes are fully reversible; the XRD patterns and the PL and absorption spectra revert to their initial states after the materials are left for a few minutes in the dark. We speculate that photoexcitation may cause halide segregation into iodide-rich minority and bromide-enriched majority domains, the former acting as a recombination center trap. This instability may limit achievable voltages from some mixed-halide perovskite solar cells and could have implications for the photostability of halide perovskites used in optoelectronics.

On the Boiling Points of the Alkyl Halides.

Science.gov (United States)

Correia, John

1988-01-01

Discusses the variety of explanations in organic chemistry textbooks of a physical property of organic compounds. Focuses on those concepts explaining attractive forces between molecules. Concludes that induction interactions play a major role in alkyl halides and other polar organic molecules and should be given wider exposure in chemistry texts.…

Enhanced 1.53 μm emission of Er{sup 3+} ions in phosphate glass via energy transfer from Cu{sup +} ions

Energy Technology Data Exchange (ETDEWEB)

Jiménez, José A., E-mail: jose.jimenez@unf.edu [Department of Chemistry, University of North Florida, Jacksonville, Florida 32224 (United States); Sendova, Mariana [Optical Spectroscopy and Nano-Materials Lab, New College of Florida, Sarasota, Florida 34243 (United States)

2014-07-21

Optimizing the efficiency of Er{sup 3+} emission in the near-infrared telecommunication window in glass matrices is currently a subject of great interest in photonics research. In this work, Cu{sup +} ions are shown to be successfully stabilized at a high concentration in Er-containing phosphate glass by a single-step melt-quench method, and demonstrated to transfer energy to Er{sup 3+} thereby enhancing the near-infrared emission about 15 times. The spectroscopic data indicate an energy conversion process where Cu{sup +} ions first absorb photons broadly around 360 nm and subsequently transfer energy from the Stokes-shifted emitting states to resonant Er{sup 3+} absorption transitions in the visible. Consequently, the Er{sup 3+} electronic excited states decay and the {sup 4}I{sub 3/2} metastable state is populated, leading to the enhanced emission at 1.53 μm. Monovalent copper ions are thus recognized as sensitizers of Er{sup 3+} ions, suggesting the potential of Cu{sup +} co-doping for applications in the telecommunications, solar cells, and solid-state lasing realizable under broad band near-ultraviolet optical pumping.

Binuclear trivalent and tetravalent uranium halides and cyanides supported by cyclooctatetraene ligands

International Nuclear Information System (INIS)

Wang, Cong-Zhi; Wu, Qun-Yan; Lan, Jian-Hui; Shi, Wei-Qun; Gibson, John K.

2017-01-01

Although the first organoactinide chloride Cp_3UCl (Cp = η"5-C_5H_5) was synthesized more than 50 years ago, binuclear uranium halides remain very rare in organoactinide chemistry. Herein, a series of binuclear trivalent and tetravalent uranium halides and cyanides with cyclooctatetraene ligands, (COT)_2U_2X_n (COT = η"8-C_8H_8; X=F, Cl, CN; n=2, 4), have been systematically studied using scalar-relativistic density functional theory (DFT). The structures with bridging halide or cyanide ligands were predicted to be the most stable complexes of (COT)_2U_2X_n, and all the complexes show weak antiferromagnetic interactions between the uranium centers. However, for each species, there is no significant uranium-uranium bonding interaction. The bonding between the metal and the ligands shows some degree of covalent character, especially between the metal and terminal halide or cyanide ligands. The U-5f and 6d orbitals are predominantly involved in the metal-ligand bonding. All the (COT)_2U_2X_n species were predicted to be more stable compared to the mononuclear half-sandwich complexes at room temperature in the gas phase such that (COT)_2U_2X_4 might be accessible through the known (COT)_2U complex. The tetravalent derivatives (COT)_2U_2X_4 are more energetically favorable than the trivalent (COT)_2U_2X_2 analogs, which may be attributed to the greater number of strong metal-ligand bonds in the former complexes.

Physicochemical properties of mixed phosphorus halides

International Nuclear Information System (INIS)

Sladkov, I.B.; Tugarinova, N.S.

1996-01-01

Certain physicochemical properties (thermodynamic characteristics at boiling point, critical constants, density of liquid on the saturation line) of mixed phosphorus halides (PI 3 , PI 2 F, PIF 2 , PI 2 Cl, PICl 2 , PI 1 Br, PIBr 2 , PIClF, PIBrCl, etc.) are determined by means of approximate methods. Reliability of the results obtained is confirmed by comparison of calculated and experimental data for phosphorus compounds of the same type. 7 refs., 3 figs., 4 tabs

Structure and transport of aqueous electrolytes: From simple halides to radionuclide ions

Energy Technology Data Exchange (ETDEWEB)

Hartkamp, Remco, E-mail: hartkamp@mit.edu; Coasne, Benoit, E-mail: benoit.coasne@enscm.fr [Institut Charles Gerhardt Montpellier, CNRS (UMR 5253), Université Montpellier 2, ENSCM, 8 rue de l’Ecole Normale, 34296 Montpellier Cedex 05 (France); MultiScale Material Science for Energy and Environment, CNRS/MIT (UMI 3466), Department of Civil and Environmental Engineering, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139 (United States)

2014-09-28

Molecular simulations are used to compare the structure and dynamics of conventional and radioactive aqueous electrolytes: chloride solutions with sodium, potassium, cesium, calcium, and strontium. The study of Cs{sup +} and Sr{sup 2+} is important because these radioactive ions can be extremely harmful and are often confused by living organisms for K{sup +} and Ca{sup 2+}, respectively. Na{sup +}, Ca{sup 2+}, and Sr{sup 2+} are strongly bonded to their hydration shell because of their large charge density. We find that the water molecules in the first hydration shell around Na{sup +} form hydrogen bonds between each other, whereas molecules in the first hydration shell around Ca{sup 2+} and Sr{sup 2+} predominantly form hydrogen bonds with water molecules in the second shell. In contrast to these three ions, K{sup +} and Cs{sup +} have low charge densities so that they are weakly bonded to their hydration shell. Overall, the structural differences between Ca{sup 2+} and Sr{sup 2+} are small, but the difference between their coordination numbers relative to their surface areas could potentially be used to separate these ions. Moreover, the different decays of the velocity-autocorrelation functions corresponding to these ions indicates that the difference in mass could be used to separate these cations. In this work, we also propose a new definition of the pairing time that is easy to calculate and of physical significance regardless of the problem at hand.

A spectrophotometric study of aqueous Au(III) halide-hydroxide complexes at 25-80 °C

Science.gov (United States)

Usher, Al; McPhail, D. C.; Brugger, Joël

2009-06-01

The mobility and transport of gold in low-temperature waters and brines is affected by the aqueous speciation of gold, which is sensitive in particular to pH, oxidation and halide concentrations. In this study, we use UV-Vis spectrophotometry to identify and measure the thermodynamic properties of Au(III) aqueous complexes with chloride, bromide and hydroxide. Au(III) forms stable square planar complexes with hydroxide and halide ligands. Based on systematic changes in the absorption spectra of solutions in three binary systems NaCl-NaBr, NaCl-NaOH and NaBr-NaOH at 25 °C, we derived log dissociation constants for the following mixed and end-member halide and hydroxide complexes: [AuCl 3Br] -, [AuCl 2Br 2] -, [AuBr 3Cl] - and [AuBr 4] -; [AuCl 3(OH)] -, [AuCl 2(OH) 2] -, [AuCl(OH) 3] - and [Au(OH) 4] -; and [AuBr 3(OH)] -, [AuBr 2(OH) 2] - and [AuBr(OH) 3] -. These are the first reported results for the mixed chloride-bromide complexes. Increasing temperature to 80 °C resulted in an increase in the stability of the mixed chloride-bromide complexes, relative to the end-member chloride and bromide complexes. For the [AuCl (4-n)(OH) n] - series of complexes ( n = 0-4), there is an excellent agreement between our spectrophotometric results and previous electrochemical results of Chateau et al. [Chateau et al. (1966)]. In other experiments, the iodide ion (I -) was found to be unstable in the presence of Au(III), oxidizing rapidly to I 2(g) and causing Au to precipitate. Predicted Au(III) speciation indicates that Au(III) chloride-bromide complexes can be important in transporting gold in brines with high bromide-chloride ratios (e.g., >0.05), under oxidizing (atmospheric), acidic (pH < 5) conditions. Native gold solubility under atmospheric oxygen conditions is predicted to increase with decreasing pH in acidic conditions, increasing pH in alkaline conditions, increasing chloride, especially at acid pH, and increasing bromide for bromide/chloride ratios greater than 0

Emission Enhancement and Intermittency in Polycrystalline Organolead Halide Perovskite Films

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Cheng Li

2016-08-01

Full Text Available Inorganic-organic halide organometal perovskites have demonstrated very promising performance for opto-electronic applications, such as solar cells, light-emitting diodes, lasers, single-photon sources, etc. However, the little knowledge on the underlying photophysics, especially on a microscopic scale, hampers the further improvement of devices based on this material. In this communication, correlated conventional photoluminescence (PL characterization and wide-field PL imaging as a function of time are employed to investigate the spatially- and temporally-resolved PL in CH3NH3PbI3−xClx perovskite films. Along with a continuous increase of the PL intensity during light soaking, we also observe PL blinking or PL intermittency behavior in individual grains of these films. Combined with significant suppression of PL blinking in perovskite films coated with a phenyl-C61-butyric acid methyl ester (PCBM layer, it suggests that this PL intermittency is attributed to Auger recombination induced by photoionized defects/traps or mobile ions within grains. These defects/traps are detrimental for light conversion and can be effectively passivated by the PCBM layer. This finding paves the way to provide a guideline on the further improvement of perovskite opto-electronic devices.

Chemical Origin of the Stability Difference between Copper(I)- and Silver(I)-Based Halide Double Perovskites.

Science.gov (United States)

Xiao, Zewen; Du, Ke-Zhao; Meng, Weiwei; Mitzi, David B; Yan, Yanfa

2017-09-25

Recently, Cu I - and Ag I -based halide double perovskites have been proposed as promising candidates for overcoming the toxicity and instability issues inherent within the emerging Pb-based halide perovskite absorbers. However, up to date, only Ag I -based halide double perovskites have been experimentally synthesized; there are no reports on successful synthesis of Cu I -based analogues. Here we show that, owing to the much higher energy level for the Cu 3d 10 orbitals than for the Ag 4d 10 orbitals, Cu I atoms energetically favor 4-fold coordination, forming [CuX 4 ] tetrahedra (X=halogen), but not 6-fold coordination as required for [CuX 6 ] octahedra. In contrast, Ag I atoms can have both 6- and 4-fold coordinations. Our density functional theory calculations reveal that the synthesis of Cu I halide double perovskites may instead lead to non-perovskites containing [CuX 4 ] tetrahedra, as confirmed by our material synthesis efforts. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of avalanche-type barrier discharge on a silver halide photographic material in the case of blocked ionic conductivity

International Nuclear Information System (INIS)

Boychenko, A. P.

2012-01-01

Imaging of avalanche-type barrier gas discharge excited by single videopulses ∼7 μs long is studied via chemical activation of an ion subsystem of microcrystals of silver halide photographic emulsions by 1-phenyl-5-mercaptotetrazole. Using “Retina” commercial X-ray film and specially fabricated photoemulsion microcrystals with effective surface and deep electron traps as an example, the selective gas-discharge sensitivity of photographic layers to applied-voltage polarity is detected. It is shown that their sensitivity to barrier discharge ignited by negative-polarity pulses (on the electrode with a photographic material) is higher than in the case of positive pulses, irrespective of the photographic material’s position in the capacitor system.

Photovoltaic Rudorffites: Lead-Free Silver Bismuth Halides Alternative to Hybrid Lead Halide Perovskites.

Science.gov (United States)

Turkevych, Ivan; Kazaoui, Said; Ito, Eisuke; Urano, Toshiyuki; Yamada, Koji; Tomiyasu, Hiroshi; Yamagishi, Hideo; Kondo, Michio; Aramaki, Shinji

2017-10-09

Hybrid CPbX 3 (C: Cs, CH 3 NH 3 ; X: Br, I) perovskites possess excellent photovoltaic properties but are highly toxic, which hinders their practical application. Unfortunately, all Pb-free alternatives based on Sn and Ge are extremely unstable. Although stable and non-toxic C 2 ABX 6 double perovskites based on alternating corner-shared AX 6 and BX 6 octahedra (A=Ag, Cu; B=Bi, Sb) are possible, they have indirect and wide band gaps of over 2 eV. However, is it necessary to keep the corner-shared perovskite structure to retain good photovoltaic properties? Here, we demonstrate another family of photovoltaic halides based on edge-shared AX 6 and BX 6 octahedra with the general formula A a B b X x (x=a+3 b) such as Ag 3 BiI 6 , Ag 2 BiI 5 , AgBiI 4 , AgBi 2 I 7 . As perovskites were named after their prototype oxide CaTiO 3 discovered by Lev Perovski, we propose to name these new ABX halides as rudorffites after Walter Rüdorff, who discovered their prototype oxide NaVO 2 . We studied structural and optoelectronic properties of several highly stable and promising Ag-Bi-I photovoltaic rudorffites that feature direct band gaps in the range of 1.79-1.83 eV and demonstrated a proof-of-concept FTO/c-m-TiO 2 /Ag 3 BiI 6 /PTAA/Au (FTO: fluorine-doped tin oxide, PTAA: poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine], c: compact, m: mesoporous) solar cell with photoconversion efficiency of 4.3 %. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

In silico prediction of monovalent and chimeric tetravalent vaccines for prevention and treatment of dengue fever.

Science.gov (United States)

Vijayakumar, Subramaniyan; Ramesh, Venkatachalam; Prabhu, Srinivasan; Manogar, Palani

2017-11-01

Reverse vaccinology method was used to predict the monovalent peptide vaccine candidate to produce antibodies for therapeutic purpose and to predict tetravalent vaccine candidate to act as a common vaccine to cover all the fever dengue virus serotypes. Envelope (E)-proteins of DENV-1-4 serotypes were used for vaccine prediction using NCBI, Uniprot/Swissprot, Swiss-prot viewer, VaxiJen V2.0, TMHMM, BCPREDS, Propred-1, Propred and MHC Pred,. E-proteins of DENV-1-4 serotypes were identified as antigen from which T cell epitopes, through B cell epitopes, were predicted to act as peptide vaccine candidates. Each selected T cell epitope of E-protein was confirmed to act as vaccine and to induce complementary antibody against particular serotype of dengue virus. Chimeric tetravalent vaccine was formed by the conjugation of four vaccines, each from four dengue serotypes to act as a common vaccine candidate for all the four dengue serotypes. It can be justifiably concluded that the monovalent 9-mer T cell epitope for each DENV serotypes can be used to produce specific antibody agaomst dengue virus and a chimeric common tetravalent vaccine candidate to yield a comparative vaccine to cover any of the four dengue virus serotype. This vaccine is expected to act as highly immunogenic against preventing dengue fever.

Advances and Promises of Layered Halide Hybrid Perovskite Semiconductors

NARCIS (Netherlands)

Pedesseau, Laurent; Sapori, Daniel; Traore, Boubacar; Robles, Roberto; Fang, Hong-Hua; Loi, Maria Antonietta; Tsai, Hsinhan; Nie, Wanyi; Blancon, Jean-Christophe; Neukirch, Amanda; Tretiak, Sergei; Mohite, Aditya D.; Katan, Claudine; Even, Jacky; Kepenekian, Mikael

2016-01-01

Layered halide hybrid organic inorganic perovskites (HOP) have been the subject of intense investigation before the rise of three-dimensional (3D) HOP and their impressive performance in solar cells. Recently, layered HOP have also been proposed as attractive alternatives for photostable solar cells

Strong Carrier-Phonon Coupling in Lead Halide Perovskite Nanocrystals

NARCIS (Netherlands)

Iaru, Claudiu M; Geuchies, Jaco J|info:eu-repo/dai/nl/370526090; Koenraad, Paul M; Vanmaekelbergh, Daniël|info:eu-repo/dai/nl/304829137; Silov, Andrei Yu

2017-01-01

We highlight the importance of carrier-phonon coupling in inorganic lead halide perovskite nanocrystals. The low-temperature photoluminescence (PL) spectrum of CsPbBr3 has been investigated under a nonresonant and a nonstandard, quasi-resonant excitation scheme, and phonon replicas of the main PL

Homocoupling of aryl halides in flow: Space integration of lithiation and FeCl3 promoted homocoupling

Directory of Open Access Journals (Sweden)

Aiichiro Nagaki

2011-08-01

Full Text Available The use of FeCl3 resulted in a fast homocoupling of aryllithiums, and this enabled its integration with the halogen–lithium exchange reaction of aryl halides in a flow microreactor. This system allows the homocoupling of two aryl halides bearing electrophilic functional groups, such as CN and NO2, in under a minute.

Femtosecond time-resolved photodissociation dynamics of methyl halide molecules on ultrathin gold films

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Mihai E. Vaida

2011-09-01

Full Text Available The photodissociation of small organic molecules, namely methyl iodide, methyl bromide, and methyl chloride, adsorbed on a metal surface was investigated in real time by means of femtosecond-laser pump–probe mass spectrometry. A weakly interacting gold surface was employed as substrate because the intact adsorption of the methyl halide molecules was desired prior to photoexcitation. The gold surface was prepared as an ultrathin film on Mo(100. The molecular adsorption behavior was characterized by coverage dependent temperature programmed desorption spectroscopy. Submonolayer preparations were irradiated with UV light of 266 nm wavelength and the subsequently emerging methyl fragments were probed by photoionization and mass spectrometric detection. A strong dependence of the excitation mechanism and the light-induced dynamics on the type of molecule was observed. Possible photoexcitation mechanisms included direct photoexcitation to the dissociative A-band of the methyl halide molecules as well as the attachment of surface-emitted electrons with transient negative ion formation and subsequent molecular fragmentation. Both reaction pathways were energetically possible in the case of methyl iodide, yet, no methyl fragments were observed. As a likely explanation, the rapid quenching of the excited states prior to fragmentation is proposed. This quenching mechanism could be prevented by modification of the gold surface through pre-adsorption of iodine atoms. In contrast, the A-band of methyl bromide was not energetically directly accessible through 266 nm excitation. Nevertheless, the one-photon-induced dissociation was observed in the case of methyl bromide. This was interpreted as being due to a considerable energetic down-shift of the electronic A-band states of methyl bromide by about 1.5 eV through interaction with the gold substrate. Finally, for methyl chloride no photofragmentation could be detected at all.

Large polarons in lead halide perovskites

OpenAIRE

Miyata, Kiyoshi; Meggiolaro, Daniele; Trinh, M. Tuan; Joshi, Prakriti P.; Mosconi, Edoardo; Jones, Skyler C.; De Angelis, Filippo; Zhu, X.-Y.

2017-01-01

Lead halide perovskites show marked defect tolerance responsible for their excellent optoelectronic properties. These properties might be explained by the formation of large polarons, but how they are formed and whether organic cations are essential remain open questions. We provide a direct time domain view of large polaron formation in single-crystal lead bromide perovskites CH3NH3PbBr3 and CsPbBr3. We found that large polaron forms predominantly from the deformation of the PbBr3 ? framewor...

EVALUATION OF REACTOGENICITY, SAFETY AND IMMUNOGENICITY OF INACTIVATED MONOVALENT VACCINE IN CHILDREN

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A.N. Mironov

2010-01-01

Full Text Available NPO «Microgen» developed vaccine «PANDEFLU» — influenza inactivated subunit adsorbed monovalent vaccine, strain A/California/7/2009 (H1N1, for specific prophylaxis of pandemic influenza in different age groups of citizens. Reactogenicity, safety and immunogenicity were analyzed in a study of volunteers 18–60 years old. The article presents results of administration of vaccine «PANDEFLU» in children. The study performed in two clinical centers proves good tolerability, reactogenicity, safety and high immunogenicity of this vaccine.Key words: children, influenza, influenza virus А/H1N1, inactivated influenza vaccine, reactogenicity, safety, immunogenicity.(Voprosy sovremennoi pediatrii — Current Pediatrics. – 2010;9(4:106-109

Contribution to the physicochemical investigation of monovalent thallium and tetravalent uranium fluorides

International Nuclear Information System (INIS)

Hsini, M.S.

1983-07-01

Ionic transport properties are studied in monovalent elements and tetravalent uranium fluorides and oxyfluorides. Crystal structure of the oxyfluoride: TlUsub(2.75)OF 10 was determined by X-ray diffraction on a monocrystal. The particular role played by oxygen is evidenced in the stabilization of the crystal structure based on an original arrangement of Archimedes antiprisms: UOF 7 corresponding to a long distance order oxygen-fluorine in the anionic network. Electric conductivity measurements in AC by the complex impedance method or in DC by the Van der Pauw method allowed performance estimation of these materials which are solid electrolytes. Correlations between electrical properties and structure give information in basic diffusion mechanism in these materials [fr

Recent Advances of Rare-Earth Ion Doped Luminescent Nanomaterials in Perovskite Solar Cells

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Yu Qiao

2018-01-01

Full Text Available Organic-inorganic lead halide based perovskite solar cells have received broad interest due to their merits of low fabrication cost, a low temperature solution process, and high energy conversion efficiencies. Rare-earth (RE ion doped nanomaterials can be used in perovskite solar cells to expand the range of absorption spectra and improve the stability due to its upconversion and downconversion effect. This article reviews recent progress in using RE-ion-doped nanomaterials in mesoporous electrodes, perovskite active layers, and as an external function layer of perovskite solar cells. Finally, we discuss the challenges facing the effective use of RE-ion-doped nanomaterials in perovskite solar cells and present some prospects for future research.

Binuclear trivalent and tetravalent uranium halides and cyanides supported by cyclooctatetraene ligands

Energy Technology Data Exchange (ETDEWEB)

Wang, Cong-Zhi; Wu, Qun-Yan; Lan, Jian-Hui; Shi, Wei-Qun [Chinese Academy of Sciences, Beijing (China). Laboratory of Nuclear Energy Chemistry and Key Laboratory for Biomedical Effects of Nanomaterials and Nanosafety; Chai, Zhi-Fang [Chinese Academy of Sciences, Beijing (China). Laboratory of Nuclear Energy Chemistry and Key Laboratory for Biomedical Effects of Nanomaterials and Nanosafety; Soochow Univ., Suzhou (China). School of Radiological and Interdisciplinary Sciences (RAD-X); Gibson, John K. [Lawrence Berkeley National Laboratory, CA (United States). Chemical Sciences Division

2017-03-01

Although the first organoactinide chloride Cp{sub 3}UCl (Cp = η{sup 5}-C{sub 5}H{sub 5}) was synthesized more than 50 years ago, binuclear uranium halides remain very rare in organoactinide chemistry. Herein, a series of binuclear trivalent and tetravalent uranium halides and cyanides with cyclooctatetraene ligands, (COT){sub 2}U{sub 2}X{sub n} (COT = η{sup 8}-C{sub 8}H{sub 8}; X=F, Cl, CN; n=2, 4), have been systematically studied using scalar-relativistic density functional theory (DFT). The structures with bridging halide or cyanide ligands were predicted to be the most stable complexes of (COT){sub 2}U{sub 2}X{sub n}, and all the complexes show weak antiferromagnetic interactions between the uranium centers. However, for each species, there is no significant uranium-uranium bonding interaction. The bonding between the metal and the ligands shows some degree of covalent character, especially between the metal and terminal halide or cyanide ligands. The U-5f and 6d orbitals are predominantly involved in the metal-ligand bonding. All the (COT){sub 2}U{sub 2}X{sub n} species were predicted to be more stable compared to the mononuclear half-sandwich complexes at room temperature in the gas phase such that (COT){sub 2}U{sub 2}X{sub 4} might be accessible through the known (COT){sub 2}U complex. The tetravalent derivatives (COT){sub 2}U{sub 2}X{sub 4} are more energetically favorable than the trivalent (COT){sub 2}U{sub 2}X{sub 2} analogs, which may be attributed to the greater number of strong metal-ligand bonds in the former complexes.

On the use of dimensionless parameters in acid-base theory: VI. The buffer capacities of equimolar binary mixtures of monovalent weak protolytes as compared to that of bivalent protolytes.

Science.gov (United States)

Rilbe, H

1994-05-01

The general equation for the relative molar buffer capacity, earlier shown to be valid for bivalent acids, bases, and ampholytes, is shown to hold also for equimolar, binary mixtures of monovalent protolytes if only the parameter s = square root of K1'/4K2' is exchanged for t = s + 1/4s. The same applies to the equations for the mean valence of the two classes of protolytes. As a consequence thereof, the titration and buffer capacity curves of a bivalent protolyte are identical with those of a monovalent protolyte with a pK' value equal to the with those of a monovalent protolyte with a pK' value equal to square root of K1'K2' of the bivalent one (the isoprotic point of an ampholyte). For a hypothetical bivalent acid, base, or ampholyte with s = 1, delta pK' = log 4, this implies that the intrinsic rather than the hybrid dissociation constants are responsible for the titration and buffer capacity curves.

Spectroscopy on metal-halide lamps under varying gravity conditions

NARCIS (Netherlands)

Flikweert, A.J.

2008-01-01

Worldwide, 20% of all electricity is used for lighting. For this reason, efficient lamps are economically and ecologically important. High intensity discharge (HID) lamps are efficient lamps. The most common HID lamp these days is the metal-halide (MH) lamp. MH lamps have a good colour rendering

Dislocation unpinning model of acoustic emission from alkali halide ...

Indian Academy of Sciences (India)

AE) from alkali halide crystals. Equations are derived for the strain dependence of the transient AE pulse rate, peak value of the AE pulse rate and the total number of AE pulse emitted. It is found that the AE pulse rate should be maximum for a ...

Halide Perovskites: New Science or ``only'' future Energy Converters?

Science.gov (United States)

Cahen, David

Over the years many new ideas and systems for photovoltaic, PV, solar to electrical energy conversion have been explored, but only a few have really impacted PV's role as a more sustainable, environmentally less problematic and safer source of electrical power than fossil or nuclear fuel-based generation. Will Halide Perovskites, HaPs, be able to join the very select group of commercial PV options? To try to address this question, we put Halide Perovskite(HaP) cells in perspective with respect to other PV cells. Doing so also allows to identify fundamental scientific issues that can be important for PV and beyond. What remains to be seen is if those issues lead to new science or scientific insights or additional use of existing models. Being more specific is problematic, given the fact that this will be 4 months after writing this abstract. Israel National Nano-initiative, Weizmann Institute of Science's Alternative sustainable Energy Research Initiative; Israel Ministries of -Science and of -Infrastructure, Energy & Water.

Aluminum Pitting Corrosion in Halide Media: A Quantum Model and Empirical Evidence

Science.gov (United States)

Lashgari, Mohsen; Kianpour, Effat; Mohammadi, Esmaeil

2013-12-01

The phenomenon of localized damage of aluminum oxide surface in the presence of halide anions was scrutinized at an atomistic level, through the cluster approach and density functional theory. The phenomenon was also investigated empirically through Tafel polarization plots and scanning electron microscopy. A distinct behavior witnessed in the fluoride medium was justified through the hard-soft acid-base principle. The atomistic investigations revealed the greatest potency for chloride entrance into the metal oxide lattice and rationalized to the severity of damage. The interaction of halide anions with the oxide surface causing some displacements on the position of Al atoms provides a mechanistic insight of the phenomenon.

The nature of dynamic disorder in lead halide perovskite crystals (Conference Presentation)

Science.gov (United States)

Yaffe, Omer; Guo, Yinsheng; Hull, Trevor; Stoumpos, Costas; Tan, Liang Z.; Egger, David A.; Zheng, Fan; Szpak, Guilherme; Semonin, Octavi E.; Beecher, Alexander N.; Heinz, Tony F.; Kronik, Leeor; Rappe, Andrew M.; Kanatzidis, Mercouri G.; Owen, Jonathan S.; Pimenta, Marcos A.; Brus, Louis E.

2016-09-01

We combine low frequency Raman scattering measurements with first-principles molecular dynamics (MD) to study the nature of dynamic disorder in hybrid lead-halide perovskite crystals. We conduct a comparative study between a hybrid (CH3NH3PbBr3) and an all-inorganic lead-halide perovskite (CsPbBr3). Both are of the general ABX3 perovskite formula, and have a similar band gap and structural phase sequence, orthorhombic at low temperature, changing first to tetragonal and then to cubic symmetry as temperature increases. In the high temperature phases, we find that both compounds show a pronounced Raman quasi-elastic central peak, indicating that both are dynamically disordered.

Organometallic halide perovskite single crystals having low deffect density and methods of preparation thereof

KAUST Repository

Bakr, Osman M.

2016-02-18

The present disclosure presents a method of making a single crystal organometallic halide perovskites, with the formula: AMX3, wherein A is an organic cation, M is selected from the group consisting of: Pb, Sn, Cu, Ni, Co, Fe, Mn, Pd, Cd, Ge, and Eu, and X is a halide. The method comprises the use of two reservoirs containing different precursors and allowing the vapor diffusion from one reservoir to the other one. A solar cell comprising said crystal is also disclosed.

In-vitro Neurotoxicity of Two Malaysian Krait Species (Bungarus candidus and Bungarus fasciatus Venoms: Neutralization by Monovalent and Polyvalent Antivenoms from Thailand

Directory of Open Access Journals (Sweden)

Muhamad Rusdi Ahmad Rusmili

2014-03-01

Full Text Available Bungarus candidus and Bungarus fasciatus are two species of krait found in Southeast Asia. Envenoming by these snakes is often characterized by neurotoxicity and, without treatment, causes considerable morbidity and mortality. In this study, the in vitro neurotoxicity of each species, and the effectiveness of two monovalent antivenoms and a polyvalent antivenom, against the neurotoxic effects of the venoms, were examined in a skeletal muscle preparation. Both venoms caused concentration-dependent inhibition of indirect twitches, and attenuated responses to exogenous nicotinic receptor agonists, in the chick biventer preparation, with B. candidus venom being more potent than B. fasciatus venom. SDS-PAGE and western blot analysis indicated different profiles between the venoms. Despite these differences, most proteins bands were recognized by all three antivenoms. Antivenom, added prior to the venoms, attenuated the neurotoxic effect of the venoms. Interestingly, the respective monovalent antivenoms did not neutralize the effects of the venom from the other Bungarus species indicating a relative absence of cross-neutralization. Addition of a high concentration of polyvalent antivenom, at the t90 time point after addition of venom, partially reversed the neurotoxicity of B. fasciatus venom but not B. candidus venom. The monovalent antivenoms had no significant effect when added at the t90 time point. This study showed that B. candidus and B. fasciatus venoms display marked in vitro neurotoxicity in the chick biventer preparation and administration of antivenoms at high dose is necessary to prevent or reverse neurotoxicity.

Effect Of Metal Ions On Triphenylmethane Dye Decolorization By Laccase From Trametes Versicolor

Directory of Open Access Journals (Sweden)

Chmelová Daniela

2015-12-01

Full Text Available The aim of this study was investigate the influence of different metal ions on laccase activity and triphenylmethane dye decolorization by laccase from white-rot fungus Trametes versicolor. Laccase activity was inhibited by monovalent ions (Li+, Na+, K+ and Ag+ but the presence of divalent ions increased laccase activity at the concentration of 10 mmol/l. The effect of metal ions on decolorization of triphenylmethane dyes with different structures namely Bromochlorophenol Blue, Bromophenol Blue, Bromocresol Blue and Phenol Red was tested. The presence of metal ions (Na+, K+, Mg2+, Ca2+, Ba2+, Mn2+, Zn2+ slightly decreased triphenylmethane dye decolorization by laccase from T. versicolor except Na+ and Mg2+, which caused the increase of decolorization for all tested dyes. Decolorization of selected dyes showed that the presence of low-molecular-weight compounds is necessary for effective decolorization. Hydroxybenzotriazole (HBT is the most frequently used. Although HBT belongs to most frequently used redox mediator and generally increase decolorization efficiency, so its presence decreased decolorization percentage of Bromophenol Blue and Bromochlorophenol Blue, the influence of metal ions to dye decolorization by laccase has the similar course with or without presence of redox mediator HBT.

Cuprous halides semiconductors as a new means for highly efficient light-emitting diodes

Science.gov (United States)

Ahn, Doyeol; Park, Seoung-Hwan

2016-01-01

In group-III nitrides in use for white light-emitting diodes (LEDs), optical gain, measure of luminous efficiency, is very low owing to the built-in electrostatic fields, low exciton binding energy, and high-density misfit dislocations due to lattice-mismatched substrates. Cuprous halides I-VII semiconductors, on the other hand, have negligible built-in field, large exciton binding energies and close lattice matched to silicon substrates. Recent experimental studies have shown that the luminescence of I-VII CuCl grown on Si is three orders larger than that of GaN at room temperature. Here we report yet unexplored potential of cuprous halides systems by investigating the optical gain of CuCl/CuI quantum wells. It is found that the optical gain and the luminescence are much larger than that of group III-nitrides due to large exciton binding energy and vanishing electrostatic fields. We expect that these findings will open up the way toward highly efficient cuprous halides based LEDs compatible to Si technology. PMID:26880097

Infrared Dielectric Screening Determines the Low Exciton Binding Energy of Metal-Halide Perovskites.

Science.gov (United States)

Umari, Paolo; Mosconi, Edoardo; De Angelis, Filippo

2018-02-01

The performance of lead-halide perovskites in optoelectronic devices is due to a unique combination of factors, including highly efficient generation, transport, and collection of photogenerated charge carriers. The mechanism behind efficient charge generation in lead-halide perovskites is still largely unknown. Here, we investigate the factors that influence the exciton binding energy (E b ) in a series of metal-halide perovskites using accurate first-principles calculations based on solution of the Bethe-Salpeter equation, coupled to ab initio molecular dynamics simulations. We find that E b is strongly modulated by screening from low-energy phonons, which account for a factor ∼2 E b reduction, while dynamic disorder and rotational motion of the organic cations play a minor role. We calculate E b = 15 meV for MAPbI 3 , in excellent agreement with recent experimental estimates. We then explore how different material combinations (e.g., replacing Pb → Pb:Sn→ Sn; and MA → FA → Cs) may lead to different E b values and highlight the mechanisms underlying E b tuning.

Third-order elastic moduli for alkali-halide crystals possessing the sodium chloride structure

International Nuclear Information System (INIS)

Ray, U.

2010-01-01

The values of third-order elastic moduli for alkali halides, having NaCl-type crystal structure are calculated according to the Born-Mayer potential model, considering the repulsive interactions up to the second nearest neighbours and calculating the values of the potential parameters for each crystal, independently, from the compressibility data. This work presents the first published account of the calculation of the third-order elastic moduli taking the actual value of the potential parameter unlike the earlier works. Third-order elastic constants have been computed for alkali halides at 0 and 300 K. The results of the third-order elastic constants are compared with the available experimental and theoretical data. Very good agreement between experimental and theoretical third-order elastic constant data (except C 123 ) is found. We have also computed the values of the pressure derivatives of second-order elastic constants and Anderson-Grueneisen parameter for alkali halides, which agree reasonably well with the experimental values, indicating the satisfactory nature of our computed data for third-order elastic constants.

Development of [18F]halofluorination and [18F]fluoride ion displacement reactions for the synthesis of F-18 labelled radiopharmaceuticals

International Nuclear Information System (INIS)

Chi, D.Y.

1986-01-01

Two fluorine-18 labeling methods, [ 18 F]halofluorination and [ 18 F]fluoride ion displacement reactions, have been developed to assess their potential for labeling molecules with the positron-emitting radionuclide fluorine-18 at the no-carrier-added level. Olefin halofluorination involves the in situ generation of a halogen-fluoride reagent and subsequent addition to an olefin. The characteristics of this reaction were investigated with three model olefins (allylbenzene, 1-hexene, and propene). A two-step method for the preparation of fluoroalkyl substituted amines and amides has been achieved. The sequence involves fluoride ion displacement of trifluoromethanesulfonates (triflates) from short-chain haloalkyl triflates, followed by fluoroalkylation of the amine or amide. Alternatively, short-chain fluoroalkyl halides can be prepared by halofluorination of a terminal olefin. These reactions have been used to prepare various fluoroalkyl derivatives of 1-phenylpiperazine and N-fluoroalkyl derivatives of the neuroleptic agent spiperone. A series of fluorine-18 labeled N-fluoroalkylated spiperone derivatives were synthesized by N-alkylation of spiperone with fluoroalkyl halides

A SUBSTRATE AND A METHOD FOR DETERMINING AND/OR MONITORING ELECTROPHYSIOLOGICAL PROPERTIES OF ION CHANNELS

DEFF Research Database (Denmark)

2001-01-01

The present invention relates to a substrate and a method for obtaining an electrophysiological measuring configuration in which a cell forms a high resistive seal (giga-seal) around a measuring electrode making it suitable for determining and monitoring a current flow through the cell membrane...... and reference electrodes formed by wafer processing technology. The electrodes are adapted to conduct a current between them by delivery of ions by one electrode and receipt of ions by the other electrode and are typically silver/silver halide electrodes. This allows for effective and fast measuring of cells...

Demixing in a metal halide lamp, results from modeling

NARCIS (Netherlands)

Beks, M.L.; Hartgers, A.; Mullen, van der J.J.A.M.; Veldhuizen, van E.M.

2005-01-01

Metal Halide (MH) lamps are high pressure discharge devices, containing a complex chemical mixture, to emit light on a broad spectrum while maintaining good efficacies. Lamps of this type were first exhibited by General Electric at the 1964 World Fair in New York [1]. They typically consist of an

Crystal growth, structure and phase studies on gold halides

NARCIS (Netherlands)

Janssen, Eugenius Maria Wilhelmus Janssen

1977-01-01

Only very corrosive substances attack gold, the most noble metal. In this study the reactivity and the phase diagrams of gold with the halogens chlorine, bromine and iodine have been investigated. owing to the noble behaviour of gold, its halides are sensitive to heat; on heating they decompose into

New Proton-Ionizable, Calixarene-Based Ligands for Selective Metal Ion Separations

Energy Technology Data Exchange (ETDEWEB)

Bartsch, Richard A.

2012-06-04

The project objective was the discovery of new ligands for performing metal ion separations. The research effort entailed the preparation of new metal ion complexing agents and polymers and their evaluation in metal ion separation processes of solvent extraction, synthetic liquid membrane transport, and sorption. Structural variations in acyclic, cyclic, and bicyclic organic ligands were used to probe their influence upon the efficiency and selectivity with which metal ion separations can be performed. A unifying feature of the ligand structures is the presence of one (or more) side arm with a pendent acidic function. When a metal ion is complexed within the central cavity of the ligand, ionization of the side arm(s) produces the requisite anion(s) for formation of an overall electroneutral complex. This markedly enhances extraction/transport efficiency for separations in which movement of aqueous phase anions of chloride, nitrate, or sulfate into an organic medium would be required. Through systematic structural variations, new ligands have been developed for efficient and selective separations of monovalent metal ions (e.g., alkali metal, silver, and thallium cations) and of divalent metal ion species (e.g., alkaline earth metal, lead, and mercury cations). Research results obtained in these fundamental investigations provide important insight for the design and development of ligands suitable for practical metal ion separation applications.

Growth and Characterization of PDMS-Stamped Halide Perovskite Single Microcrystals

NARCIS (Netherlands)

Khoram, P.; Brittman, S.; Dzik, W.I.; Reek, J.N.H.; Garneett, E.C.

2016-01-01

Recently, halide perovskites have attracted considerable attention for optoelectronic applications, but further progress in this field requires a thorough understanding of the fundamental properties of these materials. Studying perovskites in their single-crystalline form provides a model system for

Fast self-diffusion of ions in CH ₃ NH ₃ PbI ₃ : the interstiticaly mechanism versus vacancy-assisted mechanism

Energy Technology Data Exchange (ETDEWEB)

Yang, Ji-Hui; Yin, Wan-Jian; Park, Ji-Sang; Wei, Su-Huai

2016-01-01

The stability of organic-inorganic halide perovskites is a major challenge for their applications and has been extensively studied. Among the possible underlying reasons, ion self-diffusion has been inferred to play important roles. While theoretical studies congruously support that iodine is more mobile, experimental studies only observe the direct diffusion of the MA ion and possible diffusion of iodine. The discrepancy may result from the incomplete understanding of ion diffusion mechanisms. With the help of first-principles calculations, we studied ion diffusion in CH3NH3PbI3 (MAPbI3) through not only the vacancy-assisted mechanisms presumed in previous theoretical studies, but also the neglected interstiticaly mechanisms. We found that compared to the diffusion through the vacancy-assisted mechanism, MA ion diffusion through the interstiticaly mechanism has a much smaller barrier which could explain experimental observations. For iodine diffusion, both mechanisms can yield relatively small barriers. Depending on the growth conditions, defect densities of vacancies and interstitials can vary and so do the diffusion species as well as diffusion mechanisms. Our work thus supports that both MA and iodine ion diffusion could contribute to the performance instability of MAPbI3. While being congruous with experimental results, our work fills the research gap by providing a full understanding of ion diffusion in halide perovskites.

Trap-Free Hot Carrier Relaxation in Lead–Halide Perovskite Films

KAUST Repository

Bretschneider, Simon A.; Laquai, Fré dé ric; Bonn, Mischa

2017-01-01

Photovoltaic devices that employ lead-halide perovskites as photoactive materials exhibit power conversion efficiencies of 22%. One of the potential routes to go beyond the current efficiencies is to extract charge carriers that carry excess energy, that is, nonrelaxed or

Trap-Free Hot Carrier Relaxation in Lead–Halide Perovskite Films

KAUST Repository

Bretschneider, Simon A.

2017-05-08

Photovoltaic devices that employ lead-halide perovskites as photoactive materials exhibit power conversion efficiencies of 22%. One of the potential routes to go beyond the current efficiencies is to extract charge carriers that carry excess energy, that is, nonrelaxed or

Simple electrolyte solutions: Comparison of DRISM and molecular dynamics results for alkali halide solutions

Science.gov (United States)

Joung, In Suk; Luchko, Tyler; Case, David A.

2013-01-01

Using the dielectrically consistent reference interaction site model (DRISM) of molecular solvation, we have calculated structural and thermodynamic information of alkali-halide salts in aqueous solution, as a function of salt concentration. The impact of varying the closure relation used with DRISM is investigated using the partial series expansion of order-n (PSE-n) family of closures, which includes the commonly used hypernetted-chain equation (HNC) and Kovalenko-Hirata closures. Results are compared to explicit molecular dynamics (MD) simulations, using the same force fields, and to experiment. The mean activity coefficients of ions predicted by DRISM agree well with experimental values at concentrations below 0.5 m, especially when using the HNC closure. As individual ion activities (and the corresponding solvation free energies) are not known from experiment, only DRISM and MD results are directly compared and found to have reasonably good agreement. The activity of water directly estimated from DRISM is nearly consistent with values derived from the DRISM ion activities and the Gibbs-Duhem equation, but the changes in the computed pressure as a function of salt concentration dominate these comparisons. Good agreement with experiment is obtained if these pressure changes are ignored. Radial distribution functions of NaCl solution at three concentrations were compared between DRISM and MD simulations. DRISM shows comparable water distribution around the cation, but water structures around the anion deviate from the MD results; this may also be related to the high pressure of the system. Despite some problems, DRISM-PSE-n is an effective tool for investigating thermodynamic properties of simple electrolytes. PMID:23387564

Halides of BET-TTF: novel hydrated molecular metals

Energy Technology Data Exchange (ETDEWEB)

Laukhina, E.; Ribera, E.; Vidal-Gancedo, J.; Canadell, E.; Veciana, J.; Rovira, C. [Universidad Autonoma de Barcelona, Bellaterra (Spain). Inst. de Ciencia de Materials; Khasanov, S.; Zorina, L.; Shibaeva, R. [Rossijskaya Akademiya Nauk, Chernogolovka (Russian Federation). Inst. Fiziki Tverdogo Tela; Laukhin, V. [Inst. of Problems of Chemical Physics, RAS, Chernogolovka (Russian Federation); Honold, M.; Nam, M.-S.; Singleton, J. [Clarendon Lab., Univ. of Oxford (United Kingdom)

2000-01-07

A hint of superconducting transition has been observed for the first time in a cation radical salt derived from bisethylenethio-tetrathiafulvalene (BET-TTF), the salt (BET-TTF){sub 2}Br.3H{sub 2}O. Here the synthesis, X-ray structure, and physical properties of two hydrated halides of BET-TTF that are isostructural and present stable metallic properties are described. (orig.)

The Electrical and Optical Properties of Organometal Halide Perovskites Relevant to Optoelectronic Performance

KAUST Repository

Adinolfi, Valerio

2017-10-12

Organometal halide perovskites are under intense study for use in optoelectronics. Methylammonium and formamidinium lead iodide show impressive performance as photovoltaic materials; a premise that has spurred investigations into light-emitting devices and photodetectors. Herein, the optical and electrical material properties of organometal halide perovskites are reviewed. An overview is given on how the material composition and morphology are tied to these properties, and how these properties ultimately affect device performance. Material attributes and techniques used to estimate them are analyzed for different perovskite materials, with a particular focus on the bandgap, mobility, diffusion length, carrier lifetime, and trap-state density.

Building up an electrocatalytic activity scale of cathode materials for organic halide reductions

International Nuclear Information System (INIS)

Bellomunno, C.; Bonanomi, D.; Falciola, L.; Longhi, M.; Mussini, P.R.; Doubova, L.M.; Di Silvestro, G.

2005-01-01

A wide investigation on the electrochemical activity of four model organic bromides has been carried out in acetonitrile on nine cathodes of widely different affinity for halide anions (Pt, Zn, Hg, Sn, Bi, Pb, Au, Cu, Ag), and the electrocatalytic activities of the latter have been evaluated with respect to three possible inert reference cathode materials, i.e. glassy carbon, boron-doped diamond, and fluorinated boron-doped diamond. A general electrocatalytic activity scale for the process is proposed, with a discussion on its modulation by the configuration of the reacting molecule, and its connection with thermodynamic parameters accounting for halide adsorption

Demixing in a metal halide lamp, results from modelling

NARCIS (Netherlands)

Beks, M.L.; Hartgers, A.; Mullen, van der J.J.A.M.

2006-01-01

Convection and diffusion in the discharge region of a metal halide lamp is studied using a computer model built with the plasma modeling package Plasimo. A model lamp contg. mercury and sodium iodide is studied. The effects of the total lamp pressure on the degree of segregation of the light

Feasibility of Cathode Surface Coating Technology for High-Energy Lithium-ion and Beyond-Lithium-ion Batteries.

Science.gov (United States)

Kalluri, Sujith; Yoon, Moonsu; Jo, Minki; Liu, Hua Kun; Dou, Shi Xue; Cho, Jaephil; Guo, Zaiping

2017-12-01

Cathode material degradation during cycling is one of the key obstacles to upgrading lithium-ion and beyond-lithium-ion batteries for high-energy and varied-temperature applications. Herein, we highlight recent progress in material surface-coating as the foremost solution to resist the surface phase-transitions and cracking in cathode particles in mono-valent (Li, Na, K) and multi-valent (Mg, Ca, Al) ion batteries under high-voltage and varied-temperature conditions. Importantly, we shed light on the future of materials surface-coating technology with possible research directions. In this regard, we provide our viewpoint on a novel hybrid surface-coating strategy, which has been successfully evaluated in LiCoO 2 -based-Li-ion cells under adverse conditions with industrial specifications for customer-demanding applications. The proposed coating strategy includes a first surface-coating of the as-prepared cathode powders (by sol-gel) and then an ultra-thin ceramic-oxide coating on their electrodes (by atomic-layer deposition). What makes it appealing for industry applications is that such a coating strategy can effectively maintain the integrity of materials under electro-mechanical stress, at the cathode particle and electrode- levels. Furthermore, it leads to improved energy-density and voltage retention at 4.55 V and 45 °C with highly loaded electrodes (≈24 mg.cm -2 ). Finally, the development of this coating technology for beyond-lithium-ion batteries could be a major research challenge, but one that is viable. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fullerenes doped with metal halides

International Nuclear Information System (INIS)

Martin, T.P.; Heinebrodt, M.; Naeher, U.; Goehlich, H.; Lange, T.; Schaber, H.

1993-01-01

The cage-like structure of fullerenes is a challenge to every experimental to put something inside - to dope the fullerenes. In fact, the research team that first identified C 60 as a football-like molecule quickly succeeded in trapping metal atoms inside and in shrinking the cage around this atom by photofragmentation. In this paper we report the results of ''shrink-wrapping'' the fullerenes around metal halide molecules. Of special interest is the critical size (the minimum number of carbon atoms) that can still enclose the dopant. A rough model for the space available inside a carbon cage gives good agreement with the measured shrinking limits. (author). 8 refs, 6 figs

Ion distributions, exclusion coefficients, and separation factors of electrolytes in a charged cylindrical nanopore: a partially perturbative density functional theory study.

Science.gov (United States)

Peng, Bo; Yu, Yang-Xin

2009-10-07

The structural and thermodynamic properties for charge symmetric and asymmetric electrolytes as well as mixed electrolyte system inside a charged cylindrical nanopore are investigated using a partially perturbative density functional theory. The electrolytes are treated in the restricted primitive model and the internal surface of the cylindrical nanopore is considered to have a uniform charge density. The proposed theory is directly applicable to the arbitrary mixed electrolyte solution containing ions with the equal diameter and different valences. Large amount of simulation data for ion density distributions, separation factors, and exclusion coefficients are used to determine the range of validity of the partially perturbative density functional theory for monovalent and multivalent counterion systems. The proposed theory is found to be in good agreement with the simulations for both mono- and multivalent counterion systems. In contrast, the classical Poisson-Boltzmann equation only provides reasonable descriptions of monovalent counterion system at low bulk density, and is qualitatively and quantitatively wrong in the prediction for the multivalent counterion systems due to its neglect of the strong interionic correlations in these systems. The proposed density functional theory has also been applied to an electrolyte absorbed into a pore that is a model of the filter of a physiological calcium channel.

Iron halide mediated atom transfer radical polymerization of methyl methacrylate with N-Alkyl-2-pyridylmethanimine as the ligand

NARCIS (Netherlands)

Zhang, H.; Schubert, U.S.

2004-01-01

The controlled atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) catalyzed by iron halide/N-(n-hexyl)-2-pyridylmethanimine (NHPMI) is described. The ethyl 2-bromoisobutyrate (EBIB)-initiated ATRP with [MMA]0/[EBIB]0/[iron halide]0/[NHPMI]0 = 150/1/1/2 was better controlled in

Effect of halide-mixing on the switching behaviors of organic-inorganic hybrid perovskite memory

Science.gov (United States)

Hwang, Bohee; Gu, Chungwan; Lee, Donghwa; Lee, Jang-Sik

2017-03-01

Mixed halide perovskite materials are actively researched for solar cells with high efficiency. Their hysteresis which originates from the movement of defects make perovskite a candidate for resistive switching memory devices. We demonstrate the resistive switching device based on mixed-halide organic-inorganic hybrid perovskite CH3NH3PbI3-xBrx (x = 0, 1, 2, 3). Solvent engineering is used to deposit the homogeneous CH3NH3PbI3-xBrx layer on the indium-tin oxide-coated glass substrates. The memory device based on CH3NH3PbI3-xBrx exhibits write endurance and long retention, which indicate reproducible and reliable memory properties. According to the increase in Br contents in CH3NH3PbI3-xBrx the set electric field required to make the device from low resistance state to high resistance state decreases. This result is in accord with the theoretical calculation of migration barriers, that is the barrier to ionic migration in perovskites is found to be lower for Br- (0.23 eV) than for I- (0.29-0.30 eV). The resistive switching may be the result of halide vacancy defects and formation of conductive filaments under electric field in the mixed perovskite layer. It is observed that enhancement in operating voltage can be achieved by controlling the halide contents in the film.

Solution enthalpies of alkali metal halides in water and heavy water mixtures with dimethyl sulfoxide

International Nuclear Information System (INIS)

Egorov, G.I.

1994-01-01

Solution enthalpies of CsF, LiCl, NaI, CsI and some other halides of alkali metals and tetrabutylammonium have been measured by the method of calorimetry. Standard solution enthalpies of all alkali metals (except rubidium) halides in water and heavy water mixtures with dimethylsulfoxide at 298.15 K have been calculated. Isotopic effects in solvation enthalpy of the electrolytes mentioned in aqueous solutions of dimethylsulfoxide have been discussed. 29 refs., 2 figs., 4 tabs

Barium halide nanocrystals in fluorozirconate based glass ceramics for scintillation application

Energy Technology Data Exchange (ETDEWEB)

Selling, J.

2007-07-01

Europium (Eu)-activated barium halide nanocrystals in fluorozirconate based glass ceramics represent a promising class of Xray scintillators. The scintillation in these glass ceramics is mainly caused by the emission of divalent Eu incorporated in hexagonal BaCl{sub 2} nanocrystals which are formed in the glass matrix upon appropriate annealing. Experiments with cerium (Ce)-activated fluorozironate glass ceramics showed that Ce is an interesting alternative. In order to get a better understanding of the scintillation mechanism in Eu- or Ce-activated barium halide nanocrystals, an investigation of the processes in the corresponding bulk material is essential. The objective of this thesis is the investigation of undoped, Eu-, and Ce-doped barium halides by X-ray excited luminescence (XL), pulse height, and scintillation decay spectra. That will help to figure out which of these crystals has the most promising scintillation properties and would be the best nanoparticles for the glass ceramics. Furthermore, alternative dopants like samarium (Sm) and manganese (Mn) were also investigated. Besides the above-mentioned optical investigation electron paramagnetic resonance (EPR) and Moessbauer measurements were carried out in order to complete the picture of Eu-doped barium halides. The EPR data of Eu-doped BaI{sub 2} is anticipated to yield more information about the crystal field and crystal structure that will help to understand the charge carrier process during the scintillation process. The main focus of the Moessbauer investigations was set on the Eu-doped fluorochlorozirconate glass ceramics. The results of this investigation should help to improve the glass ceramics. The Eu{sup 2+}/Eu{sup 3+} ratio in the glass ceramics should be determined and optimize favor of the Eu{sup 2+}. We also want to distinguish between Eu{sup 2+} in the glass matrix and Eu{sup 2+} in the nanocrystals. For a better understanding of Moessbauer spectroscopy on Eu also measurements on Eu in a

Barium halide nanocrystals in fluorozirconate based glass ceramics for scintillation application

International Nuclear Information System (INIS)

Selling, J.

2007-01-01

Europium (Eu)-activated barium halide nanocrystals in fluorozirconate based glass ceramics represent a promising class of Xray scintillators. The scintillation in these glass ceramics is mainly caused by the emission of divalent Eu incorporated in hexagonal BaCl 2 nanocrystals which are formed in the glass matrix upon appropriate annealing. Experiments with cerium (Ce)-activated fluorozironate glass ceramics showed that Ce is an interesting alternative. In order to get a better understanding of the scintillation mechanism in Eu- or Ce-activated barium halide nanocrystals, an investigation of the processes in the corresponding bulk material is essential. The objective of this thesis is the investigation of undoped, Eu-, and Ce-doped barium halides by X-ray excited luminescence (XL), pulse height, and scintillation decay spectra. That will help to figure out which of these crystals has the most promising scintillation properties and would be the best nanoparticles for the glass ceramics. Furthermore, alternative dopants like samarium (Sm) and manganese (Mn) were also investigated. Besides the above-mentioned optical investigation electron paramagnetic resonance (EPR) and Moessbauer measurements were carried out in order to complete the picture of Eu-doped barium halides. The EPR data of Eu-doped BaI 2 is anticipated to yield more information about the crystal field and crystal structure that will help to understand the charge carrier process during the scintillation process. The main focus of the Moessbauer investigations was set on the Eu-doped fluorochlorozirconate glass ceramics. The results of this investigation should help to improve the glass ceramics. The Eu 2+ /Eu 3+ ratio in the glass ceramics should be determined and optimize favor of the Eu 2+ . We also want to distinguish between Eu 2+ in the glass matrix and Eu 2+ in the nanocrystals. For a better understanding of Moessbauer spectroscopy on Eu also measurements on Eu in a CaF 2 host lattice were carried

Metal Halide Perovskite Polycrystalline Films Exhibiting Properties of Single Crystals

NARCIS (Netherlands)

Brenes, Roberto; Guo, D.; Osherov, Anna; Noel, Nakita K.; Eames, Christopher; Hutter, E.M.; Pathak, Sandeep K.; Niroui, Farnaz; Friend, Richard H.; Islam, M. Saiful; Snaith, Henry J.; Bulović, Vladimir; Savenije, T.J.; Stranks, Samuel D.

2017-01-01

Metal halide perovskites are generating enormous excitement for use in solar cells and light-emission applications, but devices still show substantial non-radiative losses. Here, we show that by combining light and atmospheric treatments, we can increase the internal luminescence quantum

Mechanoluminescence response to the plastic flow of coloured alkali halide crystals

International Nuclear Information System (INIS)

Chandra, B.P.; Bagri, A.K.; Chandra, V.K.

2010-01-01

The present paper reports the luminescence induced by plastic deformation of coloured alkali halide crystals using pressure steps. When pressure is applied onto a γ-irradiated alkali halide crystal, then initially the mechanoluminescence (ML) intensity increases with time, attains a peak value and later on it decreases with time. The ML of diminished intensity also appears during the release of applied pressure. The intensity I m corresponding to the peak of ML intensity versus time curve and the total ML intensity I T increase with increase in value of the applied pressure. The time t m corresponding to the ML peak slightly decreases with the applied pressure. After t m , initially the ML intensity decreases at a fast rate and later on it decreases at a slow rate. The decay time of the fast decrease in the ML intensity is equal to the pinning time of dislocations and the decay time for the slow decrease of ML intensity is equal to the diffusion time of holes towards the F-centres. The ML intensity increases with the density of F-centres and it is optimum for a particular temperature of the crystals. The ML spectra of coloured alkali halide crystals are similar to the thermoluminescence and afterglow spectra. The peak ML intensity and the total ML intensity increase drastically with the applied pressure following power law, whereby the pressure dependence of the ML intensity is related to the work-hardening exponent of the crystals. The ML also appears during the release of the applied pressure because of the movement of dislocation segments and movements of dislocation lines blocked under pressed condition. On the basis of the model based on the mechanical interaction between dislocation and F-centres, expressions are derived for the ML intensity, which are able to explain different characteristics of the ML. From the measurements of the plastico ML induced by the application of loads on γ-irradiated alkali halide crystals, the pinning time of dislocations

Manganese-Catalyzed Cross-Coupling of Aryl Halides and Grignard Reagents by a Radical Mechanism

DEFF Research Database (Denmark)

Antonacci, Giuseppe; Ahlburg, Andreas; Fristrup, Peter

2017-01-01

The substrate scope and the mechanism have been investigated for the MnCl2-catalyzed cross-coupling reaction between aryl halides and Grignard reagents. The transformation proceeds rapidly and in good yield when the aryl halide component is an aryl chloride containing a cyano or an ester group....... Two radical-clock experiments were carried out, and in both cases an intermediate aryl radical was successfully trapped. The cross-coupling reaction is therefore believed to proceed by an SRN1 mechanism, with a triorganomanganate complex serving as the most likely nucleophile and single-electron donor...

The electronic structure of the F-center in alkali-halides-The Bethe cluster - lattice

International Nuclear Information System (INIS)

Queiroz, S.L.A. de.

1977-07-01

The electronic structure of the F-center in alkali-halides with the NaCl structure has been studied using the Bethe Cluster lattice method. The central cluster has been taken as constituted by the vacancy and the nearest- and second-neighbors to it, respectively cations and anions. The optical transitions have been calculated and compared to experimental data on the location of the peak of the F-absorption band. The agreement obtained indicates that this method may be used to study properties of this defect in alkali halides. (Author) [pt

Hybrid Lead Halide Perovskites for Ultrasensitive Photoactive Switching in Terahertz Metamaterial Devices.

Science.gov (United States)

Manjappa, Manukumara; Srivastava, Yogesh Kumar; Solanki, Ankur; Kumar, Abhishek; Sum, Tze Chien; Singh, Ranjan

2017-08-01

The recent meteoric rise in the field of photovoltaics with the discovery of highly efficient solar-cell devices is inspired by solution-processed organic-inorganic lead halide perovskites that exhibit unprecedented light-to-electricity conversion efficiencies. The stunning performance of perovskites is attributed to their strong photoresponsive properties that are thoroughly utilized in designing excellent perovskite solar cells, light-emitting diodes, infrared lasers, and ultrafast photodetectors. However, optoelectronic application of halide perovskites in realizing highly efficient subwavelength photonic devices has remained a challenge. Here, the remarkable photoconductivity of organic-inorganic lead halide perovskites is exploited to demonstrate a hybrid perovskite-metamaterial device that shows extremely low power photoswitching of the metamaterial resonances in the terahertz part of the electromagnetic spectrum. Furthermore, a signature of a coupled phonon-metamaterial resonance is observed at higher pump powers, where the Fano resonance amplitude is extremely weak. In addition, a low threshold, dynamic control of the highly confined electric field intensity is also observed in the system, which could tremendously benefit the new generation of subwavelength photonic devices as active sensors, low threshold optically controlled lasers, and active nonlinear devices with enhanced functionalities in the infrared, optical, and the terahertz parts of the electromagnetic spectrum. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Study of the effect of positive ions impinging sensitive emulsions in mass spectrography; Etude de l'action des ions positifs sur les emulsions sensibles en spectrographie de masse

Energy Technology Data Exchange (ETDEWEB)

Cavard, A [Commissariat a l' Energie Atomique, Grenoble (France). Centre d' Etudes Nucleaires

1969-08-01

Experimental relationships have been established between the blackening of emulsions by impinging ions and the following parameters: number, mass and energy of impinging particles. Mean energy ions (about twenty keV) give rise to a latent image probably made of small specks of metallic silver located at the surface or in the bulk of the silver halide grain. A specific developer for ion sensitive emulsion was perfected. Sensitivity and detection threshold are increased by a factor of two or three, compared with values observed using a classical developer. Low energy particles sputtered from superficial layers of the emulsion by the impinging twenty keV ions, produce a latent image close to the surface of the silver halide grain. An oxidizing process bleaches superficial latent image and then reduces background fog. The improved signal over background ratio allows to observe lines undetectable when the plates are developed by usual process. (author) [French] On a etabli les relations experimentales entre le noircissement resultant de l'action des ions sur l'emulsion sensible et les parametres suivants: nombre de particules incidentes, masse et energie de ces particules. L'effet sur les grains d'halogenure d'argent a ete examine: les ions d'energie moyenne (de l'ordre de 20 keV) creent une image latente vraisemblablement constituee d'argent, situee a la fois a la surface et a l'interieur du grain. Un revelateur specifique pour le developpement des emulsions sensibles exposees aux ions a ete mis au point: il accroit la sensibilite d'un facteur deux a trois et le facteur de contraste par rapport a un revelateur usuel. Les particules de faible energie, emises par pulverisation des couches superficielles de l'emulsion au cours de l'enregistrement des spectres de masse des ions d'energie moyenne, creent essentiellement dans les grains d'halogenure d'argent, une image latente superficielle, responsable du fond. Un traitement oxydant est propose pour eliminer cette image en

Study of rare-gas dimer ions by the variational cellular method

International Nuclear Information System (INIS)

Wentzcovitch, R.M.M.

1982-01-01

The Variational Cellular Method to study ionized molecules in their ground and excited states with the scope of testing the validity of such method in these cases have been used. The ions studied are Ne +2 , Ar +2 , where the latter is the system with the largest number of electrons tested by VCM so far. The electronic transitions in these systems are important mechanisms of efficiency decay for the noble gas halide lasers ('excimer lasers'). (Author) [pt

Non-specific binding of Na+ and Mg2+ to RNA determined by force spectroscopy methods

Science.gov (United States)

Bizarro, C. V.; Alemany, A.; Ritort, F.

2012-01-01

RNA duplex stability depends strongly on ionic conditions, and inside cells RNAs are exposed to both monovalent and multivalent ions. Despite recent advances, we do not have general methods to quantitatively account for the effects of monovalent and multivalent ions on RNA stability, and the thermodynamic parameters for secondary structure prediction have only been derived at 1M [Na+]. Here, by mechanically unfolding and folding a 20 bp RNA hairpin using optical tweezers, we study the RNA thermodynamics and kinetics at different monovalent and mixed monovalent/Mg2+ salt conditions. We measure the unfolding and folding rupture forces and apply Kramers theory to extract accurate information about the hairpin free energy landscape under tension at a wide range of ionic conditions. We obtain non-specific corrections for the free energy of formation of the RNA hairpin and measure how the distance of the transition state to the folded state changes with force and ionic strength. We experimentally validate the Tightly Bound Ion model and obtain values for the persistence length of ssRNA. Finally, we test the approximate rule by which the non-specific binding affinity of divalent cations at a given concentration is equivalent to that of monovalent cations taken at 100-fold concentration for small molecular constructs. PMID:22492710

Band Gap Tuning and Defect Tolerance of Atomically Thin Two- Dimensional Organic-Inorganic Halide Perovskites

OpenAIRE

Pandey, Mohnish; Jacobsen, Karsten Wedel; Thygesen, Kristian Sommer

2016-01-01

Organic−inorganic halide perovskites have proven highly successful for photovoltaics but suffer from low stability, which deteriorates their performance over time. Recent experiments have demonstrated that low dimensional phases of the hybrid perovskites may exhibit improved stability. Here we report first-principles calculations for isolated monolayers of the organometallic halide perovskites (C4H9NH3)2MX2Y2, where M = Pb, Ge, Sn and X,Y = Cl, Br, I. The band gaps computed using the GLLB-SC ...

Sequential One-Pot Ruthenium-Catalyzed Azide−Alkyne Cycloaddition from Primary Alkyl Halides and Sodium Azide

KAUST Repository

Johansson, Johan R.

2011-04-01

An experimentally simple sequential one-pot RuAAC reaction, affording 1,5-disubstituted 1H-1,2,3-triazoles in good to excellent yields starting from an alkyl halide, sodium azide, and an alkyne, is reported. The organic azide is formed in situ by treating the primary alkyl halide with sodium azide in DMA under microwave heating. Subsequent addition of [RuClCp*(PPh 3) 2] and the alkyne yielded the desired cycloaddition product after further microwave irradiation. © 2011 American Chemical Society.

Study of the stabilization energies of halide-water clusters: An application of first-principles interaction potentials based on a polarizable and flexible model

International Nuclear Information System (INIS)

Ayala, Regla; Martinez, Jose M.; Pappalardo, Rafael R.; Sanchez Marcos, Enrique

2004-01-01

The aim of this work is to compute the stabilization energy E stab (n) of [X(H 2 O) n ] - (X≡F, Br, and I for n=1-60) clusters from Monte Carlo simulations using first-principles ab initio potentials. Stabilization energy of [X(H 2 O) n ] - clusters is defined as the difference between the vertical photodeachment energy of the cluster and the electron affinity of the isolated halide. On one hand, a study about the relation between cluster structure and the E stab (n) value, as well as the dependence of the latter with temperature is performed, on the other hand, a test on the reliability of our recently developed first-principles halide ion-water interaction potentials is carried out. Two different approximations were applied: (1) the Koopmans' theorem and (2) calculation of the difference between the interaction energy of [X(H 2 O) n ] - and [X(H 2 O) n ] clusters using the same ab initio interaction potentials. The developed methodology allows for using the same interaction potentials in the case of the ionic and neutral clusters with the proviso that the charge of the halide anion was switched off in the latter. That is, no specific parametrization of the interaction potentials to fit the magnitude under study was done. The good agreement between our predicted E stab (n) and experimental data allows us to validate the first-principles interaction potentials developed elsewhere and used in this study, and supports the fact that this magnitude is mainly determined by electrostatic factors, which can be described by our interaction potentials. No relation between the value of E stab (n) and the structure of clusters has been found. The diversity of E stab (n) values found for different clusters with similar interaction energy indicates the need for statistical information to properly estimate the stabilization energy of the halide anions. The effect of temperature in the prediction of the E stab (n) is not significant as long as it was high enough to avoid

Cerium doped lanthanum halides: fast scintillators for medical imaging

International Nuclear Information System (INIS)

Selles, O.

2006-12-01

This work is dedicated to two recently discovered scintillating crystals: cerium doped lanthanum halides (LaCl 3 :Ce 3+ and LaBr 3 :Ce 3+ ).These scintillators exhibit interesting properties for gamma detection, more particularly in the field of medical imaging: a short decay time, a high light yield and an excellent energy resolution. The strong hygroscopicity of these materials requires adapting the usual experimental methods for determining physico-chemical properties. Once determined, these can be used for the development of the industrial manufacturing process of the crystals. A proper comprehension of the scintillation mechanism and of the effect of defects within the material lead to new possible ways for optimizing the scintillator performance. Therefore, different techniques are used (EPR, radioluminescence, laser excitation, thermally stimulated luminescence). Alongside Ce 3+ ions, self-trapped excitons are involved in the scintillation mechanism. Their nature and their role are detailed. The knowledge of the different processes involved in the scintillation mechanism leads to the prediction of the effect of temperature and doping level on the performance of the scintillator. A mechanism is proposed to explain the thermally stimulated luminescence processes that cause slow components in the light emission and a loss of light yield. Eventually the study of afterglow reveals a charge transfer to deep traps involved in the high temperature thermally stimulated luminescence. (author)

Establishment of an in vivo potency assay for the recombinant hepatit is B surface antigen in monovalent and combined vaccines

Directory of Open Access Journals (Sweden)

Mabel Izquierdo-López

2014-12-01

Full Text Available In this paper the development of potency assay in animals (mice was made, with the objective of demonstrating the immunogenic power of the recombinant Hepatitis B surface antigen in monovalent and combined vaccines, produced at the Center of Genetic Engineering and Biotechnology. The potency test is a parameter in quality control and it is also a tool to demonstrate the consistency of the production process. Parameters such as duration of the test, number of animals in the test, as well as different areas for the maintenance of the animals were evaluated. The results on the applicability of the potency test, to two presentations of the vaccines; monovalent Heberbiovac HB and pentavalent liquid in one vial Heberpenta-L are shown, for which specificity studies, evaluating different vaccine lots, the behavior of linearity, and parallelism, as well as establishing quality specification of the test were performed. This assay led to the obtainment of reliable results for the vaccines evaluated, the consistent evaluation of the immunogenic power and the monitoring of different production processes.

Analisa Teknis Pemakaian Kombinasi Lampu Metal Halide Dan Led Sebagai Pemikat Ikan Pada Kapal Pukat Cincin (Purse Seine Dan Pengaruhnya Terhadap Konsumsi Bahan Bakar Genset

Directory of Open Access Journals (Sweden)

Septian Ragil Wibisono

2017-01-01

Full Text Available Saat ini lampu Metal Halide dipakai sebagai pemikat ikan  oleh nelayan Purse Seine. Peggunaan lampu tersebut memerlukan daya Genset yang besar karena satu lampu Metal Halide berdaya 1500 Watt. Semakin banyak lampu Metal Halide yang digunakan semakin besar pula konsumsi bahan bakar Genset. Dalam upaya penghematan energi bahan bakar maka digunakan lampu LED sebagai alternatif pemikat ikan. Lampu LED dikenal sebagai lampu yang hemat energi. Penelitian ini ditujukan untuk mengetahui dan membandingkan konsumsi bahan bakar Genset saat menggunakan kombinasi lampu Metal Halide dan LED. Penelitian ini dilakukan dengan mengambil data konsumsi bahan bakar Genset untuk menyalakan sejumlah lampu Metal Halide dan lampu LED, kemudian dilakukan analisa regresi untuk mendapatkan model persaamaan konsumsi bahan bakar Genset. Selanjutnya dilakukan ekstrapolasi untuk memprediksi konsumsi bahan bakar saat Genset dengan jumlah lampu tertentu. Hasilnya dengan besar fluks cahaya yang hampir sama, saat penggunaan 6 lampu Metal Halide konsumsi bahan bakar sebesar 13.606,03 liter, dan saat menggunakan kombinasi lampu 1 Metal Halide dan 25 lampu LED konsumsi bahan bakar sebesar 13.255,63 liter, yang artinya terjadi penghematan bahan bakar sebesar 2,58%.

Deviation from the trans -Effect in Ligand-Exchange Reactions of Zeise’s Ions PtCl₃(C₂H₄)^- with Heavier Halides (Br^–, I^- )

Energy Technology Data Exchange (ETDEWEB)

Hou, Gao-Lei [Physical; Govind, Niranjan [Environmental; Xantheas, Sotiris S. [Advanced; Department; Wang, Xue-Bin [Physical

2018-01-16

Four new Zeise’s family ions with mixed-halide ligands, i.e., PtCl_nX_3-n(C₂H₄)^- (X = Br, I; n = 1, 2), were synthesized via ligand-exchange reactions of KX salts with KPtCl₃(C₂H₄) in aqueous solutions, and were detected in vacuum via electrospray ionization mass spectrometry. Their photoelectron spectra reveal a series of well-resolved spectral peaks with their electron binding energies (EBEs) decreasing with increasing halide size, with I having a much stronger effect than Br, i.e., 4.57 (–Cl₃) > 4.56 (–Cl₂Br) > 4.53 (–ClBr₂) > 4.34 (–Cl₂I) > 4.30 eV (–ClI₂). Ab initio electronic structure calculations including spin-orbit coupling (SOC) predict that the cis- and trans-isomers are nearly isoenergetic with the cis-isomer for –Cl₂X, and the trans-isomer for –ClX₂ slightly favored, respectively. Excited-state spectra calculated with time-dependent density functional theory (TDDFT), and their comparison with the observed ones, suggest that for each species, both the cis- and trans-configurations coexist in the experiments and contribute to the observed spectra, a fact that clearly violates the prediction of the widely accepted trans-effect, which suggests that only one isomer would have formed.

Conformational isomerism in mixed-ligand complexes of 2,2'-bipyridine and triphenylphosphine with copper(I) halides

International Nuclear Information System (INIS)

Barron, P.F.; Engelhardt, L.M.; Healy, P.C.; Kildea, J.D.; White, A.H.

1988-01-01

Mixed-ligand complexes of triphenylphosphine and 2,2'-bipyridine and copper(I) halides have been synthesized. The 31 P NMR spectra of the complexes were measured and are reported along with data for complete structural characterization of the complexes. The results indicate a novel dichotomy of conformational isomers to be present in the chloride lattice. The Cu-P bond length was found to not vary with different halides. 8 refs., 4 figs., 6 tabs

THERMODYNAMICS OF MICELLE FORMATION BY 1-METHYL-4-ALKYLPYRIDINIUM HALIDES

NARCIS (Netherlands)

BIJMA, K; ENGBERTS, JBFN; HAANDRIKMAN, G; VANOS, NM; BLANDAMER, MJ; BUTT, MD; CULLIS, PM

This paper reports enthalpies of micellization for a series of 1-methyl-4-alkylpyridinium halide surfactants at 303.2 K with different lengths and degrees of branching of the 4-alkyl chain and different sizes of counterions using two microcalorimeters (LKB 2277 and Omega Microcal). The standard

Chemistry of gaseous lower-valent actinide halides. Technical progress report

International Nuclear Information System (INIS)

Hildenbrand, D.L.

1984-01-01

Objective is to provide thermochemical data for key actinide halide and oxyhalide systems. Progress is reported on bond dissociation energies of gaseous ThCl 4 , ThCl 3 , ThCl 2 , and ThCl; bond dissociation energies of ruthenium fluorides; and mass spectroscopy of UF 6

Students' Understanding of Alkyl Halide Reactions in Undergraduate Organic Chemistry

Science.gov (United States)

Cruz-Ramirez de Arellano, Daniel

2013-01-01

Organic chemistry is an essential subject for many undergraduate students completing degrees in science, engineering, and pre-professional programs. However, students often struggle with the concepts and skills required to successfully solve organic chemistry exercises. Since alkyl halides are traditionally the first functional group that is…

International collaboration to assess the risk of Guillain Barre Syndrome following Influenza A (H1N1) 2009 monovalent vaccines

NARCIS (Netherlands)

Dodd, Caitlin N.; Romio, Silvana A.; Black, Steven; Vellozzi, Claudia; Andrews, Nick; Sturkenboom, Miriam; Zuber, Patrick; Hua, Wei; Bonhoeffer, Jan; Buttery, Jim; Crawford, Nigel; Deceuninck, Genevieve; de Vries, Corinne; De Wals, Philippe; Gutierrez-Gimeno, M. Victoria; Heijbel, Harald; Hughes, Hayley; Hur, Kwan; Hviid, Anders; Kelman, Jeffrey; Kilpi, Tehri; Chuang, S. K.; Macartney, Kristine; Rett, Melisa; Lopez-Callada, Vesta Richardson; Salmon, Daniel; Sanchez, Francisco Gimenez; Sanz, Nuria; Silverman, Barbara; Storsaeter, Jann; Thirugnanam, Umapathi; van der Maas, Nicoline; Yih, Katherine; Zhang, Tao; Izurieta, Hector

2013-01-01

Background: The global spread of the 2009 novel pandemic influenza A (H1N1) virus led to the accelerated production and distribution of monovalent 2009 Influenza A (H1N1) vaccines (pH1N1). This pandemic provided the opportunity to evaluate the risk of Guillain-Barre syndrome (GBS), which has been an

Exciton-relaxation dynamics in lead halides

International Nuclear Information System (INIS)

Iwanaga, Masanobu; Hayashi, Tetsusuke

2003-01-01

We survey recent comprehensive studies of exciton relaxation in the crystals of lead halides. The luminescence and electron-spin-resonance studies have revealed that excitons in lead bromide spontaneously dissociate and both electrons and holes get self-trapped individually. Similar relaxation has been also clarified in lead chloride. The electron-hole separation is ascribed to repulsive correlation via acoustic phonons. Besides, on the basis of the temperature profiles of self-trapped states, we discuss the origin of luminescence components which are mainly induced under one-photon excitation into the exciton band in lead fluoride, lead chloride, and lead bromide

Plasmonic characterization of photo-induced silver nanoparticles extracted from silver halide based TEM film

Energy Technology Data Exchange (ETDEWEB)

Sudheer,, E-mail: sudheer@rrcat.gov.in; Tiwari, P.; Rai, V. N.; Srivastava, A. K. [Indus Synchrotrons Utilization Division, Raja Ramanna Centre for Advanced Technology Indore, Madhya Pradesh 452013 (India); Varshney, G. K. [Laser Bio-medical Applications & Instrumentation Division, Raja Ramanna Centre for Advanced Technology Indore, Madhya Pradesh 452013 (India)

2016-05-23

The plasmonic responses of silver nanoparticles extracted from silver halide based electron microscope film are investigated. Photo-reduction process is carried out to convert the silver halide grains into the metallic silver. The centrifuge technique is used for separating the silver nanoparticles from the residual solution. Morphological study performed by field emission scanning electron microscope (FESEM) shows that all the nanoparticles have an average diameter of ~120 nm with a high degree of mono dispersion in size. The localized surface plasmon resonance (LSPR) absorption peak at ~537 nm confirms the presence of large size silver nanoparticles.

Monovalent cations transfer through isolated human amnion: a new pharmacological model

Energy Technology Data Exchange (ETDEWEB)

Bara, M.; Guiet-Bara, A.; Durlach, J.

1985-04-01

Transfer of monovalent cations through the isolated human amnion consists of different factors: paracellular, coupling, ATPase dependent cellular transfer, leak cellular transfer. Understanding this transfer permits testing of the action of various substances. Physiological substances (Mg, taurine) increase ionic transfer and there is a vicarious effect between Mg and taurine. The tocolytic agents MgSO/sub 4/ and ethanol do not exhibit a good effect on the transfer: decrease with ethanol; equality between entry and exit fluxes with MgSO/sub 4/. On the other hand, amphotericin B increases mother-to-fetus transfer. Polluting metals (Pb, Cd, Hg, As) dramatically reduce exchanges and almost completely inhibit amnion permeability. Ingestion of ethanol also exhibits a dramatic effect on the exchange between mother and fetus through the amnion. Study of ionic transfer in vitro can be considered a pharmacological model to investigate the modifications of mother-fetus exchanges by various substances.

Synthesis, Structure, and Li-Ion Conductivity of LiLa(BH4)3X, X = Cl, Br, I

DEFF Research Database (Denmark)

GharibDoust, Seyed Hosein Payandeh; Brighi, Matteo; Sadikin, Yolanda

2017-01-01

In this work, a new type of addition reaction between La(BH4)3 and LiX, X = Cl, Br, I, is used to synthesize LiLa(BH4)3Cl and two new compounds LiLa(BH4)3X, X = Br, I. This method increases the amounts of LiLa(BH4)3X and the sample purity. The highest Li-ion conductivity is observed for LiLa(BH4...... with increasing lattice parameter, that is, increasing size of the halide ion in the structure. Thus, we conclude that the sizes of both windows are important for the lithium ion conduction in LiLa(BH4)3X compounds. The lithium ion conductivity is measured over one to three heating cycles and with different...

White-Light Emission from Layered Halide Perovskites.

Science.gov (United States)

Smith, Matthew D; Karunadasa, Hemamala I

2018-03-20

With nearly 20% of global electricity consumed by lighting, more efficient illumination sources can enable massive energy savings. However, effectively creating the high-quality white light required for indoor illumination remains a challenge. To accurately represent color, the illumination source must provide photons with all the energies visible to our eye. Such a broad emission is difficult to achieve from a single material. In commercial white-light sources, one or more light-emitting diodes, coated by one or more phosphors, yield a combined emission that appears white. However, combining emitters leads to changes in the emission color over time due to the unequal degradation rates of the emitters and efficiency losses due to overlapping absorption and emission energies of the different components. A single material that emits broadband white light (a continuous emission spanning 400-700 nm) would obviate these problems. In 2014, we described broadband white-light emission upon near-UV excitation from three new layered perovskites. To date, nine white-light-emitting perovskites have been reported by us and others, making this a burgeoning field of study. This Account outlines our work on understanding how a bulk material, with no obvious emissive sites, can emit every color of the visible spectrum. Although the initial discoveries were fortuitous, our understanding of the emission mechanism and identification of structural parameters that correlate with the broad emission have now positioned us to design white-light emitters. Layered hybrid halide perovskites feature anionic layers of corner-sharing metal-halide octahedra partitioned by organic cations. The narrow, room-temperature photoluminescence of lead-halide perovskites has been studied for several decades, and attributed to the radiative recombination of free excitons (excited electron-hole pairs). We proposed that the broad white emission we observed primarily stems from exciton self-trapping. Here, the

The role of halides on a chromium ligand field in lead borate glasses

Science.gov (United States)

Sekhar, K. Chandra; Srinivas, B.; Narsimlu, N.; Narasimha Chary, M.; Shareefuddin, Md

2017-10-01

Glasses with a composition of PbX-PbO-B2O3 (X  =  F2, Cl2 and Br2) containing Cr3+ ions were prepared by a melt quenching technique and investigated by using x-ray diffraction (XRD), optical absorption and electron paramagnetic resonance (EPR) studies. X-ray diffractograms revealed the amorphous nature of the glasses. The density and molar volume were determined. Density values increased for the PFPBCR glass system and decreased for the PCPBCR and PBPBCR glass systems with the composition. Optical absorption spectra were recorded at room temperature (RT) to evaluate the optical band gap E opt and Urbach energies. All the spectra showed characteristic peaks at around 450 nm, 600 nm and 690 nm, and they are assigned to 4 A 2g  →  4 T 1g, 4 A 2g  →  4 T 2g, 4 A 2g  →  2 E transitions respectively. From the optical absorption spectral data, the crystal field (D q ) and Racah parameters (B and C) have been evaluated. Variations in optical band gaps were explained using the electro negativity of halide ions. Electron paramagnetic resonance (EPR) studies were carried out by introducing Cr3+ as the spin probe. The EPR spectra of all the glass samples were recorded at X-band frequencies. The EPR spectra exhibit two resonance signals with effective g values at g  ≈  4.82 and g  ≈  1.99 and are attributed to isolated Cr3+ ions and exchange coupled Cr3+ pairs respectively. The number of spins along with susceptibility are also calculated from the EPR spectra.

The Role of Surface Tension in the Crystallization of Metal Halide Perovskites

KAUST Repository

Zhumekenov, Ayan A.; Burlakov, Victor M.; Saidaminov, Makhsud I.; Alofi, Abdulilah; Haque, Mohammed; Turedi, Bekir; Davaasuren, Bambar; Dursun, Ibrahim; Cho, Nam Chul; El-Zohry, Ahmed M.; de Bastiani, Michele; Giugni, Andrea; Torre, Bruno; Di Fabrizio, Enzo M.; Mohammed, Omar F.; Rothenberger, Alexander; Wu, Tao; Goriely, Alain; Bakr, Osman

2017-01-01

The exciting intrinsic properties discovered in single crystals of metal halide perovskites still await their translation into optoelectronic devices. The poor understanding and control of the crystallization process of these materials are current

Isotopic rubidium ion efflux assay for the functional characterization of nicotinic acetylcholine receptors on clonal cell lines

International Nuclear Information System (INIS)

Lukas, R.J.; Cullen, M.J.

1988-01-01

An isotopic rubidium ion efflux assay has been developed for the functional characterization of nicotinic acetylcholine receptors on cultured neurons. This assay first involves the intracellular sequestration of isotopic potassium ion analog by the ouabain-sensitive action of a sodium-potassium ATPase. Subsequently, the release of isotopic rubidium ion through nicotinic acetylcholine receptor-coupled monovalent cation channels is activated by application of nicotinic agonists. Specificity of receptor-mediated efflux is demonstrated by its sensitivity to blockade by nicotinic, but not muscarinic, antagonists. The time course of agonist-mediated efflux, within the temporal limitations of the assay, indicates a slow inactivation of receptor function on prolonged exposure to agonist. Dose-response profiles (i) have characteristic shapes for different nicotinic agonists, (ii) are described by three operationally defined parameters, and (iii) reflect different affinities of agonists for binding sites that control receptor activation and functional inhibition. The rubidium ion efflux assay provides fewer hazards but greater sensitivity and resolution than isotopic sodium or rubidium ion influx assays for functional nicotinic receptors

Monocrystallomimicry in the aerosols of ammonium and cesium halides

International Nuclear Information System (INIS)

Melikhov, I.V.; Kitova, E.N.; Kozlovskaya, EhD.; Kamenskaya, A.N.; Mikheev, N.B.; Kulyukhin, S.A.

1997-01-01

It is experimentally shown that initial CsI and NH 4 Hal nanocrystals combining into mixed aggregates of polyhedral form (pseudo monocrystals) are formed in the process of cocrystallization of ammonium halide and cesium iodide. The origination and growth of the pseudo monocrystals on the account of successive addition of initial crystals is described by the Fokker-Plank equation [ru

International collaboration to assess the risk of Guillain Barré Syndrome following Influenza A (H1N1) 2009 monovalent vaccines

NARCIS (Netherlands)

C. Dodd (Caitlin); S.A. Romio (Silvana); S. Black (Steve); C. Vellozzi (Claudia); N.J. Andrews (Nick); M.C.J.M. Sturkenboom (Miriam); P. Zuber (Patrick); W. Hua (Wei); J. Bonhoeffer (Jan); J. Buttery (Jim); N. Crawford (Nigel); G. Deceuninck (Genevieve); C.S. de Vries (Corinne); P. de Wals (Philippe); D. Gimeno (David); H. Heijbel (Harald); H. Hughes (Hayley); K. Hur (Kwan); A. Hviid (Anders); J. Kelman (Jeffrey); T. Kilpi (Tehri); S.K. Chuang (S.); T. Macartney (Thomas); M. Rett (Melisa); V.R. Lopez-Callada (Vesta Richardson); D. Salmon (Daniel); F.G. Sanchez (Francisco Gimenez); N. Sanz (Nuria); B. Silverman (Bernard); J. Storsaeter (Jann); U. Thirugnanam (Umapathi); N.A.T. van der Maas (Nicoline); K. Yih (Katherine); T. Zhang (Teng Fei); H.S. Izurieta (Hector); B.J. Addis; A. Akhtar (Aysha); J. Cope (Judith); R.L. Davis (Robert); P. Gargiullo (Paul); X. Kurz (Xavier); B. Law (Barbara); I. Sahinovic (Isabelle); J. Tokars (Jerry); P. Serrano (Pedro); A. Cheng (Aixin); N.J. Andrews (Nick); P. Charles (Pat); H. Clothier (Hazel); B. Day (Bruce); T. Day (Timothy); P. Gates (Peter); R. MacDonnell (Richard); L. Roberts (Les); V. Rodriguez-Casero (Vic-toria); T. Wijeratne (Tissa); H.A.L. Kiers (Henk); C. Blyth (Christopher); R. Booy (Robert); E. Elliott (Elizabeth); M.R. Gold (Michael); H. Marshall; P. McIntyre (Peter); P. Richmond (Peter); J. Royle (Jenny); N.W. Wood (Nicholas); Y. Zurynski (Yvonne); G. Calvo (Gonzalo); M. Campins (Magda); N. Corominas (Nuria); F. Torres (Ferran); V. Valls; A. Vilella (Ángels); A. Dutra (Amalia); A. Eick-Cost (Angelia); H.M. Jackson (Henry); K. Garman (Katherine); Z. Hu (Zheng); J. Rigo; J. Badoo (Judith); D Cho (David); L.L. Polakowski (Laura); S.K. Sandhu (Sukhminder); G. Sun (Guoying); H.-S.S. Chan (Hoi-Shan Sophelia); K.-Y. Chan (Kwok-Yin); R. Cheung (Raymond); Y-F. Cheung (Yuk-Fai); S. Cherk (Sharon); S.K Chuang (S.); D. Fok (Dennis); B.-H. Fung (Bun-Hey); K.-F. Ko (Kwai-Fu); K.W. Lau (Ka Wing); K.-K. Lau (Kwok-Kwong); P. Li (Pulin); H.-T. Liu (Hui-Tung); S.-H. Liu (Shao-Haei); K. Mok (Kin); J. So (Joanna); W. Wong (Winnie); S.-P. Wu (Shun-Ping); V. Avagyan (Vardan); R. Ball (Robert); D. Burwen (Dale); R.L. Franks (Riley); J.M. Gibbs (Jonathan); R.E. Kliman (Rebecca); S. Kropp (Silke); T.E. MaCurdy (Thomas); D.B. Martin (David); S.-D.K. Sandhu (Sukhmin-Der); B.B. Worrall (Bradford B.); D.E.F. Fuentes (Dra. Elvira Fuentes); P.C.O. González (Paola Carolina Ojeda); V.F. Reyna (Valerie ); M. Kulldorff (Martin); G. Lee (Grace); T.A. Lieu (Tracy); S. Platt; G.D. Serres (Gaston De); K. Jabin (Kamilah); B.L.S. Soh (Bee Leng Sally); L. Arnheim-Dahlström (Lisen); A. Castot (Anne); H.E. de Melker (Hester); J.P. Dieleman (Jeanne); J. Hallgren (Jonal); B.C. Jacobs (Bart); K. Johansen (Kari); P Kramarz (Piotr); M. Lapeyre (Maryse); T. Leino (Tuija); D. Mølgaard-Nielsen (Ditte); M. Mosseveld (Mees); H.K. Olberg (Henning K); C.-M. Sammon (Cor-Mac); C. Saussier (Christel); M.J. Schuemie (Martijn); A. Sommet (Agnès); P. Sparen (Pär); H. Svanström (Henrik); A.M. Vanrolleghem (Ann M.); D.M. Weibel (Daniel); J.D. Domingo (Javier Diez); J.L. Esparza (José LuísMicó); R.M.O. Lucas (Rafael M. Ortí); J.B.M. Maseres (Juan B. Mollar); J.L.A. Sánchez (José Luís Alfonso); M.G. Sánchez (Mercedes Garcés); V.Z. Viguer (Vicente Zanón); F. Cunningham (Francesca); B. Thakkar (Bharat); R. Zhang (Rongping)

2013-01-01

textabstractBackground: The global spread of the 2009 novel pandemic influenza A (H1N1) virus led to the accelerated production and distribution of monovalent 2009 Influenza A (H1N1) vaccines (pH1N1). This pandemic provided the opportunity to evaluate the risk of Guillain-Barré syndrome (GBS), which

Charge-charge liquid structure factor and the freezing of alkali halides

International Nuclear Information System (INIS)

March, N.H.; Tosi, M.P.

1980-10-01

The peak height of the charge-charge liquid structure factor Ssub(QQ) in molten alkali halides is proposed as a criterion for freezing. Available data on molten alkali chlorides, when extrapolated to the freezing point suggests Ssub(QQ)sup(max) approximately 5. (author)

Superconducting nitride halides MNX (M = Ti, Zr, Hf; X = Cl, Br, I)

Energy Technology Data Exchange (ETDEWEB)

Schurz, Christian M.; Shlyk, Larysa; Schleid, Thomas; Niewa, Rainer [Stuttgart Univ. (Germany). Inst. fuer Anorganische Chemie

2011-07-01

Two different polymorphs of the metal nitride halides MNX (M = Ti, Zr, Hf; X = Cl, Br, I) are known to crystallize in layered structures. The two crystal structures differ in the way {sub {infinity}}{sup 2}{l_brace}X[M{sub 2}N{sub 2}]X{r_brace} slabs are stacked along the c-axes. Metal atoms and/or organic molecules can be intercalated into the van-der-Waals gap between these layers. After such an electron-doping via intercalation the prototypic band insulators change into superconductors with moderate high critical temperatures T{sub c} up to 25.5 K. This review gathers information on synthesis routes, structural characteristics and properties of the prototypic nitride halides and the derivatives after electron-doping with a focus on superconductivity. (orig.)

Temperature dependent halogen activation by N2O5 reactions on halide-doped ice surfaces

Directory of Open Access Journals (Sweden)

J. A. Thornton

2012-06-01

Full Text Available We examined the reaction of N2O5 on frozen halide salt solutions as a function of temperature and composition using a coated wall flow tube technique coupled to a chemical ionization mass spectrometer (CIMS. The molar yield of photo-labile halogen compounds was near unity for almost all conditions studied, with the observed reaction products being nitryl chloride (ClNO2 and/or molecular bromine (Br2. The relative yield of ClNO2 and Br2 depended on the ratio of bromide to chloride ions in the solutions used to form the ice. At a bromide to chloride ion molar ratio greater than 1/30 in the starting solution, Br2 was the dominant product otherwise ClNO2 was primarily produced on these near pH-neutral brines. We demonstrate that the competition between chlorine and bromine activation is a function of the ice/brine temperature presumably due to the preferential precipitation of NaCl hydrates from the brine below 250 K. Our results provide new experimental confirmation that the chemical environment of the brine layer changes with temperature and that these changes can directly affect multiphase chemistry. These findings have implications for modeling air-snow-ice interactions in polar regions and likely in polluted mid-latitude regions during winter as well.

Holographic Optical Elements Recorded in Silver Halide Sensitized Gelatin Emulsions. Part I. Transmission Holographic Optical Elements

Science.gov (United States)

Kim, Jong Man; Choi, Byung So; Kim, Sun Il; Kim, Jong Min; Bjelkhagen, Hans I.; Phillips, Nicholas J.

2001-02-01

Silver halide sensitized gelatin (SHSG) holograms are similar to holograms recorded in dichromated gelatin (DCG), the main recording material for holographic optical elements (HOE s). The drawback of DCG is its low sensitivity and limited spectral response. Silver halide materials can be processed in such a way that the final hologram will have properties like a DCG hologram. Recently this technique has become more interesting since the introduction of new ultra-high-resolution silver halide emulsions. An optimized processing technique for transmission HOE s recorded in these materials is introduced. Diffraction efficiencies over 90% can be obtained for transmissive diffraction gratings. Understanding the importance of the selective hardening process has made it possible to obtain results similar to conventional DCG processing. The main advantage of the SHSG process is that high-sensitivity recording can be performed with laser wavelengths anywhere within the visible spectrum. This simplifies the manufacturing of high-quality, large-format HOE s.

Transport phenomena in metal-halide lamps : a poly-diagnostic study

NARCIS (Netherlands)

Nimalasuriya, T.

2007-01-01

Worldwide about 20% of all electricity is used for lighting. It is therefore of great interest to develop a lamp that has high e±cacy, good colour rendering and long lifetime. The metal-halide lamp is a gas discharge lamp that meets all these demands. Unfortunately there are still issues with this

HPLC determination of chloride, bromide and iodide ions in drinking water and industrial effluents using trifluoromethylmercuric nitrate as derivatizing reagent

International Nuclear Information System (INIS)

Arain, M.A.; Bhanger, M.I.; Khuhawar, M.Y.

1997-01-01

A simple procedure for the simultaneous determination of various halides in drinking water and industrial effluents of Hyderabad and Iodized salt is reported. The method utilizes derivatization of halides through trifluoromethylmercuric nitrate in aqueous solution, extraction in petroleum ether followed by reverse phase HPLC separation using c-18 Lichrosorb column, 150 x 4 mm i.d., mobile phase methanol : water (20: 80) and UV detection at 225 nm. Linear calibration ranges for chloride, bromide and iodide (0-10 ug/mL) with correlation coefficient 0.996, 0.998 and 0.989 have been determined with lowest possible detection limit as 1.0, 0.25 and 1.5 Mu g/ml, respectively. The effect of various interfering ions is also discussed. (author)

Inorganic Lead Halide Perovskite Single Crystals: Phase-Selective Low-Temperature Growth, Carrier Transport Properties, and Self-Powered Photodetection

KAUST Repository

Saidaminov, Makhsud I.

2016-12-06

A rapid, low-temperature, and solution-based route is developed for growing large-sized cesium lead halide perovskite single crystals under ambient conditions. An ultralow minority carrier concentration was measured in CsPbBr3 (≈108 holes per cm3, much lower than in any other lead halide perovskite and crystalline silicon), which enables to realize self-powered photodetectors with a high ON/OFF ratio (105).

Research Update: Physical and electrical characteristics of lead halide perovskites for solar cell applications

Directory of Open Access Journals (Sweden)

Simon A. Bretschneider

2014-04-01

Full Text Available The field of thin-film photovoltaics has been recently enriched by the introduction of lead halide perovskites as absorber materials, which allow low-cost synthesis of solar cells with efficiencies exceeding 16%. The exact impact of the perovskite crystal structure and composition on the optoelectronic properties of the material are not fully understood. Our progress report highlights the knowledge gained about lead halide perovskites with a focus on physical and optoelectronic properties. We discuss the crystal and band structure of perovskite materials currently implemented in solar cells and the impact of the crystal properties on ferroelectricity, ambipolarity, and the properties of excitons.

A Review of Luminescent Anionic Nano System: d10 Metallocyanide Excimers and Exciplexes in Alkali Halide Hosts

Directory of Open Access Journals (Sweden)

Howard H. Patterson

2013-06-01

Full Text Available Dicyanoaurate, dicyanoargentate, and dicyanocuprate ions in solution and doped in different alkali halide hosts exhibit interesting photophysical and photochemical behavior, such as multiple emission bands, exciplex tuning, optical memory, and thermochromism. This is attributed to the formation of different sizes of nanoclusters in solution and in doped hosts. A series of spectroscopic methods (luminescence, UV-reflectance, IR, and Raman as well as theoretical calculations have confirmed the existence of excimers and exciplexes. This leads to the tunability of these nano systems over a wide wavelength interval. The population of these nanoclusters varies with temperature and external laser irradiation, which explains the thermochromism and optical memory. DFT calculations indicate an MLCT transition for each nanocluster and the emission energy decreases with increasing cluster size. This is in agreement with the relatively long life-time for the emission peaks and the multiple emission peaks dependence upon cluster concentration.

A Review of Luminescent Anionic Nano System: d10 Metallocyanide Excimers and Exciplexes in Alkali Halide Hosts

Science.gov (United States)

Li, Xiaobo; Patterson, Howard H.

2013-01-01

Dicyanoaurate, dicyanoargentate, and dicyanocuprate ions in solution and doped in different alkali halide hosts exhibit interesting photophysical and photochemical behavior, such as multiple emission bands, exciplex tuning, optical memory, and thermochromism. This is attributed to the formation of different sizes of nanoclusters in solution and in doped hosts. A series of spectroscopic methods (luminescence, UV-reflectance, IR, and Raman) as well as theoretical calculations have confirmed the existence of excimers and exciplexes. This leads to the tunability of these nano systems over a wide wavelength interval. The population of these nanoclusters varies with temperature and external laser irradiation, which explains the thermochromism and optical memory. DFT calculations indicate an MLCT transition for each nanocluster and the emission energy decreases with increasing cluster size. This is in agreement with the relatively long life-time for the emission peaks and the multiple emission peaks dependence upon cluster concentration. PMID:28811397

Bis(morpholine) hydrogen bond pincer - a novel series of heteroleptic Cu(II) coordination compounds as receptors for electron rich guests

NARCIS (Netherlands)

Stilinovic, Vladimir; Uzarevic, Krunoslav; Cvrtila, Ivica; Kaitner, Branko

2012-01-01

Crystallisation from morpholine (morph) solutions of copper(II) salts with monovalent anions (A) and 1,3-diketones (Hdkt) yielded nine heteroleptic coordination compounds [Cu(dkt)(morph)(2)A]. The coordination polyhedron of the copper ion in these compounds is a square pyramid with a monovalent

Research Update: Luminescence in lead halide perovskites

Directory of Open Access Journals (Sweden)

Ajay Ram Srimath Kandada

2016-09-01

Full Text Available Efficiency and dynamics of radiative recombination of carriers are crucial figures of merit for optoelectronic materials. Following the recent success of lead halide perovskites in efficient photovoltaic and light emitting technologies, here we review some of the noted literature on the luminescence of this emerging class of materials. After outlining the theoretical formalism that is currently used to explain the carrier recombination dynamics, we review a few significant works which use photoluminescence as a tool to understand and optimize the operation of perovskite based optoelectronic devices.

Solvation of monovalent anions in formamide and methanol: Parameterization of the IEF-PCM model

International Nuclear Information System (INIS)

Boees, Elvis S.; Bernardi, Edson; Stassen, Hubert; Goncalves, Paulo F.B.

2008-01-01

The thermodynamics of solvation for a series of monovalent anions in formamide and methanol has been studied using the polarizable continuum model (PCM). The parameterization of this continuum model was guided by molecular dynamics simulations. The parameterized PCM model predicts the Gibbs free energies of solvation for 13 anions in formamide and 16 anions in methanol in very good agreement with experimental data. Two sets of atomic radii were tested in the definition of the solute cavities in the PCM and their performances are evaluated and discussed. Mean absolute deviations of the calculated free energies of solvation from the experimental values are in the range of 1.3-2.1 kcal/mol

Effects of metal ions on the catalytic degradation of dicofol by cellulase.

Science.gov (United States)

Zhai, Zihan; Yang, Ting; Zhang, Boya; Zhang, Jianbo

2015-07-01

A new technique whereby cellulase immobilized on aminated silica was applied to catalyze the degradation of dicofol, an organochlorine pesticide. In order to evaluate the performance of free and immobilized cellulase, experiments were carried out to measure the degradation efficiency. The Michaelis constant, Km, of the reaction catalyzed by immobilized cellulase was 9.16 mg/L, and the maximum reaction rate, Vmax, was 0.40 mg/L/min, while that of free cellulase was Km=8.18 mg/L, and Vmax=0.79 mg/L/min, respectively. The kinetic constants of catalytic degradation were calculated to estimate substrate affinity. Considering that metal ions may affect enzyme activity, the effects of different metal ions on the catalytic degradation efficiency were explored. The results showed that the substrate affinity decreased after immobilization. Monovalent metal ions had no effect on the reaction, while divalent metal ions had either positive or inhibitory effects, including activation by Mn2+, reversible competition with Cd2+, and irreversible inhibition by Pb2+. Ca2+ promoted the catalytic degradation of dicofol at low concentrations, but inhibited it at high concentrations. Compared with free cellulase, immobilized cellulase was affected less by metal ions. This work provided a basis for further studies on the co-occurrence of endocrine-disrupting chemicals and heavy metal ions in the environment. Copyright © 2015. Published by Elsevier B.V.

Calculation of ion currents across the inner membrane of functionally intact mitochondria

Science.gov (United States)

Kane, Daniel A; Pavlov, Evgeny V

2013-01-01

Mitochondrial ion transport systems play a central role in cell physiology. Rates of Ca2+ and K+ transport across the inner mitochondrial membrane have been derived from the measurement of ion accumulation over time within functional isolated mitochondria or mitochondria of cultured cells. Alternatively, the electrical currents generated by ionic flux have been directly measured in purified and swollen mitochondrial samples (mitoplasts) or reconstituted channels, and typically range from 1 pA to several 100s pA. However, the direct electrophysiological approach necessarily requires extensive processing of the mitochondria prior to measurement, which can only be performed on isolated mitoplasts. To compare rates of mitochondrial ion transport measured in electrophysiological experiments to those measured in intact mitochondria and cells, we converted published rates of mitochondrial ion uptake into units of ionic current. We estimate that for monovalent ions, uptake by intact mitochondria at the rate of 1 nmol ∙ mg−1 protein ∙ min−1 is equivalent to 0.2 fA of current per whole single mitochondrion (0.4 fA for divalent ions). In intact mitochondria, estimated rates of electrogenic cation uptake are limited to 1–100 fA of integral current per single mitochondrion. These estimates are orders of magnitude lower than the currents through mitochondrial channels directly measured via patch-clamp or artificial lipid bilayer approaches. PMID:24037064

Metal-halide lamp design: atomic and molecular data needed

International Nuclear Information System (INIS)

Lapatovich, Walter P

2009-01-01

Metal-halide lamps are a subset of high intensity discharge (HID) lamps so named because of their high radiance. These lamps are low temperature (∼0.5 eV), weakly ionized plasmas sustained in refractory but light transmissive envelopes by the passage of electric current through atomic and molecular vapors. For commercial applications, the conversion of electric power to light must occur with good efficiency and with sufficient spectral content throughout the visible (380-780 nm) to permit the light so generated to render colors comparable to natural sunlight. This is achieved by adding multiple metals to a basic mercury discharge. Because the vapor pressure of most metals is very much lower than mercury itself, metal-halide salts of the desired metals, having higher vapor pressures, are used to introduce the material into the basic discharge. The metal compounds are usually polyatomic iodides, which vaporize and subsequently dissociate as they diffuse into the bulk plasma. Metals with multiple visible transitions are necessary to achieve high photometric efficiency (efficacy) and good color. Compounds of Sc, Dy, Ho, Tm, Ce, Pr, Yb and Nd are commonly used. The electrons, atoms and radicals are in local thermodynamic equilibrium (LTE), but not with the radiation field. Strong thermal (10 6 K m -1 ) and density gradients are sustained in the discharge. Atomic radiation produced in the high-temperature core transits through colder gas regions where it interacts with cold atoms and un-dissociated molecules before exiting the lamp. Power balance and spectral output of the lamp are directly affected by the strength of atomic transitions. Attempts to simulate the radiative output of functional metal-halide lamps have been successful only in very simple cases. More data (e.g. the atomic transition probabilities of Ce i) are necessary to improve lamp performance, to select appropriate radiators and in scaling the lamp geometry to various wattages for specific applications.

Thermoluminescence response of a mixed ternary alkali halide crystals exposed to gamma rays

International Nuclear Information System (INIS)

Rodriguez M, R.; Perez S, R.; Vazquez P, G.; Riveros, H.; Gonzalez M, P.

2014-08-01

Ionic crystals, mainly alkali halide crystals have been the subject of intense research for a better understanding of the luminescence properties of defects induced by ionizing radiation. The defects in crystals can be produced in appreciable concentration due to elastic stresses, radiation, and addition of impurities. These defects exhibit remarkable thermoluminescence properties. This work is concerned with the Tl properties of a ternary alkali halide crystal after being irradiated with gamma and beta rays. It has been found that the Tl glow peak of the crystal follows a rule of average associated to the Tl Temperatures of the components of the mixture, similarly to the response of europium doped binary mixed crystals KCl x KBr 1-x and KBr x RbBr 1-x . (Author)

Mimicking the cell membrane: bio-inspired simultaneous functions with monovalent anion selectivity and antifouling properties of anion exchange membrane

Science.gov (United States)

Zhao, Yan; Liu, Huimin; Tang, Kaini; Jin, Yali; Pan, Jiefeng; der Bruggen, Bart Van; Shen, Jiangnan; Gao, Congjie

2016-01-01

A new bio-inspired method was applied in this study to simultaneously improve the monovalent anion selectivity and antifouling properties of anion exchange membranes (AEMs). Three-layer architecture was developed by deposition of polydopamine (PDA) and electro-deposition of N-O-sulfonic acid benzyl chitosan (NSBC). The innermost and outermost layers were PDA with different deposition time. The middle layer was prepared by NSBC. Fourier transform infrared spectroscopy and scanning electron microscopy confirmed that PDA and NSBC were successfully modified on the surfaces of AEMs. The contact angle of the membranes indicated an improved hydrophilicity of the modified membranes. A series of electrodialysis experiments in which Cl−/SO42− separation was studied, demonstrating the monovalent anion selectivity of the samples. The Cl−/SO42− permselectivity of the modified membranes can reach up to 2.20, higher than that of the commercial membrane (only 0.78) during 90 minutes in electrodialysis (ED). The increase value of the resistance of the membranes was also measured to evaluate the antifouling properties. Sodium dodecyl benzene sulfonate (SDBS) was used as the fouling material in the ED process and the membrane area resistance of modified membrane increase value of was only 0.08 Ωcm2 30 minutes later. PMID:27853255

Mimicking the cell membrane: bio-inspired simultaneous functions with monovalent anion selectivity and antifouling properties of anion exchange membrane

Science.gov (United States)

Zhao, Yan; Liu, Huimin; Tang, Kaini; Jin, Yali; Pan, Jiefeng; der Bruggen, Bart Van; Shen, Jiangnan; Gao, Congjie

2016-11-01

A new bio-inspired method was applied in this study to simultaneously improve the monovalent anion selectivity and antifouling properties of anion exchange membranes (AEMs). Three-layer architecture was developed by deposition of polydopamine (PDA) and electro-deposition of N-O-sulfonic acid benzyl chitosan (NSBC). The innermost and outermost layers were PDA with different deposition time. The middle layer was prepared by NSBC. Fourier transform infrared spectroscopy and scanning electron microscopy confirmed that PDA and NSBC were successfully modified on the surfaces of AEMs. The contact angle of the membranes indicated an improved hydrophilicity of the modified membranes. A series of electrodialysis experiments in which Cl-/SO42- separation was studied, demonstrating the monovalent anion selectivity of the samples. The Cl-/SO42- permselectivity of the modified membranes can reach up to 2.20, higher than that of the commercial membrane (only 0.78) during 90 minutes in electrodialysis (ED). The increase value of the resistance of the membranes was also measured to evaluate the antifouling properties. Sodium dodecyl benzene sulfonate (SDBS) was used as the fouling material in the ED process and the membrane area resistance of modified membrane increase value of was only 0.08 Ωcm2 30 minutes later.

Students' Understanding of Alkyl Halide Reactions in Undergraduate Organic Chemistry

Science.gov (United States)

Cruz-Ramírez de Arellano, Daniel; Towns, Marcy H.

2014-01-01

Organic chemistry is an essential subject for many undergraduate students completing degrees in science, engineering, and pre-professional programs. However, students often struggle with the concepts and skills required to successfully solve organic chemistry exercises. Since alkyl halides are traditionally the first functional group that is…

Epitaxial Growth of a Methoxy-Functionalized Quaterphenylene on Alkali Halide Surfaces

DEFF Research Database (Denmark)

Balzer, Frank; Sun, Rong; Parisi, Jürgen

2015-01-01

The epitaxial growth of the methoxy functionalized para-quaterphenylene (MOP4) on the (001) faces of the alkali halides NaCl and KCl and on glass is investigated by a combination of lowenergy electron diffraction (LEED), polarized light microscopy (PLM), atomic force microscopy (AFM), and X...

Solvation of positive ions in water: the dominant role of water-water interaction

International Nuclear Information System (INIS)

Krekeler, Christian; Site, Luigi Delle

2007-01-01

Local polarization effects, induced by monovalent and divalent positive ions in water, influence (and in turn are influenced by) the large-scale structural properties of the solvent. Experiments can only distinguish this process of interplay in a generic qualitative way. Instead, first-principles calculations can address the question at both the electronic and atomistic scale, accounting for electronic polarization as well as geometrical conformations. For this reason we study the extension of the scales' interconnection by means of first-principle Car-Parrinello molecular dynamics applied to systems of different size. In this way we identify the general aspects dominating the physics of the first solvation shell and their connection to the effects related to the formation of the outer shells and eventually the bulk. We show that while the influence of the ions is extended to the first shell only, the water-water interaction is instead playing a dominant role even within the first shell independently of the size or the charge of the ion. (fast track communication)

Structural stability, acidity, and halide selectivity of the fluoride riboswitch recognition site

KAUST Repository

Chawla, Mohit

2015-01-14

Using static and dynamics DFT methods we show that the Mg2+/F-/phosphate/water cluster at the center of the fluoride riboswitch is stable by its own and, once assembled, does not rely on any additional factor from the overall RNA fold. Further, we predict that the pKa of the water molecule bridging two Mg cations is around 8.4. We also demonstrate that the halide selectivity of the fluoride riboswitch is determined by the stronger Mg-F bond, which is capable of keeping together the cluster. Replacing F- with Cl- results in a cluster that is unstable under dynamic conditions. Similar conclusions on the structure and energetics of the cluster in the binding pocket of fluoride-inhibited pyrophosphatase suggest that the peculiarity of fluoride is in its ability to establish much stronger metal-halide bonds.

Structural stability, acidity, and halide selectivity of the fluoride riboswitch recognition site

KAUST Repository

Chawla, Mohit; Credendino, Raffaele; Poater, Albert; Oliva, Romina M.; Cavallo, Luigi

2015-01-01

Using static and dynamics DFT methods we show that the Mg2+/F-/phosphate/water cluster at the center of the fluoride riboswitch is stable by its own and, once assembled, does not rely on any additional factor from the overall RNA fold. Further, we predict that the pKa of the water molecule bridging two Mg cations is around 8.4. We also demonstrate that the halide selectivity of the fluoride riboswitch is determined by the stronger Mg-F bond, which is capable of keeping together the cluster. Replacing F- with Cl- results in a cluster that is unstable under dynamic conditions. Similar conclusions on the structure and energetics of the cluster in the binding pocket of fluoride-inhibited pyrophosphatase suggest that the peculiarity of fluoride is in its ability to establish much stronger metal-halide bonds.

Metal-Mediated Halogen Exchange in Aryl and Vinyl Halides: a Review

Science.gov (United States)

Evano, Gwilherm; Nitelet, Antoine; Thilmany, Pierre; Dewez, Damien F.

2018-04-01

Halogenated arenes and alkenes are of prime importance in many areas of science, especially in the pharmaceutical, agrochemical and chemical industries. While the simplest ones are commercially available, some of them are still hardly accessible depending on their substitution patterns and the nature of the halogen atom. Reactions enabling the selective and efficient replacement of the halogen atom of an aryl or alkenyl halide by another one, lighter or heavier, are therefore of major importance since they can be used for example to turn a less reactive aryl/alkenyl chloride into the more reactive iodinated derivatives or, in a reversed sense, to block an undesired reactivity, for late-stage modifications or for the introduction of a radionuclide. If some halogen exchange reactions are possible with activated substrates, they usually require catalysis with metal complexes. Remarkably efficient processes have been developed for metal-mediated halogen exchange in aryl and vinyl halides: they are overviewed, in a comprehensive manner, in this review article.

Antimicrobial properties of zeolite-X and zeolite-A ion-exchanged with silver, copper, and zinc against a broad range of microorganisms.

Science.gov (United States)

Demirci, Selami; Ustaoğlu, Zeynep; Yılmazer, Gonca Altın; Sahin, Fikrettin; Baç, Nurcan

2014-02-01

Zeolites are nanoporous alumina silicates composed of silicon, aluminum, and oxygen in a framework with cations, water within pores. Their cation contents can be exchanged with monovalent or divalent ions. In the present study, the antimicrobial (antibacterial, anticandidal, and antifungal) properties of zeolite type X and A, with different Al/Si ratio, ion exchanged with Ag(+), Zn(2+), and Cu(2+) ions were investigated individually. The study presents the synthesis and manufacture of four different zeolite types characterized by scanning electron microscopy and X-ray diffraction. The ion loading capacity of the zeolites was examined and compared with the antimicrobial characteristics against a broad range of microorganisms including bacteria, yeast, and mold. It was observed that Ag(+) ion-loaded zeolites exhibited more antibacterial activity with respect to other metal ion-embedded zeolite samples. The results clearly support that various synthetic zeolites can be ion exchanged with Ag(+), Zn(2+), and Cu(2+) ions to acquire antimicrobial properties or ion-releasing characteristics to provide prolonged or stronger activity. The current study suggested that zeolite formulations could be combined with various materials used in manufacturing medical devices, surfaces, textiles, or household items where antimicrobial properties are required.

Tailoring Mixed-Halide, Wide-Gap Perovskites via Multistep Conversion Process

NARCIS (Netherlands)

Bae, D.; Palmstrom, A.; Roelofs, K.; Mei, Bastian Timo; Chorkendorf, I.; Bent, S.F.; Vesborg, P.C.

2016-01-01

Wide-band-gap mixed-halide CH3NH3PbI3–XBrX-based solar cells have been prepared by means of a sequential spin-coating process. The spin-rate for PbI2 as well as its repetitive deposition are important in determining the cross-sectional shape and surface morphology of perovskite, and, consequently,

Homocoupling of benzyl halides catalyzed by POCOP-nickel pincer complexes

KAUST Repository

Chen, Tao

2012-08-01

Two types of POCOP-nickel(II) pincer complexes were prepared by mixing POCOP pincer ligands and NiX 2 in toluene at reflux. The resulting nickel complexes efficiently catalyze the homocoupling reactions of benzyl halides in the presence of zinc. The coupled products were obtained in excellent to quantitative yields. © 2012 Elsevier Ltd. All rights reserved.

Enthalpic pairwise self-association of L-carnitine in aqueous solutions of some alkali halides at T = 298.15 K

International Nuclear Information System (INIS)

Wang, Hua-Qin; Cheng, Wei-Na; Zhu, Li-Yuan; Hu, Xin-Gen

2016-01-01

Highlights: • Dilution enthalpies of L-carnitine in aqueous alkali halide solutions by ITC. • The second virial coefficients of enthalpy (h_2) have been calculated. • The values of h_2 increase with increasing molalities of aqueous salt solutions. • The signs of h_2 turn from negative in pure water to positive in salt solutions. • The trends is ascribed to the salt effects on pairwise self-associations. - Abstract: Knowledge of the influence of ions of various nature on intermolecular hydrophilic and hydrophobic interactions in solutions is required in many research fields. In this paper, dilution enthalpies of zwitterion L-carnitine in aqueous NaCl, KCl and NaBr solutions of various molalities (b = 0 to 3.0 mol · kg"−"1) have been determined respectively at T = (298.15 ± 0.01) K and p = (0.100 ± 0.005) MPa by isothermal titration calorimetry (ITC). In light of the MacMillan–Mayer theory, the 2nd virial enthalpic coefficients (h_2) have been calculated. The h_2 coefficients increase gradually with increasing molality (b) of the three aqueous alkali halides solutions, from small negative values in pure water to relatively larger positive values in solution. The trends of h_2 coefficients are ascribed to the salt effects on the balance between hydrophilic and hydrophobic interactions in pairwise self-associations. It is considered that the size of cations and anions exert influences on h_2 coefficients through their surface charge densities and hydration (or dehydration) abilities.

Removal of radioactive ions from nuclear waste solutions by electrodialysis

Energy Technology Data Exchange (ETDEWEB)

Sugimoto, S [Radia Industries Co. Ltd., Takasaki, Gunma (Japan)

1978-10-01

Removal of radioactive ions was studied from low and medium level radioactive waste solutions by electrodialysis using ion exchange membranes. The test solutions contained /sup 137/Cs/sup +/, /sup 106/Ru/sup 3 +/ or fission products (F.P.) as active ions and NaCl, Na/sub 2/SO/sub 4/ or Ca(NO/sub 3/)/sub 2/ as inactive coexisting salts. The decontamination factor of the active ions was in the order: /sup 137/Cs/sup +/ (greater than 99%) > /sup 90/Sr/sup 2 +/ > F.P. > /sup 106/Ru/sup 3 +/. The dialysis time required to attain the saturation was the shortest for monovalent cations K/sup +/, Cs/sup +/ and Na/sup +/, intermediate for divalent cation Sr/sup 2 +/, and the longest for trivalent cation Ru/sup 3 +/. The ratio of the decontamination factor of an active ion eta sub( a) to the desalination factor of an inactive ion eta sub( b) was nearly equal to unity for /sup 24/Na, /sup 42/K, /sup 137/Cs and /sup 90/Sr. On the other hand, the apparent selective permeability of an active ion (A/sup +/) against Na/sup +/ ion, T sub(Na/sup +/) sup( a) was higher than unity for all the active ions tested, and was in the order of /sup 137/Cs > /sup 90/Sr > /sup 42/K > /sup 24/Na, where T sub(Na/sup +/) sup( a) is defined by the ratio of ..gamma..sub( a) to ..gamma..sub(Na/sup +/) with ..gamma..sub( a) being the ratio of dilution of A in the diluate the ..gamma..sub(Na/sup +/) being that of Na/sup +/ in the same diluate. The decontamination factor of the active ions did not depend significantly on the species and concentration of the coexistent salts or on the concentration of the active ions.

Inverse kinetic solvent isotope effect in TiO2 photocatalytic dehalogenation of non-adsorbable aromatic halides: a proton-induced pathway.

Science.gov (United States)

Chang, Wei; Sun, Chunyan; Pang, Xibin; Sheng, Hua; Li, Yue; Ji, Hongwei; Song, Wenjing; Chen, Chuncheng; Ma, Wanhong; Zhao, Jincai

2015-02-09

An efficient redox reaction between organic substrates in solution and photoinduced h(+) vb /e(-) cb on the surface of photocatalysts requires the substrates or solvent to be adsorbed onto the surface, and is consequentially marked by a normal kinetic solvent isotope effect (KSIE ≥ 1). Reported herein is a universal inverse KSIE (0.6-0.8 at 298 K) for the reductive dehalogenation of aromatic halides which cannot adsorb onto TiO2 in a [D0 ]methanol/[D4 ]methanol solution. Combined with in situ ATR-FTIR spectroscopy investigations, a previously unknown pathway for the transformation of these aromatic halides in TiO2 photocatalysis was identified: a proton adduct intermediate, induced by released H(+) /D(+) from solvent oxidation, accompanies a change in hybridization from sp(2) to sp(3) at a carbon atom of the aromatic halides. The protonation event leads these aromatic halides to adsorb onto the TiO2 surface and an ET reaction to form dehalogenated products follows. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

First-principles thermodynamics study of phase stability in inorganic halide perovskite solid solutions

Science.gov (United States)

Bechtel, Jonathon S.; Van der Ven, Anton

2018-04-01

Halide substitution gives rise to a tunable band gap as a function of composition in halide perovskite materials. However, photoinduced phase segregation, observed at room temperature in mixed halide A Pb (IxBr1-x) 3 systems, limits open circuit voltages and decreases photovoltaic device efficiencies. We investigate equilibrium phase stability of orthorhombic P n m a γ -phase CsM (XxY1-x) 3 perovskites where M is Pb or Sn, and X and Y are Br, Cl, or I. Finite-temperature phase diagrams are constructed using a cluster expansion effective Hamiltonian parameterized from first-principles density-functional-theory calculations. Solid solution phases for CsM (IxBr1-x) 3 and CsM (BrxCl1-x) 3 are predicted to be stable well below room temperature while CsM (IxCl1-x) 3 systems have miscibility gaps that extend above 400 K. The height of the miscibility gap correlates with the difference in volume between end members. Also layered ground states are found on the convex hull at x =2 /3 for CsSnBr2Cl ,CsPbI2Br , and CsPbBrCl2. The impact of these ground states on the finite temperature phase diagram is discussed in the context of the experimentally observed photoinduced phase segregation.

Rocksalt or cesium chloride: Investigating the relative stability of the cesium halide structures with random phase approximation based methods

Science.gov (United States)

Nepal, Niraj K.; Ruzsinszky, Adrienn; Bates, Jefferson E.

2018-03-01

The ground state structural and energetic properties for rocksalt and cesium chloride phases of the cesium halides were explored using the random phase approximation (RPA) and beyond-RPA methods to benchmark the nonempirical SCAN meta-GGA and its empirical dispersion corrections. The importance of nonadditivity and higher-order multipole moments of dispersion in these systems is discussed. RPA generally predicts the equilibrium volume for these halides within 2.4% of the experimental value, while beyond-RPA methods utilizing the renormalized adiabatic LDA (rALDA) exchange-correlation kernel are typically within 1.8%. The zero-point vibrational energy is small and shows that the stability of these halides is purely due to electronic correlation effects. The rAPBE kernel as a correction to RPA overestimates the equilibrium volume and could not predict the correct phase ordering in the case of cesium chloride, while the rALDA kernel consistently predicted results in agreement with the experiment for all of the halides. However, due to its reasonable accuracy with lower computational cost, SCAN+rVV10 proved to be a good alternative to the RPA-like methods for describing the properties of these ionic solids.

Ground state depletion – A step towards mid-IR lasing of doped silver halides

Energy Technology Data Exchange (ETDEWEB)

Tsur, Yuval, E-mail: yuvaltsu@post.tau.ac.il [Raymond and Beverly Sackler Faculty of Exact Sciences, Tel-Aviv University, Tel-Aviv 6997801 (Israel); Goldring, Sharone [Applied Physics Division, Soreq NRC, Yavne 81800 (Israel); Galun, Ehud [DDR& D, Ministry of Defense (Israel); Katzir, Abraham [Raymond and Beverly Sackler Faculty of Exact Sciences, Tel-Aviv University, Tel-Aviv 6997801 (Israel)

2016-07-15

We show for the first time ground state absorption saturation in a doped silver halide crystal (AgCl{sub x}Br{sub 1−x}), specifically with cobalt. Spectroscopic studies showed absorption bands in the 1.4–2.5 μm region and emission bands in the 3.8–5.0 μm region, with a 1.5 ms lifetime at low temperatures. Absorption saturation indicates a good low and room temperature lasing feasibility at 4.1 μm. In addition, a comparison of cobalt, nickel and iron as dopants is presented. These doped silver halide crystals can be extruded to form optical fibers, possibly introducing a new family of fiber lasers for the middle infrared.

A mild and efficient procedure for the synthesis of ethers from various alkyl halides

Directory of Open Access Journals (Sweden)

Mosstafa Kazemi

2013-10-01

Full Text Available A simple, mild and practical procedure has been developed for the synthesis of symmetrical and unsymmetrical ethers by using DMSO, TBAI in the presence of K2CO3. We extended the utility of Potassium carbonate as an efficient base for the preparation of ethers. A wide range of alkyl aryl and dialkyl ethers are synthezied from treatment of aliphatic alcohols and phenols with various alkyl halides in the prescence of efficient base Potassium carbonate. Secondary alkyl halides were easily converted to corresponding ethers in releatively good yields . This is a mild, simple and practical procedure for the preparation of ethers in high yields and suitable times under mild condition.

Investigation of sodalites for conditioning halide salts (NaCl and NaI): Comparison of two synthesis routes

Energy Technology Data Exchange (ETDEWEB)

Bardez, Isabelle; Campayo, Lionel; Rigaud, Danielle; Chartier, Myriam; Calvet, Aurelie [CEA, Laboratoire d' Etudes des Materiaux Ceramiques pour le Conditionnement, Site de Marcoule, Batiment 208, B.P. 17171, 30207 Bagnols sur Ceze cedex (France)

2008-07-01

Sodalites with the general formula Na{sub 8}Al{sub 6}Si{sub 6}O{sub 24}X{sub 2} (where X = Cl or I) were investigated for ceramic conditioning of halide salts (NaCl and NaI). Because of the tendency of halides to volatilize at high temperature, two synthesis routes were tested to optimize the halide content in the sodalite phase. The first is based on heating at high temperature of a [nepheline NaAlSiO{sub 4} + salt] mixture prepared by a dry process. The second, performed at low temperature, consists of the reaction in aqueous media between kaolinite (Al{sub 2}Si{sub 2}O{sub 5}(OH){sub 4}), sodium hydroxide (NaOH) and the salt. The present study compares these two syntheses and examines differences between chloro-sodalite and iodo-sodalite based on X-ray diffraction and infrared spectroscopy. The next step will consist in sintering the resulting powder samples to obtain dense ceramics. (authors)

Impact of the organic halide salt on final perovskite composition for photovoltaic applications

KAUST Repository

Moore, David T.; Sai, Hiroaki; Wee Tan, Kwan; Estroff, Lara A.; Wiesner, Ulrich

2014-01-01

The methylammonium lead halide perovskites have shown significant promise as a low-cost, second generation, photovoltaic material.Despite recent advances, however, there are still a number of fundamental aspects of their formation as well

Long-wavelength limit of the static structure factors for mixtures of two simple molten salts with a common ion and generalized Bhatia-Thornton formalism: Molecular dynamics study of molten mixture Ag(Br0.7I0.3)

International Nuclear Information System (INIS)

Bitrian, Vicente; Trullas, Joaquim; Silbert, Moises

2008-01-01

The relation between thermodynamic properties and the long-wavelength limit of the structure factors for mixtures of two simple molten salts with a common ion is derived. While the long-wavelength limit of the partial structure factors for binary ionic systems is directly related to the isothermal compressibility, for ternary ionic systems it is shown that it is also related to the mean square thermal fluctuation in the relative concentration of the non-common ions. This result leads to a generalization of the Bhatia-Thornton formalism. From the local fluctuations in the total number-density, charge-density, and relative concentration, six static structure factors, and the corresponding spatial correlation functions, are defined. By introducing three complementary structure factors, it is possible to describe either these mixtures as a system of cations and anions irrespective of the species of the non-common ions, or solely the binary subsystem of the non-common ions. The generalized structure factors and their long-wavelength limits are illustrated by molecular dynamics simulation results of the molten mixture Ag(Br 0.7 I 0.3 ). The mixture retains the charge order characteristic of pure molten monovalent salts and the topological order observed in monovalent ionic melts in which the cations are smaller than the anions, while the main trends of the anionic chemical order are those of simple binary alloys. The long-wavelength fluctuations in the local relative concentration are found to be very sensitive to the choice of the short-range interactions between the non-common ions

(e,2e) momentum spectroscopic study of the C=C π orbitals of the vinyl halides

International Nuclear Information System (INIS)

Gorunganthu, R.R.; Coplan, M.A.; Leung, K.T.; Tossell, J.A.; Moore, J.H.; Department of Chemistry, University of Waterloo, Waterloo, Ontario N2L 3G1, Canada; Department of Chemistry, University of Maryland, College Park, Maryland 20742)

1989-01-01

The distribution of electron momentum density has been measured for the outermost occupied orbitals of the vinyl halides and ethylene using the (e,2e) technique. In contrast to the ionization potentials for these π orbitals which decrease monotonically from vinyl fluoride to vinyl iodide, the values of the momenta where the distributions are a maximum, p max , increase from the fluoride through the bromide and then shift back to a lower value for the iodide. This observation can be analyzed in terms of B(r), the Fourier transform of the observed momentum distribution, and ΔB(r), the difference between B(r) functions. The shape of ΔB(r) for the fluoride, chloride, and bromide in comparison to ethylene reflects the effect of the carbon--halogen antibonding interaction in these vinyl halides. On the other hand, in vinyl iodide the antibonding interaction is compensated for by the diffuse iodine 5p character of the molecular orbital. The relation of these observations to chemical properties of the vinyl halides is discussed along with differences between experiment and calculations at low momentum

Thermoluminescence response of a mixed ternary alkali halide crystals exposed to gamma rays

Energy Technology Data Exchange (ETDEWEB)

Rodriguez M, R.; Perez S, R. [Universidad de Sonora, Departamento de Investigacion en Fisica, Apdo. Postal 5-088, 83190 Hermosillo, Sonora (Mexico); Vazquez P, G.; Riveros, H. [UNAM, Instituto de Fisica, Apdo. Postal 20-364, 01000 Mexico D. F. (Mexico); Gonzalez M, P., E-mail: mijangos@cifus.uson.mx [ININ, Carretera Mexico-Toluca s/n, 52750 Ocoyoacac, Estado de Mexico (Mexico)

2014-08-15

Ionic crystals, mainly alkali halide crystals have been the subject of intense research for a better understanding of the luminescence properties of defects induced by ionizing radiation. The defects in crystals can be produced in appreciable concentration due to elastic stresses, radiation, and addition of impurities. These defects exhibit remarkable thermoluminescence properties. This work is concerned with the Tl properties of a ternary alkali halide crystal after being irradiated with gamma and beta rays. It has been found that the Tl glow peak of the crystal follows a rule of average associated to the Tl Temperatures of the components of the mixture, similarly to the response of europium doped binary mixed crystals KCl{sub x}KBr{sub 1-x} and KBr{sub x}RbBr{sub 1-x}. (Author)

Sustained release of antibiotic complexed by multivalent ion: in vitro and in vivo study for the treatment of peritonitis.

Science.gov (United States)

Na, Seung Yeon; Oh, Se Heang; Kim, Tae Ho; Yoon, Jin A; Lee, In Soo; Lee, Jin Ho

2014-12-10

The main aims of this study are (i) the development of an antibiotic complexed with multivalent ion, which can allow sustained release of the antibiotic without any additional matrix or difficult process and (ii) the feasibility study of the ion-complexed antibiotic as a therapeutic technique for peritonitis treatment. An ion-complexed antibiotic is prepared by simple mixing of two aqueous solutions containing an ionized (water-soluble) drug (tetracycline) and a multivalent counter ionic compound. The ion-complexed antibiotic shows a continuous release of the antibiotic up to 21 days, and thus prolonged anti-bacterial effect by gradual ionic exchange between the multivalent ions in the complex and same-charged monovalent ions in surrounding medium. From the in vivo animal study using a cecum perforated peritonitis mouse model, the ion-complexed antibiotic group shows sufficient anti-bacterial effect and thus effectively treat the peritonitis because of the extermination of the contaminated enteric bacteria in the peritoneum during wound healing of injury cecum (by the sustained release of antibiotic from the ion complex). These results suggest that the ion-complexed antibiotic system may be promising for the effective treatment of the peritonitis caused by frequent gastrointestinal defect in clinical fields. Copyright © 2014 Elsevier B.V. All rights reserved.

Designing mixed metal halide ammines for ammonia storage using density functional theory and genetic algorithms

DEFF Research Database (Denmark)

Jensen, Peter Bjerre; Lysgaard, Steen; Quaade, Ulrich J.

2014-01-01

electrolyte membrane fuel cells (PEMFC). We use genetic algorithms (GAs) to search for materials containing up to three different metals (alkaline-earth, 3d and 4d) and two different halides (Cl, Br and I) – almost 27000 combinations, and have identified novel mixtures, with significantly improved storage......Metal halide ammines have great potential as a future, high-density energy carrier in vehicles. So far known materials, e.g. Mg(NH3)6Cl2 and Sr(NH3)8Cl2, are not suitable for automotive, fuel cell applications, because the release of ammonia is a multi-step reaction, requiring too much heat...

Modulation of electronic and optical properties in mixed halide perovskites CsPbCl3xBr3(1-x) and CsPbBr3xI3(1-x)

Science.gov (United States)

Zhou, Ziqi; Cui, Yu; Deng, Hui-Xiong; Huang, Le; Wei, Zhongming; Li, Jingbo

2017-03-01

The recent discovery of lead halide perovskites with band gaps in the visible presents important potential in the design of high efficient solar cells. CsPbCl3, CsPbBr3 and CsPbI3 are stable compounds within this new family of semiconductors. By performing the first-principles calculation, we explore the structural, electronic and optical properties of CsPbCl3xBr3(1-x) and CsPbBr3xI3(1-x) with various compositions of halide atoms. Structural stability is demonstrated with halide atoms distributing randomly at the halide atomic sites. CsPbCl3xBr3(1-x) and CsPbBr3xI3(1-x) exhibit the modulation of their band gaps by varying the halide composition. Our results also indicate that CsPbCl3xBr3(1-x) and CsPbBr3xI3(1-x) with different halide compositions are suitable to application to solar cells for the general features are well preserved. Good absorption to lights of different wavelengths has been obtained in these mixed halide perovskites.

Effects of the material composition in the TL curves of alkaline halides with Eu2+ exposed to β radiation

International Nuclear Information System (INIS)

Perez S, R.; Piters, T.; Aceves, R.; Rodriguez M, R.

2006-01-01

The solid state dosemeters plays a very important paper in the growing use of the ionizing radiation. When being increased the use of the radioactive isotopes in the medicine and in the industry, the necessity to have materials but adapted in each case it has increased. To synthesize such materials, it is necessary to enlarge the knowledge on the paper that its play the physical characteristics of the crystals such as the crystalline structure, the lattice constant, imbibed nano structures, dislocations, ions size, electronic states of the ions, etc., on the effects of the ionizing radiation. In the past its have been carried out many studies approaching these problems in some materials, but we consider that its are insufficient before the challenges of the applications. To contribute to the understanding of these effects, we present a study focused to alkaline halide crystals impurified with Eu 2+ ions, making an analysis on the paper that its play a) the ions concentration of Eu 2+ in KBr: Eu 2+ , b) the different sites of trapping of electrons and holes in KBr: Eu 2+ , KCl: Eu 2+ , RbBr:Eu 2+ , RbCl: Eu 2+ and c) the composition of the crystalline solid solutions KCl x Br 1-X : Eu 2+ and RbCI x KBr 1-x : Eu 2+ on the thermoluminescence curve when these materials are exposed to small dose of β irradiation. The increase in the concentration of Eu 2+ ions produces a smaller relative intensity of the emissions of high temperature for a given dose and it is found that in a RbCl x KBr 1-x : Eu 2+ with the greater/smaller concentration of Cl - ions, the temperature of the characteristic emission is near to the 453/373 K. The composition x of halogenous ions and not the one of alkaline in the crystalline solid solution dominates the landslide of the temperature of the emission. (Author)

Intrinsic potential of cell membranes: opposite effects of lipid transmembrane asymmetry and asymmetric salt ion distribution

DEFF Research Database (Denmark)

Gurtovenko, Andrey A; Vattulainen, Ilpo

2009-01-01

Using atomic-scale molecular dynamics simulations, we consider the intrinsic cell membrane potential that is found to originate from a subtle interplay between lipid transmembrane asymmetry and the asymmetric distribution of monovalent salt ions on the two sides of the cell membrane. It turns out......Cl saline solution and the PE leaflet is exposed to KCl, the outcome is that the effects of asymmetric lipid and salt ion distributions essentially cancel one another almost completely. Overall, our study highlights the complex nature of the intrinsic potential of cell membranes under physiological...... that both the asymmetric distribution of phosphatidylcholine (PC) and phosphatidylethanolamine (PE) lipids across a membrane and the asymmetric distribution of NaCl and KCl induce nonzero drops in the transmembrane potential. However, these potential drops are opposite in sign. As the PC leaflet faces a Na...

Photopolymerizable organic compositions and diaryliodonium salts used therein

International Nuclear Information System (INIS)

Crivello, J.V.; Lee, J.L.

1987-01-01

Arylketone containing iodonium salts is described of the formula [RR/sup 1/]/sup +/X/sup -/, where R is a C/sub (6-13/) monovalent aromatic hydrocarbon radical or halo substituted C/sub (6-13/) monovalent aromatic hydrocarbon radical. R/sup 1/ is a monovalent aryl ketone group which is attached to iodine to form a carbon-iodine linkage selected from the class and X/sup -/ is a counter ion selected from the class consisting of tosylate, tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, and hexafluoroantimonate

The importance of moisture in hybrid lead halide perovskite thin film fabrication

NARCIS (Netherlands)

Eperon, G.E.; Habisreutinger, S.N.; Leijtens, T.; Bruijnaers, B.J.; van Franeker, J.J.; deQuilettes, D.W.; Pathak, S.; Sutton, R.J.; Grancini, G.; Ginger, D.S.; Janssen, R.A.J.; Petrozza, A.; Snaith, H.J.

2015-01-01

Moisture, in the form of ambient humidity, has a significant impact on methylammonium lead halide perovskite films. In particular, due to the hygroscopic nature of the methylammonium component, moisture plays a significant role during film formation. This issue has so far not been well understood

40 CFR 63.2465 - What requirements must I meet for process vents that emit hydrogen halide and halogen HAP or HAP...

Science.gov (United States)

2010-07-01

... process vents that emit hydrogen halide and halogen HAP or HAP metals? 63.2465 Section 63.2465 Protection... and halogen HAP or HAP metals? (a) You must meet each emission limit in Table 3 to this subpart that... section. (b) If any process vents within a process emit hydrogen halide and halogen HAP, you must...

Long-wavelength limit of the static structure factors for mixtures of two simple molten salts with a common ion and generalized Bhatia-Thornton formalism: Molecular dynamics study of molten mixture Ag(Br{sub 0.7}I{sub 0.3})

Energy Technology Data Exchange (ETDEWEB)

Bitrian, Vicente [Departament de Fisica i Enginyeria Nuclear, Universitat Politecnica de Catalunya, Campus Nord UPC, Edifici B4-B5, Despatx B4-204, Jordi Girona 1-3, 08034 Barcelona (Spain); Trullas, Joaquim [Departament de Fisica i Enginyeria Nuclear, Universitat Politecnica de Catalunya, Campus Nord UPC, Edifici B4-B5, Despatx B4-204, Jordi Girona 1-3, 08034 Barcelona (Spain)], E-mail: quim.trullas@upc.edu; Silbert, Moises [School of Mathematics, University of East Anglia, Norwich NR4 7QF (United Kingdom)

2008-12-15

The relation between thermodynamic properties and the long-wavelength limit of the structure factors for mixtures of two simple molten salts with a common ion is derived. While the long-wavelength limit of the partial structure factors for binary ionic systems is directly related to the isothermal compressibility, for ternary ionic systems it is shown that it is also related to the mean square thermal fluctuation in the relative concentration of the non-common ions. This result leads to a generalization of the Bhatia-Thornton formalism. From the local fluctuations in the total number-density, charge-density, and relative concentration, six static structure factors, and the corresponding spatial correlation functions, are defined. By introducing three complementary structure factors, it is possible to describe either these mixtures as a system of cations and anions irrespective of the species of the non-common ions, or solely the binary subsystem of the non-common ions. The generalized structure factors and their long-wavelength limits are illustrated by molecular dynamics simulation results of the molten mixture Ag(Br{sub 0.7}I{sub 0.3}). The mixture retains the charge order characteristic of pure molten monovalent salts and the topological order observed in monovalent ionic melts in which the cations are smaller than the anions, while the main trends of the anionic chemical order are those of simple binary alloys. The long-wavelength fluctuations in the local relative concentration are found to be very sensitive to the choice of the short-range interactions between the non-common ions.

[BMIM][PF(6)] promotes the synthesis of halohydrin esters from diols using potassium halides.

Science.gov (United States)

Oromí-Farrús, Mireia; Eras, Jordi; Villorbina, Gemma; Torres, Mercè; Llopis-Mestre, Veronica; Welton, Tom; Canela, Ramon

2008-10-01

Haloesterification of diverse diols with various carboxylic acids was achieved using potassium halides (KX) as the only halide source in ionic liquids. The best yield was obtained in [BMIM][PF(6)] when 1,2-octanediol, palmitic acid and KBr were used. This yield was 85% and the regioisomer with the bromine in primary position was present in a 75:25 ratio. The regioisomeric ratio could be improved using either KCl or some phenylcarboxylic acids. [BMIM][PF(6)] acts as both reaction media and catalyst of the reaction. To the best of our knowledge, this type of combined reaction using an ionic liquid is unprecedented. The other solvents tested did not lead either to the same yield or to the same regioisomeric ratio.

Alloying effects on superionic conductivity in lithium indium halides for all-solid-state batteries

Science.gov (United States)

Zevgolis, Alysia; Wood, Brandon C.; Mehmedović, Zerina; Hall, Alex T.; Alves, Thomaz C.; Adelstein, Nicole

2018-04-01

Alloying of anions is a promising engineering strategy for tuning ionic conductivity in halide-based inorganic solid electrolytes. We explain the alloying effects in Li3InBr6-xClx, in terms of strain, chemistry, and microstructure, using first-principles molecular dynamics simulations and electronic structure analysis. We find that strain and bond chemistry can be tuned through alloying and affect the activation energy and maximum diffusivity coefficient. The similar conductivities of the x = 3 and x = 6 compositions can be understood by assuming that the alloy separates into Br-rich and Cl-rich regions. Phase-separation increases diffusivity at the interface and in the expanded Cl-region, suggesting microstructure effects are critical. Similarities with other halide superionic conductors are highlighted.

Protonation of octadecylamine Langmuir monolayer by adsorption of halide counterions

Science.gov (United States)

Sung, Woongmo; Avazbaeva, Zaure; Lee, Jonggwan; Kim, Doseok

Langmuir monolayer consisting of octadecylamine (C18H37NH2, ODA) was investigated by heterodyne vibrational sum-frequency generation (HD-VSFG) spectroscopy in conjunction with surface pressure-area (π- A) isotherm, and the result was compared with that from cationic-lipid (DPTAP) Langmuir monolayer. In case of ODA monolayer on pure water, both SF intensity of water OH band and the surface pressure were significantly smaller than those of the DPTAP monolayer implying that only small portion of the amine groups (-NH3+ is protonated in the monolayer. In the presence of sodium halides (NaCl and NaI) in the subphase water, it was found that the sign of Imχ (2) of water OH band remained the same as that of the ODA monolayer on pure water, but there was a substantial increase in the SF amplitude. From this, we propose that surface excess of the halide counterions (Cl- and I-) makes the solution condition near the ODA monolayer/water interface more acidic so that ODA molecules in the monolayer are more positively charged, which works to align the water dipoles at the interface.

Evaluation of radioiodinated and radiocopper labeled monovalent fragments of monoclonal antibody chCE7 for targeting of neuroblastoma

International Nuclear Information System (INIS)

Carrel, Francois; Amstutz, Hanspeter; Novak-Hofer, Ilse; Schubiger, P. August

1997-01-01

Monovalent fragments of antineuroblastoma antibody mAb chCE7 were evaluated for their in vitro and in vivo tumor cell binding properties. Single chain fragments were constructed from the variable region genes cloned from hybridoma cells, expressed in E.coli and purified by metal chelate affinity chromatography. Radioiodinated CE7-scFv fragments were found to bind with high affinity (K d ∼10 -9 M) to target cells in vitro but formed aggregates at 37 deg. C, and bound to serum proteins in vitro and in vivo. Circular Dichroism spectra revealed the protein to be in a conformationally altered form and no permanent 'refolding' could be achieved. In contrast, chCE7-Fab fragments were found to bind to target tumor cells with similar affinity than the parent mAb chCE7 (K d ∼10 -10 M), showed no tendency to aggregate and were stable in serum both in vitro and in vivo. Kinetics of association and dissociation of radioiodinated scFv and Fab fragments were found to be rapid. Radioiodination with the Iodogen method led to impaired immunoreactivity which was found to further increase the off- rates of radioiodinated fragments from tumor cells. Radioiodination with the Bolton-Hunter reagent as well as labeling of chCE7-Fab fragments with 67 Cu via the macrocyclic CPTA ligand led to fully immunoreactive Fab fragments. Radioiodinated and radiocopper labeled monovalent CE7 fragments did not internalize into target tumor cells as the parent mAb and its F(ab') 2 fragment. A comparison of the biodistribution in tumor bearing nude mice of the radiocopper labeled monovalent, non internalizing Fab fragments with the internalizing divalent F(ab') 2 fragments showed in both cases high levels of radioactivity in the kidneys. Concerning tumor uptake, radioactivity from both internalizing and non internalizing fragments remained associated with tumor tissue for longer times than in case of the corresponding radioiodinated fragments. When compared with the radioiodinated forms, tumor uptake

Divalent cation shrinks DNA but inhibits its compaction with trivalent cation.

Science.gov (United States)

Tongu, Chika; Kenmotsu, Takahiro; Yoshikawa, Yuko; Zinchenko, Anatoly; Chen, Ning; Yoshikawa, Kenichi

2016-05-28

Our observation reveals the effects of divalent and trivalent cations on the higher-order structure of giant DNA (T4 DNA 166 kbp) by fluorescence microscopy. It was found that divalent cations, Mg(2+) and Ca(2+), inhibit DNA compaction induced by a trivalent cation, spermidine (SPD(3+)). On the other hand, in the absence of SPD(3+), divalent cations cause the shrinkage of DNA. As the control experiment, we have confirmed the minimum effect of monovalent cation, Na(+) on the DNA higher-order structure. We interpret the competition between 2+ and 3+ cations in terms of the change in the translational entropy of the counterions. For the compaction with SPD(3+), we consider the increase in translational entropy due to the ion-exchange of the intrinsic monovalent cations condensing on a highly charged polyelectrolyte, double-stranded DNA, by the 3+ cations. In contrast, the presence of 2+ cation decreases the gain of entropy contribution by the ion-exchange between monovalent and 3+ ions.

A novel antibody engineering strategy for making monovalent bispecific heterodimeric IgG antibodies by electrostatic steering mechanism.

Science.gov (United States)

Liu, Zhi; Leng, Esther C; Gunasekaran, Kannan; Pentony, Martin; Shen, Min; Howard, Monique; Stoops, Janelle; Manchulenko, Kathy; Razinkov, Vladimir; Liu, Hua; Fanslow, William; Hu, Zhonghua; Sun, Nancy; Hasegawa, Haruki; Clark, Rutilio; Foltz, Ian N; Yan, Wei

2015-03-20

Producing pure and well behaved bispecific antibodies (bsAbs) on a large scale for preclinical and clinical testing is a challenging task. Here, we describe a new strategy for making monovalent bispecific heterodimeric IgG antibodies in mammalian cells. We applied an electrostatic steering mechanism to engineer antibody light chain-heavy chain (LC-HC) interface residues in such a way that each LC strongly favors its cognate HC when two different HCs and two different LCs are co-expressed in the same cell to assemble a functional bispecific antibody. We produced heterodimeric IgGs from transiently and stably transfected mammalian cells. The engineered heterodimeric IgG molecules maintain the overall IgG structure with correct LC-HC pairings, bind to two different antigens with comparable affinity when compared with their parental antibodies, and retain the functionality of parental antibodies in biological assays. In addition, the bispecific heterodimeric IgG derived from anti-HER2 and anti-EGF receptor (EGFR) antibody was shown to induce a higher level of receptor internalization than the combination of two parental antibodies. Mouse xenograft BxPC-3, Panc-1, and Calu-3 human tumor models showed that the heterodimeric IgGs strongly inhibited tumor growth. The described approach can be used to generate tools from two pre-existent antibodies and explore the potential of bispecific antibodies. The asymmetrically engineered Fc variants for antibody-dependent cellular cytotoxicity enhancement could be embedded in monovalent bispecific heterodimeric IgG to make best-in-class therapeutic antibodies. © 2015 by The American Society for Biochemistry and Molecular Biology, Inc.

Combinatorial screening of halide perovskite thin films and solar cells by mask-defined IR laser molecular beam epitaxy

OpenAIRE

Kawashima, Kazuhiro; Okamoto, Yuji; Annayev, Orazmuhammet; Toyokura, Nobuo; Takahashi, Ryota; Lippmaa, Mikk; Itaka, Kenji; Suzuki, Yoshikazu; Matsuki, Nobuyuki; Koinuma, Hideomi

2017-01-01

Abstract As an extension of combinatorial molecular layer epitaxy via ablation of perovskite oxides by a pulsed excimer laser, we have developed a laser molecular beam epitaxy (MBE) system for parallel integration of nano-scaled thin films of organic?inorganic hybrid materials. A pulsed infrared (IR) semiconductor laser was adopted for thermal evaporation of organic halide (A-site: CH3NH3I) and inorganic halide (B-site: PbI2) powder targets to deposit repeated A/B bilayer films where the thic...

Analogy between temperature dependent radiation effects in alkali halide crystals and crystalline ammonia

International Nuclear Information System (INIS)

Blum, A.

1977-01-01

Pikaev, Ershov, and Makarov recently reported the characteristic shape of Arrhenius-type dependence for F-centers slow part (millisecond) decay in alkali halide crystals irradiated at different temperatures. The decay rate is constant when the temperature is below the limiting value (T/sub lim/) and exhibits constant activation energy (E/sub A/) at temperatures above T/sub lim/ up to the melting point. A similar dependence has been observed for crystalline ammonia radiolysis yields (H 2 and N 2 ) in the temperature range from 77 to 195 0 K (ammonia melting point) with a limiting value of 105 0 K for N 2 and 119 0 K for H 2 . The coincidence between the alkali halide and ammonia data does not seem to be formal and there are indications showing a closer analogy between these two cases

Intrinsic Defect Physics in Indium-based Lead-free Halide Double Perovskites.

Science.gov (United States)

Xu, Jian; Liu, Jian-Bo; Liu, Bai-Xin; Huang, Bing

2017-09-21

Lead-free halide double perovskites (HDPs) are expected to be promising photovoltaic (PV) materials beyond organic-inorganic halide perovskite, which is hindered by its structural instability and toxicity. The defect- and stability-related properties of HDPs are critical for the use of HDPs as important PV absorbers, yet their reliability is still unclear. Taking Cs 2 AgInBr 6 as a representative, we have systemically investigated the defect properties of HDPs by theoretical calculations. First, we have determined the stable chemical potential regions to grow stoichiometric Cs 2 AgInBr 6 without structural decomposition. Second, we reveal that Ag-rich and Br-poor are the ideal chemical potential conditions to grow n-type Cs 2 AgInBr 6 with shallow defect levels. Third, we find the conductivity of Cs 2 AgInBr 6 can change from good n-type, to poorer n-type, to intrinsic semiconducting depending on the growth conditions. Our studies provided important guidance for experiments to fabricate Pb-free perovskite-based solar cell devices with superior PV performances.

Sodium-Metal-Halide Battery Energy Storage for DoD Installations

Science.gov (United States)

2017-10-24

electrical equipment for AC interface PDE Pacific Data Electric V&F Voltage and Frequency, power quality measurements VA Volt-Amp, units for apparent...Metal-Halide technology could operate at extreme ambient temperatures, but the early prototypes did struggle with managing sand ingress.  The...peak power Not tested 3. PV smoothing Measure improvement in power quality Power meter measurements Power quality improvements 15-min

Rapid Microwave-Assisted Copper-Catalyzed Nitration of Aromatic Halides with Nitrite Salts

Energy Technology Data Exchange (ETDEWEB)

Paik, Seung Uk; Jung, Myoung Geun [Keimyung University, Daegu (Korea, Republic of)

2012-02-15

A rapid and efficient copper-catalyzed nitration of aryl halides has been established under microwave irradiation. The catalytic systems were found to be the most effective with 4-substituted aryl iodides leading to nearly complete conversions. Nitration of aromatic compounds is one of the important industrial processes as underlying intermediates in the manufacture of a wide range of chemicals such as dyes, pharmaceuticals, agrochemicals and explosives. General methods for the nitration of aromatic compounds utilize strongly acidic conditions employing nitric acid or a mixture of nitric and sulfuric acids, sometimes leading to problems with poor regioselectivity, overnitration, oxidized byproducts and excess acid waste in many cases of functionalized aromatic compounds. Several other nitrating agents or methods avoiding harsh reaction conditions have been explored using metal nitrates, nitrite salts, and ionic liquid-mediated or microwave-assisted nitrations. Recently, copper or palladium compounds have been successfully used as efficient catalysts for the arylation of amines with aryl halides under mild conditions.

Efficient Photon Recycling and Radiation Trapping in Cesium Lead Halide Perovskite Waveguides

KAUST Repository

Dursun, Ibrahim

2018-05-26

Cesium lead halide perovskite materials have attracted considerable attention for potential applications in lasers, light emitting diodes and photodetectors. Here, we provide the experimental and theoretical evidence for photon recycling in CsPbBr3 perovskite microwires. Using two-photon excitation, we recorded photoluminescence (PL) lifetimes and emission spectra as a function of the lateral distance between PL excitation and collection positions along the microwire, with separations exceeding 100 µm. At longer separations, the PL spectrum develops a red-shifted emission peak accompanied by an appearance of well-resolved rise times in the PL kinetics. We developed quantitative modeling that accounts for bimolecular recombination and photon recycling within the microwire waveguide and is sufficient to account for the observed decay modifications. It relies on a high radiative efficiency in CsPbBr3 perovskite microwires and provides crucial information about the potential impact of photon recycling and waveguide trapping on optoelectronic properties of cesium lead halide perovskite materials.

Rapid Microwave-Assisted Copper-Catalyzed Nitration of Aromatic Halides with Nitrite Salts

International Nuclear Information System (INIS)

Paik, Seung Uk; Jung, Myoung Geun

2012-01-01

A rapid and efficient copper-catalyzed nitration of aryl halides has been established under microwave irradiation. The catalytic systems were found to be the most effective with 4-substituted aryl iodides leading to nearly complete conversions. Nitration of aromatic compounds is one of the important industrial processes as underlying intermediates in the manufacture of a wide range of chemicals such as dyes, pharmaceuticals, agrochemicals and explosives. General methods for the nitration of aromatic compounds utilize strongly acidic conditions employing nitric acid or a mixture of nitric and sulfuric acids, sometimes leading to problems with poor regioselectivity, overnitration, oxidized byproducts and excess acid waste in many cases of functionalized aromatic compounds. Several other nitrating agents or methods avoiding harsh reaction conditions have been explored using metal nitrates, nitrite salts, and ionic liquid-mediated or microwave-assisted nitrations. Recently, copper or palladium compounds have been successfully used as efficient catalysts for the arylation of amines with aryl halides under mild conditions

Radiation processes in organic halides (Cl, Br, I) studied by ESR spectroscopy

International Nuclear Information System (INIS)

Symons, M.C.R.

1980-01-01

Electron-loss from alkyl halides (Cl, Br, I) gives Rhal. + which may dimerise to give (Rhal-halR) + σ* radicals with characteristic ESR spectra, or may lose H + to give α-halo radicals (R 2 Chal) also with well characterised ESR spectra. Electron-capture gives dissociation, but there may be weak residual charge-transfer interaction between R. and hal - which gives rise to well defined hyperfine coupling from the halide nuclei. Loss of β-hydrogen gives β-halo radicals, R 2 C-CH 2 hal (Cl,Br) whose conformation, established by ESR spectroscopy, is such that the halogen atom lies out of the radical plane so that overlap between the half-filled 2p(π) orbital and the C-hal (σ) orbital is maximised. Electron addition to α-halocarboxylates and related compounds probably gives β-halo radical anions, (R 2 C[hal]CO 2 H) - with a similar preferred conformation. Alternative structures are considered for these species. (author)

Energetics and dynamics in organic–inorganic halide perovskite photovoltaics and light emitters

International Nuclear Information System (INIS)

Sum, Tze Chien; Chen, Shi; Xing, Guichuan; Liu, Xinfeng; Wu, Bo

2015-01-01

The rapid transcendence of organic–inorganic metal halide perovskite solar cells to above the 20% efficiency mark has captivated the broad photovoltaic community. As the efficiency race continues unabated, it is essential that fundamental studies keep pace with these developments. Further gains in device efficiencies are expected to be increasingly arduous and harder to come by. The key to driving the perovskite solar cell efficiencies towards their Shockley–Queisser limit is through a clear understanding of the interfacial energetics and dynamics between perovskites and other functional materials in nanostructured- and heterojunction-type devices. In this review, we focus on the current progress in basic characterization studies to elucidate the interfacial energetics (energy-level alignment and band bending) and dynamical processes (from the ultrafast to the ultraslow) in organic–inorganic metal halide perovskite photovoltaics and light emitters. Major findings from these studies will be distilled. Open questions and scientific challenges will also be highlighted. (topical review)

Relationship between thermoluminescence and X-ray induced luminescence in alkali halides

International Nuclear Information System (INIS)

Aguilar, M.; Lopez, F.J.; Jaque, F.

1978-01-01

The wavelength spectra of thermoluminescence and X-ray induced luminescence in pure and divalent cation doped alkali halides, in the temperature range LNT-RT have been studied. The more important conclusion is that the wavelength spectra in both cases are very similar. This allows a new point of view to be presented on thermoluminescence mechanisms. (author)

A review on bis-hydrazonoyl halides: Recent advances in their synthesis and their diverse synthetic applications leading to bis-heterocycles of biological interest

Directory of Open Access Journals (Sweden)

Ahmad Sami Shawali

2016-11-01

Full Text Available This review covers a summary of the literature data published on the chemistry of bis-hydrazonoyl halides over the last four decades. The biological activities of some of the bis-heterocyclic compounds obtained from these bis-hydrazonoyl halides are also reviewed and discussed.

Yeast Kch1 and Kch2 membrane proteins play a pleiotropic role in membrane potential establishment and monovalent cation homeostasis regulation

Czech Academy of Sciences Publication Activity Database

Felcmanová, Kristina; Nevečeřalová, Petra; Sychrová, Hana; Zimmermannová, Olga

2017-01-01

Roč. 17, č. 5 (2017), č. článku fox053. ISSN 1567-1356 R&D Projects: GA ČR(CZ) GA16-03398S; GA MŠk(CZ) LH14297 Institutional support: RVO:67985823 Keywords : Kch proteins * plasma-membrane potential * monovalent cation homeostasis * intracellular pH * Saccharomyces cerevisiae * Candida albicans Subject RIV: EB - Genetics ; Molecular Biology OBOR OECD: Mycology Impact factor: 3.299, year: 2016

Special features of the formation of high-conductivity phases of halides of alkali metals at superhigh pressures

International Nuclear Information System (INIS)

Babushkin, A.N.; Babushkina, G.V.

1999-01-01

The halides of alkali metals are the simplest crystals with the ionic nature of chemical bonds and are used widely as modelling materials in high-pressure physics. As a result of previous theoretical and experimental (optical, structural, electro-physical and shock-waves) investigations it was shown that these materials may be characterised by the overlapping of the valency and conduction bands and by the formation of groups of free charge carriers at pressures of the megabaric level. However, the authors know of no data on the direct investigations of the electrophysical properties of the halides of alkali metals at such high static pressures. The end of this investigation was to examine the temperature dependences of the electrical conductivity and thermal EMF of halides of alkali metals AX (A = Na, K, Rb, Cs, X = Cl, Br, I) in a wide temperature range at pressures from 10 to 50 GPa in order to reveal the general leisure since governing the change of their electronic structures, in particular, the transition to the state with the activation-type or metallic conductivity

Calcium looping process for high purity hydrogen production integrated with capture of carbon dioxide, sulfur and halides

Science.gov (United States)

Ramkumar, Shwetha; Fan, Liang-Shih

2013-07-30

A process for producing hydrogen comprising the steps of: (i) gasifying a fuel into a raw synthesis gas comprising CO, hydrogen, steam, sulfur and halide contaminants in the form of H.sub.2S, COS, and HX, wherein X is a halide; (ii) passing the raw synthesis gas through a water gas shift reactor (WGSR) into which CaO and steam are injected, the CaO reacting with the shifted gas to remove CO.sub.2, sulfur and halides in a solid-phase calcium-containing product comprising CaCO.sub.3, CaS and CaX.sub.2; (iii) separating the solid-phase calcium-containing product from an enriched gaseous hydrogen product; and (iv) regenerating the CaO by calcining the solid-phase calcium-containing product at a condition selected from the group consisting of: in the presence of steam, in the presence of CO.sub.2, in the presence of synthesis gas, in the presence of H.sub.2 and O.sub.2, under partial vacuum, and combinations thereof.

Designing mixed metal halide ammines for ammonia storage using density functional theory and genetic algorithms.

Science.gov (United States)

Jensen, Peter Bjerre; Lysgaard, Steen; Quaade, Ulrich J; Vegge, Tejs

2014-09-28

Metal halide ammines have great potential as a future, high-density energy carrier in vehicles. So far known materials, e.g. Mg(NH3)6Cl2 and Sr(NH3)8Cl2, are not suitable for automotive, fuel cell applications, because the release of ammonia is a multi-step reaction, requiring too much heat to be supplied, making the total efficiency lower. Here, we apply density functional theory (DFT) calculations to predict new mixed metal halide ammines with improved storage capacities and the ability to release the stored ammonia in one step, at temperatures suitable for system integration with polymer electrolyte membrane fuel cells (PEMFC). We use genetic algorithms (GAs) to search for materials containing up to three different metals (alkaline-earth, 3d and 4d) and two different halides (Cl, Br and I) - almost 27,000 combinations, and have identified novel mixtures, with significantly improved storage capacities. The size of the search space and the chosen fitness function make it possible to verify that the found candidates are the best possible candidates in the search space, proving that the GA implementation is ideal for this kind of computational materials design, requiring calculations on less than two percent of the candidates to identify the global optimum.

NMR longitudinal relaxation enhancement in metal halides by heteronuclear polarization exchange during magic-angle spinning

Energy Technology Data Exchange (ETDEWEB)

Shmyreva, Anna A. [Center for Magnetic Resonance, St. Petersburg State University, St. Petersburg 198504 (Russian Federation); Safdari, Majid; Furó, István [Department of Chemistry, KTH Royal Institute of Technology, SE-10044 Stockholm (Sweden); Dvinskikh, Sergey V., E-mail: sergeid@kth.se [Department of Chemistry, KTH Royal Institute of Technology, SE-10044 Stockholm (Sweden); Laboratory of Biomolecular NMR, St. Petersburg State University, St. Petersburg 199034 (Russian Federation)

2016-06-14

Orders of magnitude decrease of {sup 207}Pb and {sup 199}Hg NMR longitudinal relaxation times T{sub 1} upon magic-angle-spinning (MAS) are observed and systematically investigated in solid lead and mercury halides MeX{sub 2} (Me = Pb, Hg and X = Cl, Br, I). In lead(II) halides, the most dramatic decrease of T{sub 1} relative to that in a static sample is in PbI{sub 2}, while it is smaller but still significant in PbBr{sub 2}, and not detectable in PbCl{sub 2}. The effect is magnetic-field dependent but independent of the spinning speed in the range 200–15 000 Hz. The observed relaxation enhancement is explained by laboratory-frame heteronuclear polarization exchange due to crossing between energy levels of spin-1/2 metal nuclei and adjacent quadrupolar-spin halogen nuclei. The enhancement effect is also present in lead-containing organometal halide perovskites. Our results demonstrate that in affected samples, it is the relaxation data recorded under non-spinning conditions that characterize the local properties at the metal sites. A practical advantage of fast relaxation at slow MAS is that spectral shapes with orientational chemical shift anisotropy information well retained can be acquired within a shorter experimental time.

Effects of Annealing Conditions on Mixed Lead Halide Perovskite Solar Cells and Their Thermal Stability Investigation.

Science.gov (United States)

Yang, Haifeng; Zhang, Jincheng; Zhang, Chunfu; Chang, Jingjing; Lin, Zhenhua; Chen, Dazheng; Xi, He; Hao, Yue

2017-07-21

In this work, efficient mixed organic cation and mixed halide (MA 0.7 FA 0.3 Pb(I 0.9 Br 0.1 )₃) perovskite solar cells are demonstrated by optimizing annealing conditions. AFM, XRD and PL measurements show that there is a better perovskite film quality for the annealing condition at 100 °C for 30 min. The corresponding device exhibits an optimized PCE of 16.76% with V OC of 1.02 V, J SC of 21.55 mA/cm² and FF of 76.27%. More importantly, the mixed lead halide perovskite MA 0.7 FA 0.3 Pb(I 0.9 Br 0.1 )₃ can significantly increase the thermal stability of perovskite film. After being heated at 80 °C for 24 h, the PCE of the MA 0.7 FA 0.3 Pb(I 0.9 Br 0.1 )₃ device still remains at 70.00% of its initial value, which is much better than the control MAPbI₃ device, where only 46.50% of its initial value could be preserved. We also successfully fabricated high-performance flexible mixed lead halide perovskite solar cells based on PEN substrates.

Holographic Optical Elements Recorded in Silver Halide Sensitized Gelatin Emulsions. Part 2. Reflection Holographic Optical Elements

Science.gov (United States)

Kim, Jong Man; Choi, Byung So; Choi, Yoon Sun; Kim, Jong Min; Bjelkhagen, Hans I.; Phillips, Nicholas J.

2002-03-01

Silver halide sensitized gelatin (SHSG) holograms are similar to holograms recorded in dichromated gelatin (DCG), the main recording material for holographic optical elements (HOEs). The drawback of DCG is its low energetic sensitivity and limited spectral response. Silver halide materials can be processed in such a way that the final hologram will have properties like a DCG hologram. Recently this technique has become more interesting since the introduction of new ultra-fine-grain silver halide (AgHal) emulsions. In particular, high spatial-frequency fringes associated with HOEs of the reflection type are difficult to construct when SHSG processing methods are employed. Therefore an optimized processing technique for reflection HOEs recorded in the new AgHal materials is introduced. Diffraction efficiencies over 90% can be obtained repeatably for reflection diffraction gratings. Understanding the importance of a selective hardening process has made it possible to obtain results similar to conventional DCG processing. The main advantage of the SHSG process is that high-sensitivity recording can be performed with laser wavelengths anywhere within the visible spectrum. This simplifies the manufacturing of high-quality, large-format HOEs, also including high-quality display holograms of the reflection type in both monochrome and full color.

IR-spectroscopic study and electrical properties of glasses in the Ba(PO3)2-Ba(Hal)2 systems

International Nuclear Information System (INIS)

Sokolov, I.A.; Tarlakov, Yu.P.; Murin, I.V.; Pronkin, A.A.

2000-01-01

Temperature-concentration dependence of electric conductivity of glasses in the systems Ba(PO 3 ) 2 -Ba(Hal) 2 , where Hal = Cl, Br, I, is studied by the method of conductometry, the numbers of iodide-ions transfer are determined and their concentration dependence is found. Data of IR spectroscopy permitted ascertained participation of halide ions in formation of anionic constituent of the glass structure at the expense of bridge bonds formation, as well as formation of structural-chemical units of [(Hal) - Ba 2+ O - POO 2/2 ] type, their dissociation giving rise to formation of halide ions their dissociation giving rise to formation of halide ions taking part in electric current transfer [ru

40 CFR Table 3 to Subpart Ffff of... - Emission Limits for Hydrogen Halide and Halogen HAP Emissions or HAP Metals Emissions From...

Science.gov (United States)

2010-07-01

... Halogen HAP Emissions or HAP Metals Emissions From Process Vents 3 Table 3 to Subpart FFFF of Part 63... to Subpart FFFF of Part 63—Emission Limits for Hydrogen Halide and Halogen HAP Emissions or HAP... following table that applies to your process vents that contain hydrogen halide and halogen HAP emissions or...

Quantitative positron annihilation studies in citrates, halides and oxyhalides chemisorbed on γ-alumina catalyst

International Nuclear Information System (INIS)

Luo, X.H.; Jean, Y.C.; Cheng, K.L.

1987-01-01

A quantitative study of the γ-alumina catalyst chemisorbed by nitrates, halides, and oxyhalides has been conducted with the positron annihilation spectroscopy (PAS). Catalysts containing Fe, Co, or Ni have been extensively used in chemical industry and petroleum refining. The positron or Ps annihilation can provide a profile information about the bulk, near surface, and void. It is an in-situ surface technique. The PAS technique has shown its capability to determine the nitrate or chloride in γ-alumina as low as 0.02% in solids. It is interesting to note that the PAS may offer the oxidation state information in solids. This is not surprising because the positron annihilation is sensitive to the electron density variation in environments. Positron annihilation models for halides and oxyhalides are proposed

Halide anion solvation and recognition by a macro tri-cyclic tetra-ammonium host in an ionic liquid: a molecular dynamics stud

International Nuclear Information System (INIS)

Chaumont, A.; Wipff, G.

2006-01-01

We report a molecular dynamics study of halide anions X - and their inclusion complexes X - - L 4+ with a macro-tri-cyclic tetrahedral host L 4+ built from four quaternary ammonium sites, in an ionic liquid (IL) based on the 1-butyl-3-methyl-imidazolium (BMI + ) cation and the PF 6 - anion. The 'dry' and 'humid' forms of the [BMI][PF 6 ] IL are compared, showing the importance of IL ions in the 'dry' IL and, in some cases, of water molecules in the 'humid' IL. In the 'dry' IL the F - , Cl - , Br - and I - un-complexed halides are surrounded by 4-5 BMI + cations whose binding mode evolves from hydrogen bonding to facial coordination along this series. Solvent humidity has the largest impact on the solvation of F - whose first shell BMI + cations are all displaced by H 2 O molecules, while the first solvation shell of Cl - , Br - and I - comprises 3-4 BMI + cations plus ca. 4 H 2 O molecules. The solvation of the L 4+ host and of its X - - L 4+ complex mainly involves PF 6 - anions in the 'dry' IL, and additional H 2 O molecules in the 'humid' IL. The question of anion binding selectivity is addressed by free energy perturbation calculations which predict that, in the 'dry' liquid, F - is preferred over Cl - , Br - and I - , which contrasts with the aqueous solution where L 4+ is selective for Cl - . In the 'humid' liquid however, there is no F - /Cl - discrimination, showing the importance of small amounts of water on the complexation selectivity. (authors)

Radiophotoluminescence of alkali-halide crystals stimulated by Bessel laser beam

CERN Document Server

Lyakh, V V; Kochubey, D I; Gyunsburg, K E; Zvezdova, N P; Kochubey, D I; Sedova, Y G; Koronkevich, V P; Poleschuk, A G; Sedukhin, A G

2000-01-01

A new approach to realization of optimal high-resolution reading of deep X-ray images in X-ray-sensitive materials on the base of alkali-halide crystals modified with admixtures has been suggested and investigated experimentally. A possibility to use diffraction axicons with ring aperture for forming micron bright light beams (spatially truncated Bessel beams) which can efficiently de-excite radiophotoluminescence centers lying at large depth in crystals is also presented.

F-center and self-trapped exciton formation in strongly excited alkali halide crystals

International Nuclear Information System (INIS)

Kravchenko, V.A.; Yakovlev, V.Yu.

1988-01-01

Method of luminescent and absorption spectroscopy with time resolution was used to study the effect of density of electron pulse excitation (t p =10 -8 s, P=(10 5 -10 8 ) WXcm -2 ) on efficiency of η ε two-halide autolocalized exciton (TALE) and F-centers (η F ) formation in CsI, CsBr, KBr, KI alkali halide crystals. It was established that for all studied systems the elevation of P power of electron beam (EB) from 10 5 up to 5X10 7 WXcm -2 resulted to sufficient decrease of production efficiency and yield of TALE luminescence. In the case when F-centers of colour are induced predominantly by pulsed irradiation in crystals, F-center yield is independent of P. If F-centers and TALE are produced in comparable amounts (CsBr crystals, T=80 K), η ε decrease with P growth is accompanied by η F growth

Surfactant and counter-ion distribution in styrene-butyl acrylate-acrylic acid dry latex submonolayers

Directory of Open Access Journals (Sweden)

Keslarek Amauri José

2004-01-01

Full Text Available Styrene-butyl acrylate-acrylic acid latex submonolayers prepared using a non-reactive phosphate surfactant together with a reactive sulfonate surfactant were examined in a transmission microscope using electron energy loss spectroscopy imaging (ESI-TEM. Phosphorus is nearly absent from the particles core but it is detected in a thick shell and in unusual, strongly scattering structures with a low carbon content, and largely made out of inorganic phosphate. P is also dispersed outside the particles, while S is uniformly distributed within then. The Na and N elemental maps show that the respective monovalent ions (Na+ and NH4+ have different distributions, in the latex: Na signal within the particles is stronger than in the background, while N is accumulated at the particle borders. The distributions of surfactant and counter-ions are thus different from some current assumptions, but they support recent results on the distribution of ionic constituents in latex films, by scanning electric potential microscopy.

Analysis of the physical atomic forces between noble gas atoms, alkali ions and halogen ions

Science.gov (United States)

Wilson, J. W.; Heinbockel, J. H.; Outlaw, R. A.

1986-01-01

The physical forces between atoms and molecules are important in a number of processes of practical importance, including line broadening in radiative processes, gas and crystal properties, adhesion, and thin films. The components of the physical forces between noble gas atoms, alkali ions, and halogen ions are analyzed and a data base for the dispersion forces is developed from the literature based on evaluations with the harmonic oscillator dispersion model for higher order coefficients. The Zener model of the repulsive core is used in the context of the recent asymptotic wave functions of Handler and Smith; and an effective ionization potential within the Handler and Smith wave functions is defined to analyze the two body potential data of Waldman and Gordon, the alkali-halide molecular data, and the noble gas crystal and salt crystal data. A satisfactory global fit to this molecular and crystal data is then reproduced by the model to within several percent. Surface potentials are evaluated for noble gas atoms on noble gas and salt crystal surfaces with surface tension neglected. Within this context, the noble gas surface potentials on noble gas and salt crystals are considered to be accurate to within several percent.

Surface passivation of mixed-halide perovskite CsPb(BrxI1-x)3 nanocrystals by selective etching for improved stability.

Science.gov (United States)

Jing, Qiang; Zhang, Mian; Huang, Xiang; Ren, Xiaoming; Wang, Peng; Lu, Zhenda

2017-06-08

In recent years, there has been an unprecedented rise in the research of halide perovskites because of their important optoelectronic applications, including photovoltaic cells, light-emitting diodes, photodetectors and lasers. The most pressing question concerns the stability of these materials. Here faster degradation and PL quenching are observed at higher iodine content for mixed-halide perovskite CsPb(Br x I 1-x ) 3 nanocrystals, and a simple yet effective method is reported to significantly enhance their stability. After selective etching with acetone, surface iodine is partially etched away to form a bromine-rich surface passivation layer on mixed-halide perovskite nanocrystals. This passivation layer remarkably stabilizes the nanocrystals, making their PL intensity improved by almost three orders of magnitude. It is expected that a similar passivation layer can also be applied to various other kinds of perovskite materials with poor stability issues.

Nature of the superionic transition in Ag+ and Cu+ halides

International Nuclear Information System (INIS)

Keen, D.A.; Hull, S.; Barnes, A.C.; Berastegui, P.; Crichton, W.A.; Madden, P.A.; Tucker, M.G.; Wilson, M.

2003-01-01

Silver and copper halides generally display an abrupt (first-order) transition to the superionic state. However, powder diffraction studies and molecular dynamics (MD) simulations of AgI under hydrostatic pressure both indicate that a continuous superionic transition occurs on heating. The gradual onset of the highly conducting state is accompanied by an increasing fraction of dynamic Frenkel defects, a peak in the specific heat and anomalous behavior of the lattice expansion. Similar methods have been employed to investigate the proposed continuous superionic transition between the two ambient pressure face centered cubic phases of CuI. This is difficult to examine experimentally, because the hexagonal β phase exists over a narrow temperature range between the γ (cation ordered) and α (cation disordered) phases. MD simulations performed with the simulation box constrained to remain cubic at all temperatures show that, although limited Cu + Frenkel disorder occurs within γ-CuI, CuI undergoes an abrupt superionic transition at 670 K to the superionic α phase. This is supported by powder neutron diffraction studies of CuI lightly doped with Cs + to prevent stabilization of the β phase. The implications of these results on the phase transitions of other copper and silver halide superionic conductors are discussed

Dehalogenation of aromatic halides by polyaniline/zero-valent iron composite nanofiber: Kinetics and mechanisms

CSIR Research Space (South Africa)

Giri, S

2016-03-01

Full Text Available Dehalogenation of aryl halides was demonstrated using polyaniline/zero valent iron composite nanofiber (termed as PANI/Fe0) as a cheap, efficient and environmentally friendly heterogeneous catalyst. The catalyst was prepared via rapid mixing...

Kinetics of halide release of haloalkane dehalogenase : Evidence for a slow conformational change

NARCIS (Netherlands)

Schanstra, JP; Janssen, DB; Schanstra, Joost P.

1996-01-01

Haloalkane dehalogenase converts haloalkanes to their corresponding alcohols and halides, The reaction mechanism involves the formation of a covalent alkyl-enzyme complex which is hydrolyzed by water. The active site is a hydrophobic cavity buried between the main domain and the cap domain of the

2-D images of the metal-halide lamp obtained by experiment and model

NARCIS (Netherlands)

Flikweert, A.J.; Beks, M.L.; Nimalasuriya, T.; Kroesen, G.M.W.; Mullen, van der J.J.A.M.; Stoffels, W.W.

2008-01-01

The metal-halide lamp shows color segregation caused by diffusion and convection. Two-dimensional imaging of the arc discharge under varying gravity conditions aids in the understanding of the flow phenomena. In this paper, we show results obtained by experiments and by numerical simulations in

Behaviour of alkali halides as materials for optical components of high power lasers

International Nuclear Information System (INIS)

Apostol, D.I.; Mihailescu, N.I.; Ghiordanescu, V.; Nistor, C.L.; Nistor, V.S.; Teodorescu, V.; Voda, M.

1978-01-01

The physical phenomena taking place in alkali halides when a CO 2 laser radiation is passing through have been reviewed. A special emphasis has been put on the specific qualities which such materials should have for being used as components for high power lasers. (author)

INTERRELATION OF ACIDITY-BASICITY, SOLUBILITY AND ABILITY TO INTERACTION OF HALIDES OF MX AND M'X2 (M - Li ÷ Cs, M' - Be ÷ Ba, X - Cl ÷ I TYPES

Directory of Open Access Journals (Sweden)

V. F. Zinchenko

2015-11-01

Full Text Available The size-charge factor of basicity for definition of the acid-base properties of alkaline both alkaline-earth metals and Be halides is offered. The certain interrelation of the specified factor, and also the magnitudes connected with energy of a crystal lattice (temperature of boiling and enthalpy of evaporation of salt with its solubility in water, and also with enthalpy of hydration is established. It is shown that the minimum solubility possess alkaline metals halides (KCl for chlorides, RbBr for Rubidium halides and CsI for alkaline metals halides as a whole at which value of the factor of basicity is equal to 0.83, i.e. it is slightly less than 1. Among alkaline-earth metals halides the lowest solubility has BaCl2 with the highest value of the factor of basicity (0.4. An absolute value of enthalpy of hydration for salts crystal-hydrates possesses tens kJ/mol H2O and increases with reduction of the factor of basicity at transition from metals chlorides to iodides, and also at cationic substitution by easier analogue. Qualitative correlation between a difference of basicity of binary halides and their ability to interaction with formation of complex compounds of various degree of durability is established. At an average difference of basicities 0.4 in halide systems are formed incongruently melting, and at 0.6-0.8 and more – congruently melting compounds. Forecasting of solubility of complex halide of CsSrCl3 composition on the basis of its value of equalized basicity is carried out.

Quaternary oxide halides of group 15 with zinc and cadmium; Quaternaere Oxidhalogenide der Gruppe 15 mit Zink und Cadmium

Energy Technology Data Exchange (ETDEWEB)

Rueck, Nadia

2014-07-30

The present thesis ''Quaternary oxide halides of group 15 with zinc and cadmium'' deals with the chemical class of oxide halides, which contain d-block element cations and pnicogens. Over the past few years compounds containing pnicogene cations are intensively investigated. The reason for this is the free electron pair of the Pn{sup 3+} cation, which is responsible for some interesting properties. Free electron pairs do not only impact the spatial structure of molecules but also the properties of materials. The object of this work was the synthesis and characterization of compounds containing Pn{sup 3+} cations with free electron pairs. Due to the structure-determining effect of these free electron pairs and in combination with halides it is possible to synthesize compounds with low-dimensional structures like chains and layers. In these compounds the structure is separated into halophilic and chalcophilic sub-structures, which are held together only by weak Van der Waals forces.

Hot working alkali halides for laser window applications

International Nuclear Information System (INIS)

Koepke, B.G.; Anderson, R.H.; Stokes, R.J.

1975-01-01

The techniques used to hot work alkali halide crystals into laser window blanks are reviewed. From the point of view of high power laser window applications one of the materials with a high figure of merit is KCl. Thus the materials examined are KCl and alloys of KCl-KBr containing 5 mole percent KBr. The fabrication techniques include conventional and constrained press forging, isostatic press forging and hot rolling. Optical properties are paramount to the ultimate usefulness of these materials. Results on the optical properties of the hot worked material are included together with mechanical properties and microstructural data

Synthesis of halide- and solvent free metal borohydrides

DEFF Research Database (Denmark)

Grinderslev, Jakob; Møller, Kasper Trans; Richter, Bo

have challenges due to their high desorption kinetics and limited reversibility at moderate conditions.[2],[3],[4] In this work, we present a new approach to synthesize halide- and solvent free metal borohydrides starting from the respective metal hydride. The synthetic strategy ensures that no metal...... to the metal. Hence, the powdered M(BH4)3∙DMS is heated to 140 °C for 4 hours to obtain pure M(BH4)3. The rare-earth metal borohydrides have been investigated by infrared spectroscopy and thermal analysis (TGA-DSC-MS). Furthermore, the structural trends are investigated by synchrotron radiation powder X...

Composition-Dependent Energy Splitting between Bright and Dark Excitons in Lead Halide Perovskite Nanocrystals.

Science.gov (United States)

Chen, Lan; Li, Bin; Zhang, Chunfeng; Huang, Xinyu; Wang, Xiaoyong; Xiao, Min

2018-03-14

Perovskite semiconductor nanocrystals with different compositions have shown promise for applications in light-emitting devices. Dark excitonic states may suppress light emission from such nanocrystals by providing an additional nonradiative recombination channel. Here, we study the composition dependence of dark exciton dynamics in nanocrystals of lead halides by time-resolved photoluminescence spectroscopy at cryogenic temperatures. The presence of a spin-related dark state is revealed by magneto-optical spectroscopy. The energy splitting between bright and dark states is found to be highly sensitive to both halide elements and organic cations, which is explained by considering the effects of size confinement and charge screening, respectively, on the exchange interaction. These findings suggest the possibility of manipulating dark exciton dynamics in perovskite semiconductor nanocrystals by composition engineering, which will be instrumental in the design of highly efficient light-emitting devices.

Electrically Driven Ion Separations in Permeable Membranes

Energy Technology Data Exchange (ETDEWEB)

Bruening, Merlin [Michigan State Univ., East Lansing, MI (United States)

2017-04-21

Membranes are attractive for a wide range of separations due to their low energy costs and continuous operation. To achieve practical fluxes, most membranes consist of a thin, selective skin on a highly permeable substrate that provides mechanical strength. Thus, this project focused on creating new methods for forming highly selective ultrathin skins as well as modeling transport through these coatings to better understand their unprecedented selectivities. The research explored both gas and ion separations, and the latter included transport due to concentration, pressure and electrical potential gradients. This report describes a series of highlights of the research and then provides a complete list of publications supported by the grant. These publications have been cited more than 4000 times. Perhaps the most stunning finding is the recent discovery of monovalent/divalent cation and anion selectivities around 1000 when modifying cation- and anion-exchange membranes with polyelectrolyte multilayers (PEMs). This discovery builds on many years of exciting research. (Citation numbers refer to the journal articles in the bibliography.)

Multielement ultratrace analysis in tungsten using secondary ion mass spectrometry

International Nuclear Information System (INIS)

Wilhartitz, P.; Virag, A.; Friedbacher, G.; Grasserbauer, M.

1987-01-01

The ever increasing demands on properties of materials create a trend also towards ultrapure products. Characterization of these materials is only possible with modern, highly sophisticated analytical techniques such as activation analysis and mass spectrometry, particularly SSMS, SIMS and GDMS. Analytical strategies were developed for the determination of about 40 elements in a tungsten matrix with high-performance SIMS. Difficulties like the elimination of interferences had to be overcome. Extrapolated detection limits were established in the range of pg/g (alkali metals, halides) to ng/g (e.g. Ta, Th). Depth profiling and ion imaging gave additional information about the lateral and the depth distribution of the elements. (orig.)

Thermochromic halide perovskite solar cells.

Science.gov (United States)

Lin, Jia; Lai, Minliang; Dou, Letian; Kley, Christopher S; Chen, Hong; Peng, Fei; Sun, Junliang; Lu, Dylan; Hawks, Steven A; Xie, Chenlu; Cui, Fan; Alivisatos, A Paul; Limmer, David T; Yang, Peidong

2018-03-01

Smart photovoltaic windows represent a promising green technology featuring tunable transparency and electrical power generation under external stimuli to control the light transmission and manage the solar energy. Here, we demonstrate a thermochromic solar cell for smart photovoltaic window applications utilizing the structural phase transitions in inorganic halide perovskite caesium lead iodide/bromide. The solar cells undergo thermally-driven, moisture-mediated reversible transitions between a transparent non-perovskite phase (81.7% visible transparency) with low power output and a deeply coloured perovskite phase (35.4% visible transparency) with high power output. The inorganic perovskites exhibit tunable colours and transparencies, a peak device efficiency above 7%, and a phase transition temperature as low as 105 °C. We demonstrate excellent device stability over repeated phase transition cycles without colour fade or performance degradation. The photovoltaic windows showing both photoactivity and thermochromic features represent key stepping-stones for integration with buildings, automobiles, information displays, and potentially many other technologies.

Thermochromic halide perovskite solar cells

Science.gov (United States)

Lin, Jia; Lai, Minliang; Dou, Letian; Kley, Christopher S.; Chen, Hong; Peng, Fei; Sun, Junliang; Lu, Dylan; Hawks, Steven A.; Xie, Chenlu; Cui, Fan; Alivisatos, A. Paul; Limmer, David T.; Yang, Peidong

2018-03-01

Smart photovoltaic windows represent a promising green technology featuring tunable transparency and electrical power generation under external stimuli to control the light transmission and manage the solar energy. Here, we demonstrate a thermochromic solar cell for smart photovoltaic window applications utilizing the structural phase transitions in inorganic halide perovskite caesium lead iodide/bromide. The solar cells undergo thermally-driven, moisture-mediated reversible transitions between a transparent non-perovskite phase (81.7% visible transparency) with low power output and a deeply coloured perovskite phase (35.4% visible transparency) with high power output. The inorganic perovskites exhibit tunable colours and transparencies, a peak device efficiency above 7%, and a phase transition temperature as low as 105 °C. We demonstrate excellent device stability over repeated phase transition cycles without colour fade or performance degradation. The photovoltaic windows showing both photoactivity and thermochromic features represent key stepping-stones for integration with buildings, automobiles, information displays, and potentially many other technologies.

Improving the Stability of Metal Halide Perovskite Materials and Light-Emitting Diodes.

Science.gov (United States)

Cho, Himchan; Kim, Young-Hoon; Wolf, Christoph; Lee, Hyeon-Dong; Lee, Tae-Woo

2018-01-25

Metal halide perovskites (MHPs) have numerous advantages as light emitters such as high photoluminescence quantum efficiency with a direct bandgap, very narrow emission linewidth, high charge-carrier mobility, low energetic disorder, solution processability, simple color tuning, and low material cost. Based on these advantages, MHPs have recently shown unprecedented radical progress (maximum current efficiency from 0.3 to 42.9 cd A -1 ) in the field of light-emitting diodes. However, perovskite light-emitting diodes (PeLEDs) suffer from intrinsic instability of MHP materials and instability arising from the operation of the PeLEDs. Recently, many researchers have devoted efforts to overcome these instabilities. Here, the origins of the instability in PeLEDs are reviewed by categorizing it into two types: instability of (i) the MHP materials and (ii) the constituent layers and interfaces in PeLED devices. Then, the strategies to improve the stability of MHP materials and PeLEDs are critically reviewed, such as A-site cation engineering, Ruddlesden-Popper phase, suppression of ion migration with additives and blocking layers, fabrication of uniform bulk polycrystalline MHP layers, and fabrication of stable MHP nanoparticles. Based on this review of recent advances, future research directions and an outlook of PeLEDs for display applications are suggested. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Robust Multilayer Graphene-Organic Frameworks for Selective Separation of Monovalent Anions.

Science.gov (United States)

Zhao, Yan; Zhu, Jiajie; Li, Jian; Zhao, Zhijuan; Charchalac Ochoa, Sebastian Ignacio; Shen, Jiangnan; Gao, Congjie; Van der Bruggen, Bart

2018-05-30

The chemical and mechanical stability of graphene nanosheets was used in this work to design a multilayer architecture of graphene, grafted with sulfonated 4,4'-diaminodiphenyl sulfone (SDDS). Quaternized poly(phenylene oxide) (QPPO) was synthesized and mixed with SDDS (rGO-SDDS-rGO@QPPO), yielding a multilayer graphene-organic framework (MGOF) with positive as well as negative functional groups that can be applied as a versatile electrodriven membrane in electrodialysis (ED). Multilayer graphene-organic frameworks are a new class of multilayer structures, with an architecture having a tunable interlayer spacing connected by cationic polymer material. MGOF membranes were demonstrated to allow for an excellent selective separation of monovalent anions in aqueous solution. Furthermore, different types of rGO-SDDS-rGO@QPPO membranes were found to have a good mechanical strength, with a tensile strength up to 66.43 MPa. The membrane (rGO-SDDS-rGO@QPPO-2) also has a low surface electric resistance (2.79 Ω·cm 2 ) and a low water content (14.5%) and swelling rate (4.7%). In addition, the selective separation between Cl - and SO 4 2- of the MGOF membranes could be as high as 36.6%.

A comparative study of semi-empirical interionic potentials for alkali halides - II

International Nuclear Information System (INIS)

Khwaja, F.A.; Naqvi, S.H.

1985-08-01

A comprehensive study of some semi-empirical interionic potentials is carried out through the calculation of the cohesive energy, relative stability and pressure induced solid-solid phase transformations in alkali halides. The theoretical values of these properties of the alkali halides are obtained using a new set of van der Waals coefficients and zero-point energy in the expression for interionic potential. From the comparison of the present calculations with some previous sophisticated ab-initio quantum-mechanical calculations and other semi-empirical approaches, it is concluded that the present calculations in the simplest central pairwise interaction description with the new values of the van der Waals coefficients and zero-point energy are in better agreement with the experimental data than the previous calculations. It is also concluded that in some cases the better choice of the interionic potential alone in the simplest semi-empirical picture of interaction gives an agreement of the theoretical predictions with the experimental data much superior to the ab-initio quantum mechanical approaches. (author)

Resonance Raman and excitation energy dependent charge transfer mechanism in halide-substituted hybrid perovskite solar cells.

Science.gov (United States)

Park, Byung-wook; Jain, Sagar M; Zhang, Xiaoliang; Hagfeldt, Anders; Boschloo, Gerrit; Edvinsson, Tomas

2015-02-24

Organo-metal halide perovskites (OMHPs) are materials with attractive properties for optoelectronics. They made a recent introduction in the photovoltaics world by methylammonium (MA) lead triiodide and show remarkably improved charge separation capabilities when chloride and bromide are added. Here we show how halide substitution in OMHPs with the nominal composition CH3NH3PbI2X, where X is I, Br, or Cl, influences the morphology, charge quantum yield, and local interaction with the organic MA cation. X-ray diffraction and photoluminescence data demonstrate that halide substitution affects the local structure in the OMHPs with separate MAPbI3 and MAPbCl3 phases. Raman spectroscopies as well as theoretical vibration calculations reveal that this at the same time delocalizes the charge to the MA cation, which can liberate the vibrational movement of the MA cation, leading to a more adaptive organic phase. The resonance Raman effect together with quantum chemical calculations is utilized to analyze the change in charge transfer mechanism upon electronic excitation and gives important clues for the mechanism of the much improved photovoltage and photocurrent also seen in the solar cell performance for the materials when chloride compounds are included in the preparation.

Role of ions in the regulation of light-harvesting

Directory of Open Access Journals (Sweden)

Radek Kana

2016-12-01

Full Text Available Regulation of photosynthetic light harvesting in the thylakoids is one of the major key factors affecting the efficiency of photosynthesis. Thylakoid membrane is negatively charged and influences both the structure and the function of the primarily photosynthetic reactions through its electrical double layer. Further, there is a heterogeneous organization of soluble ions (K+, Mg2+, Cl- attached to the thylakoid membrane that, together with fixed charges (negatively charged amino acids, lipids, provides an electrical field. The electrical double layer is affected by the valence of the ions and interferes with the regulation of state transitions, protein interactions, and excitation energy spillover from Photosystem II to Photosystem I. These effects are reflected in changes in the intensity of chlorophyll a fluorescence, which is also a measure of photoprotective non-photochemical quenching of the excited state of chlorophyll a. A triggering of non-photochemical quenching proceeds via lumen acidification and is coupled to the export of positive counter-ions (Mg2+, K+ to the stroma or/and negative ions (e.g., Cl- into the lumen. The effect of protons and anions in the lumen and of the cations (Mg2+, K+ in the stroma are, thus, functionally tightly interconnected. In this review, we discuss the consequences of the model of electrical double layer, proposed by James Barber (J. Barber (1980 Biochim Biophys Acta 594:253-308 in light of light-harvesting regulation. Further, we explain differences between electrostatic screening and neutralization, and we emphasize the opposite effect of monovalent (K+ and divalent (Mg2+ ions on light-harvesting and on screening of the negative charges on the thylakoid membrane; this effect needs to be incorporated in all future models of photosynthetic regulation by ion channels and transporters.

Amination of Aryl Halides and Esters Using Intensified Continuous Flow Processing

Directory of Open Access Journals (Sweden)

Thomas M. Kohl

2015-09-01

Full Text Available Significant process intensification of the amination reactions of aryl halides and esters has been demonstrated using continuous flow processing. Using this technology traditionally difficult amination reactions have been performed safely at elevated temperatures. These reactions were successfully conducted on laboratory scale coil reactor modules with 1 mm internal diameter (ID and on a preparatory scale tubular reactor with 6 mm ID containing static mixers.

Immunogenicity and safety of monovalent RIVM meningococcal B OMP vesicle F91 vaccine administered to children that received hexavalent meningococcal B vaccine 2.5 years ago

NARCIS (Netherlands)

Lafeber AB; Limpt CJP van; Berbers GAM; Labadie J; Kleijn ED de; Groot R de; Rumke HC; Alphen AJW van; Sophia Kinderziekenhuis /; LVO

2000-01-01

This report describes the results with respect to immunogenicity as well as reactogenicity of a monovalent P1.7h,4 OMV vaccine (MonoMen) used as booster vaccination in children previously vaccinated with a hexavalent MenB vaccine. The participants in this study were immunised in 1995-1996 with

REPLACEMENT OF TRYPTOPHAN RESIDUES IN HALOALKANE DEHALOGENASE REDUCES HALIDE BINDING AND CATALYTIC ACTIVITY

NARCIS (Netherlands)

KENNES, C; PRIES, F; KROOSHOF, GH; BOKMA, E; Kingma, Jacob; JANSSEN, DB

1995-01-01

Haloalkane dehalogenase catalyzes the hydrolytic cleavage of carbon-halogen bonds in short-chain haloalkanes. Two tryptophan residues of the enzyme (Trp125 and Trp175) form a halide-binding site in the active-site cavity, and were proposed to play a role in catalysis. The function of these residues

Seroprevalence of influenza A H1N1 and seroconversion of mothers and infants induced by a single dose of monovalent vaccine.

Science.gov (United States)

Chao, Anne; Huang, Yhu-Chering; Chang, Yao-Lung; Wang, Tzu-Hao; Chang, Shuenn-Dyh; Wu, Ting-Shu; Wu, Tsu-Lan; Chao, An-Shine

2013-09-01

To determine the prevalence of preexisting antibodies against the pandemic 2009 Influenza A (H1N1) virus in pregnant women and to evaluate the seroprotection of the mothers and infants by a single injection of monovalent vaccine during the pandemic. Seropositivity rate of H1N1 among the nonvaccinated were compared with the vaccinated women. A single dose of vaccine, either nonadjuvanted AdimFlu-S or MF59-adjuvanted vaccine, was injected to the voluntarily vaccinated group. Maternal and cord blood sera were collected to evaluate the antibody response of the H1N1 virus. Seropositivity was defined as a hemagglutination inhibition titer to H1N1 (A/Taiwan/126/09) ≥ 1:40. A total of 210 healthy, singleton, pregnant women were enrolled between January 2010 and May 2010. Seropositivity (≥ 1:40) of maternal hemagglutination inhibition was significantly higher in the vaccinated group (78%) than the nonvaccinated group (9.5%); 41.6% (20/48) of seropositive titers were >1:80. In nine vaccinated cases resulting in negative serum titers (75% could be achieved in the paired maternal and cord serum samples by a single injection of monovalent H1N1 vaccine. Copyright © 2013. Published by Elsevier B.V.

Kinetics of cesium lead halide perovskite nanoparticle growth; focusing and de-focusing of size distribution

Science.gov (United States)

Koolyk, Miriam; Amgar, Daniel; Aharon, Sigalit; Etgar, Lioz

2016-03-01

In this work we study the kinetics of cesium lead halide perovskite nanoparticle (NP) growth; the focusing and de-focusing of the NP size distribution. Cesium lead halide perovskite NPs are considered to be attractive materials for optoelectronic applications. Understanding the kinetics of the formation of these all-inorganic perovskite NPs is critical for reproducibly and reliably generating large amounts of uniformly sized NPs. Here we investigate different growth durations for CsPbI3 and CsPbBr3 NPs, tracking their growth by high-resolution transmission electron microscopy and size distribution analysis. As a result, we are able to provide a detailed model for the kinetics of their growth. It was observed that the CsPbI3 NPs exhibit focusing of the size distribution in the first 20 seconds of growth, followed by de-focusing over longer growth durations, while the CsPbBr3 NPs show de-focusing of the size distribution starting from the beginning of the growth. The monomer concentration is depleted faster in the case of CsPbBr3 than in the case of CsPbI3, due to faster diffusion of the monomers, which increases the critical radius and results in de-focusing of the population. Accordingly, focusing is not observed within 40 seconds of growth in the case of CsPbBr3. This study provides important knowledge on how to achieve a narrow size distribution of cesium lead halide perovskite NPs when generating large amounts of these promising, highly luminescent NPs.In this work we study the kinetics of cesium lead halide perovskite nanoparticle (NP) growth; the focusing and de-focusing of the NP size distribution. Cesium lead halide perovskite NPs are considered to be attractive materials for optoelectronic applications. Understanding the kinetics of the formation of these all-inorganic perovskite NPs is critical for reproducibly and reliably generating large amounts of uniformly sized NPs. Here we investigate different growth durations for CsPbI3 and CsPbBr3 NPs, tracking

Characteristics of separation of carnitine and metal ions in cheese whey model solution by loose reverse osmosis membrane

Energy Technology Data Exchange (ETDEWEB)

Xu, J.; Echizen, H.; Xing, X.; Yamamoto, S.; Unno, H. [Tokyo Institute of Technology, Tokyo (Japan)

1996-04-20

Aiming at recovering carnitine from cheese whey by using loose reverse osmosis membranes, rejection characteristics of several components in the whey were examined by using model solutions. An electroneutral membrane was found to be most effective for the separation. The rejection of carnitine was above 0.95 independent of the pH of solutions, while monovalent metal ions showed low rejections of 0.1-0.3. On the other hand, the rejections of divalent metal ions deceased with increase of the pH, and reached a minimum of about 0.5. As a result, mono-and divalent metal ions could be removed simultaneously by adjusting the pH of the feed solutions. To clarify the effect of pH on the rejection the permeate of MgCl2 aqueous solution was examined. The rejections of MgCl2 were greatly affected by the pH and showed the same tendency as the mixed station. The effect of the pH on permeation of electrolyte was considered to be caused mainly by the adsorption of ions on the membrane. 16 refs., 6 figs., 2 tabs.

Radiation chemistry of the alkali halides

International Nuclear Information System (INIS)

Robinson, V.J.; Chandratillake, M.R.

1987-01-01

By far the most thoroughly investigated group of compounds in solid-state radiation chemistry are the alkali halides. Some of the reasons are undoubtedly practical: large single crystals of high purity are readily prepared. The crystals are transparent over a wide range of wavelengths. They are more sensitive to radiation damage than most other ionic solids. The crystals have simple well-defined structures, and the products of radiolysis have also in many cases been clearly identified by a variety of experimental techniques, the most important being optical methods and electron paramagnetic resonance (EPR). In recent years the application of pulse techniques-radiolysis and laser photolysis-has yielded a wealth of information concerning the mechanisms of the primary processes of radiation damage, on the one hand, and of thermal and photolytic reactions that the radiolysis products undergo, on the other

Multicolor tunable emission induced by Cu ion doping of perovskite zirconate

Energy Technology Data Exchange (ETDEWEB)

Lee, D.J. [Department of Physics, Soongsil University, Seoul 156-743 (Korea, Republic of); Lee, Y.S., E-mail: ylee@ssu.ac.kr [Department of Physics, Soongsil University, Seoul 156-743 (Korea, Republic of); Noh, H.-J. [Department of Physics, Chonnam National University, Gwangju 500-757 (Korea, Republic of)

2016-01-15

We report on a multicolor tunable emission induced by Cu ion doping of perovskite zirconate SrZrO{sub 3} with a fairly large bandgap (5.6 eV). X-ray photoelectron spectroscopy of our samples revealed the existence of two mixed valence states of the doped Cu ions, +1 and +2, with a ratio of 3:1. In photoluminescence excitation spectroscopy the absorption structures of the 3d states in monovalent Cu{sup +} and divalent Cu{sup 2+} were identified near 5 eV and 3.5 eV, respectively. Interestingly, in relation to the valence states of the Cu ions, the emission spectra depended strongly on the photo-excitation energy (E{sub ex}). For E{sub ex}<3.8 eV (UVA) two orange and green emissions were observed with the involvement of the Cu{sup 2+} state. For E{sub ex}>3.8 eV (UVB/UVC), however, the Cu{sup +} state, instead of the Cu{sup 2+} state, was dominant in the emission process, causing the visible emission to be turned into violet. Our results were indicative of the complementary role of the different Cu-ion valence states in a wide range of visible emission with respect to E{sub ex}. - Highlights: • Visible emission induced by the Cu doping of SrZrO3. • Tunable colors from orange to violet with respect to the photo-excitation energy. • Multicolor emission should be related to the mixed valence states of the doped Cu ions.

Correlated linear response calculations of the C6 dispersion coefficients of hydrogen halides

Czech Academy of Sciences Publication Activity Database

Sauer, S. P. A.; Paidarová, Ivana

2007-01-01

Roč. 3, 2-4 (2007), s. 399-421 ISSN 1574-0404 R&D Projects: GA AV ČR IAA401870702 Institutional research plan: CEZ:AV0Z40400503 Keywords : hydrogen halides * C6 dospersion coefficients * van der Waals coefficients * polarizability at imaginary frequences * SOPPA Subject RIV: CF - Physical ; Theoretical Chemistry

Can Ferroelectric Polarization Explain the High Performance of Hybrid Halide Perovskite Solar Cells?

NARCIS (Netherlands)

Sherkar, Tejas; Koster, L. Jan Anton

The power conversion efficiency of photovoltaic cells based on the use of hybrid halide perovskites, CH3NH3PbX3 (X = Cl, Br, I), now exceeds 20%. Recently, it was suggested that this high performance originates from the presence of ferroelectricity in the perovskite, which is hypothesized to lower

Na-ion batteries based on the inorganic BN nanocluster anodes: DFT studies.

Science.gov (United States)

Nejati, K; Hosseinian, A; Bekhradnia, A; Vessally, E; Edjlali, L

2017-06-01

It has been recently indicated that the Li-ion batteries may be replaced by Na-ion batteries because of their low safety, high cost, and low-temperature performance, and lack of the Li mineral reserves. Here, using density functional theory calculations, we studied the potential application of B 12 N 12 nanoclusters as anode in Na-ion batteries. Our calculations indicate that the adsorption energy of Na + and Na are about -23.4 and -1.4kcal/mol, respectively, and the pristine BN cage to improve suffers from a low cell voltage (∼0.92V) as an anode in Na-ion batteries. We presented a strategy to increase the cell voltage and performance of Na-ion batteries. We showed that encapsulation of different halides (X=F - , Cl - , or Br - ) into BN cage significantly increases the cell voltage. By increasing the atomic number of X, the Gibbs free energy change of cell becomes more negative and the cell voltage is increased up to 3.93V. The results are discussed based on the structural, energetic, frontier molecular orbital, charge transfer and electronic properties and compared with the performance of other nanostructured anodes. Copyright © 2017 Elsevier Inc. All rights reserved.

Spectral and Dynamical Properties of Single Excitons, Biexcitons, and Trions in Cesium-Lead-Halide Perovskite Quantum Dots.

Science.gov (United States)

Makarov, Nikolay S; Guo, Shaojun; Isaienko, Oleksandr; Liu, Wenyong; Robel, István; Klimov, Victor I

2016-04-13

Organic-inorganic lead-halide perovskites have been the subject of recent intense interest due to their unusually strong photovoltaic performance. A new addition to the perovskite family is all-inorganic Cs-Pb-halide perovskite nanocrystals, or quantum dots, fabricated via a moderate-temperature colloidal synthesis. While being only recently introduced to the research community, these nanomaterials have already shown promise for a range of applications from color-converting phosphors and light-emitting diodes to lasers, and even room-temperature single-photon sources. Knowledge of the optical properties of perovskite quantum dots still remains vastly incomplete. Here we apply various time-resolved spectroscopic techniques to conduct a comprehensive study of spectral and dynamical characteristics of single- and multiexciton states in CsPbX3 nanocrystals with X being either Br, I, or their mixture. Specifically, we measure exciton radiative lifetimes, absorption cross-sections, and derive the degeneracies of the band-edge electron and hole states. We also characterize the rates of intraband cooling and nonradiative Auger recombination and evaluate the strength of exciton-exciton coupling. The overall conclusion of this work is that spectroscopic properties of Cs-Pb-halide quantum dots are largely similar to those of quantum dots of more traditional semiconductors such as CdSe and PbSe. At the same time, we observe some distinctions including, for example, an appreciable effect of the halide identity on radiative lifetimes, considerably shorter biexciton Auger lifetimes, and apparent deviation of their size dependence from the "universal volume scaling" previously observed for many traditional nanocrystal systems. The high efficiency of Auger decay in perovskite quantum dots is detrimental to their prospective applications in light-emitting devices and lasers. This points toward the need for the development of approaches for effective suppression of Auger

Defect formation and desorption of metal atoms from alkali halide crystals under low energy electron bombardment studied by optical absorption and mass spectroscopy

International Nuclear Information System (INIS)

Seifert, N.R.

1993-04-01

This work presents an extensive investigation of electronically induced desorption of ground-state alkali atoms from alkali halides and for the first time correlates directly the desorption with the stability and spatial distribution of the defects formed during bombardment. The electron impact results in the formation of stable F-centers and F-center clusters in the bulk of the crystals. In striking contrast a significant metallization of the surface is observed. Even at temperatures as low as 90 deg C the metallization is achieved within the time resolution of our detection system, which can only be explained by the rapid diffusion of hot holes. Superimposed to the fast and short diffusion of hot holes is the slow F-center diffusion. Measuring the distribution of defects with low energy ion sputtering techniques indicates that at least in the case of LiF the observed diffusion constant of F-centers agrees with values derived by using methods different from that applied here. At low temperatures the formation of F-center clusters and metal on the surface dominates. Colloid formation clearly requires higher temperatures (typically around 200 deg C). This is a strong evidence that efficient F-center diffusion is necessary for the formation of metallic particles (colloids) in the bulk of the crystals. Desorption of alkali atoms from alkali halides at temperatures around room temperature is due to weakly bound alkali atoms. For elevated temperatures the stability of the metallic clusters in the bulk of the crystals (i.e. colloids) are the rate limiting process. (author)

Conversion of ion-exchange resins, catalysts and sludges to glass with optional noble metal recovery using the GMODS process

International Nuclear Information System (INIS)

Forsberg, C.W.; Beahm, E.C.

1996-01-01

Chemical processing and cleanup of waste streams (air and water) typically result in products, clean air, clean water, and concentrated hazardous residues (ion exchange resins, catalysts, sludges, etc.). Typically, these streams contain significant quantities of complex organics. For disposal, it is desirable to destroy the organics and immobilize any heavy metals or radioactive components into stable waste forms. If there are noble metals in the residues, it is desirable to recover these for reuse. The Glass Material Oxidation and Dissolution System (GMODS) is a new process that directly converts radioactive and hazardous chemical wastes to borosilicate glass. GMODS oxidizes organics with the residue converted to glass; converts metals, ceramics, and amorphous solids to glass; converts halides (eg chlorides) to borosilicate glass and a secondary sodium halide stream; and recovers noble metals. GMODS has been demonstrated on a small laboratory scale (hundreds of grams), and the equipment needed for larger masses has been identified

Organometallic halide perovskite single crystals having low deffect density and methods of preparation thereof

KAUST Repository

Bakr, Osman; Shi, Dong

2016-01-01

The present disclosure presents a method of making a single crystal organometallic halide perovskites, with the formula: AMX3, wherein A is an organic cation, M is selected from the group consisting of: Pb, Sn, Cu, Ni, Co, Fe, Mn, Pd, Cd, Ge, and Eu

Halide salts and their structural properties in presence of secondary amine based molecule: A combined experimental and theoretical analysis

Science.gov (United States)

Ghosh, Pritam; Hazra, Abhijit; Ghosh, Meenakshi; Chandra Murmu, Naresh; Banerjee, Priyabrata

2018-04-01

Biologically relevant halide salts and its solution state structural properties are always been significant. In general, exposure of halide salts into polar solution medium results in solvation which in turn separates the cationic and anionic part of the salt. However, the conventional behaviour of salts might alter in presence of any secondary amine based compound, i.e.; moderately strong Lewis acid. In its consequence, to investigate the effect of secondary amine based compound in the salt solution, novel (E)-2-(4-bromobenzylidene)-1-(perfluorophenyl) hydrazine has been synthesized and used as secondary amine source. The secondary amine compound interestingly shows a drastic color change upon exposure to fluoride salts owing to hydrogen bonding interaction. Several experimental methods, e.g.; SCXRD, UV-Vis, FT-IR, ESI-MS and DLS together with modern DFT (i.e.; DFT-D3) have been performed to explore the structural properties of the halide salts upon exposure to secondary amine based compound. The effect of counter cation of the fluoride salt in binding with secondary amine source has also been investigated.

Dark electrical bias effect on moisture-induced degradation in inverted lead halide perovskite solar cells measured by advanced chemical probes

KAUST Repository

Barbe, Jeremy; Kumar, Vikas; Newman, Michael; Lee, Harrison; Jain, Sagar Motilal; Chen, Hu; Charbonneau, Cé cile; Rodenburg, C; Tsoi, Wing

2018-01-01

Emerging lead halide perovskite materials have enormous potential for a range of optoelectronic devices, such as solar cells, light emitting diodes, transistors and lasers. However, the large-scale commercialization of these technologies will depend on the ability of the active material to be stable under environmental and operating conditions. In this work, we measured the first time the electrical bias-induced degradation of inverted perovskite solar cells in the dark in different environments and concluded that humidity coupled with electrical bias results in fast degradation of CH3NH3PbI3 into PbI2. Micro-Raman and photoluminescence show that the degradation starts from the edge of the cell due to moisture ingress. By using novel local Raman-transient photocurrent measurements, we were able to probe local ion migration at the degraded region and non-degraded region and found that the formation of PbI2 can passivate perovskite by reducing ion migration. The degradation is far from uniform across different grains as revealed by secondary electron hyperspectral imaging, an advanced scanning electron microscopy technique which allows probing the composition of individual grain from the cross-section. By using potential step chronoamperometry, we also found that the bias degradation is closely related to the density of mobile ions. The unique combination of established methods with several novel analytical tools provides an insight into the origin of the bias-degradation of inverted perovskite solar cells from nano-scale to cell level, and demonstrates the potential of these novel tools for studying the degradation in other perovskite systems.

Dark electrical bias effect on moisture-induced degradation in inverted lead halide perovskite solar cells measured by advanced chemical probes

KAUST Repository

Barbe, Jeremy

2018-02-12

Emerging lead halide perovskite materials have enormous potential for a range of optoelectronic devices, such as solar cells, light emitting diodes, transistors and lasers. However, the large-scale commercialization of these technologies will depend on the ability of the active material to be stable under environmental and operating conditions. In this work, we measured the first time the electrical bias-induced degradation of inverted perovskite solar cells in the dark in different environments and concluded that humidity coupled with electrical bias results in fast degradation of CH3NH3PbI3 into PbI2. Micro-Raman and photoluminescence show that the degradation starts from the edge of the cell due to moisture ingress. By using novel local Raman-transient photocurrent measurements, we were able to probe local ion migration at the degraded region and non-degraded region and found that the formation of PbI2 can passivate perovskite by reducing ion migration. The degradation is far from uniform across different grains as revealed by secondary electron hyperspectral imaging, an advanced scanning electron microscopy technique which allows probing the composition of individual grain from the cross-section. By using potential step chronoamperometry, we also found that the bias degradation is closely related to the density of mobile ions. The unique combination of established methods with several novel analytical tools provides an insight into the origin of the bias-degradation of inverted perovskite solar cells from nano-scale to cell level, and demonstrates the potential of these novel tools for studying the degradation in other perovskite systems.

Higher cytotoxicity of divalent antibody-toxins than monovalent antibody-toxins

International Nuclear Information System (INIS)

Won, JaeSeon; Nam, PilWon; Lee, YongChan; Choe, MuHyeon

2009-01-01

Recombinant antibody-toxins are constructed via the fusion of a 'carcinoma-specific' antibody fragment to a toxin. Due to the high affinity and high selectivity of the antibody fragments, antibody-toxins can bind to surface antigens on cancer cells and kill them without harming normal cells [L.H. Pai, J.K. Batra, D.J. FitzGerald, M.C. Willingham, I. Pastan, Anti-tumor activities of immunotoxins made of monoclonal antibody B3 and various forms of Pseudomonas exotoxin, Proc. Natl. Acad. Sci. USA 88 (1991) 3358-3362]. In this study, we constructed the antibody-toxin, Fab-SWn-PE38, with SWn (n = 3, 6, 9) sequences containing n-time repeated (G 4 S) between the Fab fragment and PE38 (38 kDa truncated form of Pseudomonas exotoxin A). The SWn sequence also harbored one cysteine residue that could form a disulfide bridge between two Fab-SWn-PE38 monomers. We assessed the cytotoxicity of the monovalent (Fab-SWn-PE38), and divalent ([Fab-SWn-PE38] 2 ) antibody-toxins. The cytotoxicity of the dimer against the CRL1739 cell line was approximately 18.8-fold higher than that of the monomer on the ng/ml scale, which was approximately 37.6-fold higher on the pM scale. These results strongly indicate that divalency provides higher cytotoxicity for an antibody-toxin.

NEW THIO S2- ADDUCTS WITH ANTIMONY (III AND V HALIDE: SYNTHESIS AND INFRARED STUDY

Directory of Open Access Journals (Sweden)

HASSAN ALLOUCH

2013-12-01

Full Text Available Five new S2- adducts with SbIII and SbV halides have been synthesized and studied by infrared. Discrete structures have been suggested, the environment around the antimony being tetrahedral, trigonal bipyramidal or octahedral.

Band Gap Tuning and Defect Tolerance of Atomically Thin Two-Dimensional Organic-Inorganic Halide Perovskites.

Science.gov (United States)

Pandey, Mohnish; Jacobsen, Karsten W; Thygesen, Kristian S

2016-11-03

Organic-inorganic halide perovskites have proven highly successful for photovoltaics but suffer from low stability, which deteriorates their performance over time. Recent experiments have demonstrated that low dimensional phases of the hybrid perovskites may exhibit improved stability. Here we report first-principles calculations for isolated monolayers of the organometallic halide perovskites (C 4 H 9 NH 3 ) 2 MX 2 Y 2 , where M = Pb, Ge, Sn and X,Y = Cl, Br, I. The band gaps computed using the GLLB-SC functional are found to be in excellent agreement with experimental photoluminescence data for the already synthesized perovskites. Finally, we study the effect of different defects on the band structure. We find that the most common defects only introduce shallow or no states in the band gap, indicating that these atomically thin 2D perovskites are likely to be defect tolerant.

Band Gap Tuning and Defect Tolerance of Atomically Thin Two- Dimensional Organic-Inorganic Halide Perovskites

DEFF Research Database (Denmark)

Pandey, Mohnish; Jacobsen, Karsten Wedel; Thygesen, Kristian Sommer

2016-01-01

Organic−inorganic halide perovskites have proven highly successful for photovoltaics but suffer from low stability, which deteriorates their performance over time. Recent experiments have demonstrated that low dimensional phases of the hybrid perovskites may exhibit improved stability. Here we...... report first-principles calculations for isolated monolayers of the organometallic halide perovskites (C4H9NH3)2MX2Y2, where M = Pb, Ge, Sn and X,Y = Cl, Br, I. The band gaps computed using the GLLB-SC functional are found to be in excellent agreement with experimental photoluminescence data...... for the already synthesized perovskites. Finally, we study the effect of different defects on the band structure. We find that the most common defects only introduce shallow or no states in the band gap, indicating that these atomically thin 2D perovskites are likely to be defect tolerant....

Luminescent unit computerization to research spectral characteristics of fine film alkali halide crystal

International Nuclear Information System (INIS)

Zhalimbetov, T.; Zhabetov, A.; Moldagaliev, A.; Sarmukhanov, E.; Shunkeev, K.; Shunkeev, S.; Abdullin, K.; Tokmoldin, C.

2002-01-01

The fundamental optical absorption of ion crystals characterizes the creation of different free low energetic electronic excitation (the excitons and electron-hole pairs), but their straight registration is not possible because of incommensurable big absorption factor of alkali halide monocrystals. So to registration the spectrums of alkali halide monocrystal very fine layers are necessary. We have received fine films of Nal and KCl in system of KCl-Nal-KCl, KCl-KI-KCl on the base of universal vacuum post VUP-4, VUP-5 by thermal evaporation. A unique spectral unit has been created For this on the basic the SDL-2 complex. Complex consists of radiator, systems of condensers, monochromators MDR-12 and MDR-23, receivers of radiation, controller by unit. Connect and control of monochromators by means of IBM-compatible computer has been created. Kinematics schemes of monochromators provide consequent removing on output slot of monochromatic radiation in operating range of each diffraction lattice and indication its wavelength. The tumbling diffraction lattices is done the crossbar engines SHDR-711. For this special plate of control and block of reinforcement for crossbar engines in monochromators MDR-12 and MDR-23 are designed and constructed. Created controller of monochromators consists of double cascade preamplifier on transistors n-p-n type (815G) and logical scheme, constructed on summers and K555 series triggers. The preamplifier is used for reinforcement of signal to available amplifier on transistors KT837D. The logical scheme reduces the number of used categories of bidirectional port and enables unhooking the feeding to the windings of crossbar engine at conservation of previous combination of signals. The connection controller of monochromators is done through controller of port of computer with use the parallel interface. For installing computerized system of collection and data processing is provided marketed by means of modern object-oriented programming

Thermoluminescence in alkali halides irradiated at 80K

International Nuclear Information System (INIS)

Jimenez de Castro, M.

1978-01-01

The thermoluminescence, the thermally stimulated currents and the thermal stability of the F centres induced in pure NaCl and KC1 crystals by X irradiation at 80K have been studied in detail, in the range between 80 and 300K. The thermoluminescent processes induced by illumination at 80K with F light in samples previously irradiated at room temperature has also been studied. It has been clearly observed the existence of thermoluminescent processes due to electrons and holes thermally released from traps, in which the F centres are not involved. The existence of hole-F centre recombination has not been observed. There are several thermoluminescent processes in both materials which are scribed to the recombination of F centres with mobile interstitial halogen atoms thermally released from traps, which are likely monovalent impurities in this temperature interval. The light emitting stage in these processes is originated by the formation of self trapped excitons. (Author) 66 refs

Inorganic hole conductor-based lead halide perovskite solar cells with 12.4% conversion efficiency

KAUST Repository

Qin, Peng

2014-05-12

Organo-lead halide perovskites have attracted much attention for solar cell applications due to their unique optical and electrical properties. With either low-temperature solution processing or vacuum evaporation, the overall conversion efficiencies of perovskite solar cells with organic hole-transporting material were quickly improved to over 15% during the last 2 years. However, the organic hole-transporting materials used are normally quite expensive due to complicated synthetic procedure or high-purity requirement. Here, we demonstrate the application of an effective and cheap inorganic p-type hole-transporting material, copper thiocyanate, on lead halide perovskite-based devices. With low-temperature solution-process deposition method, a power conversion efficiency of 12.4% was achieved under full sun illumination. This work represents a well-defined cell configuration with optimized perovskite morphology by two times of lead iodide deposition, and opens the door for integration of a class of abundant and inexpensive material for photovoltaic application. © 2014 Macmillan Publishers Limited.

Excitonic and electron-hole mechanisms of the creation of Frenkel defect in alkali halides

International Nuclear Information System (INIS)

Lushchik, A.; Kirm, M.; Lushchik, Ch.; Vasil'chenko, E.

2000-01-01

Excitonic and electron-hole (e-h) mechanisms of stable F centre creation by VUV radiation in alkali halide crystals are discussed. In KCl at 4.2 K, the efficiency of stable F-H pair creation is especially high at the direct optical formation of triplet excitons with n=1. At 200-400 K, the creation processes of stable F centres in KCl are especially efficient at the formation of one-halide exciton in the Urbach tail of an exciton absorption. In KCl and KBr, the decay of a cation exciton (∼20 eV) causes the formation of two e-h pairs, while in NaCl a cation exciton (33.5 eV) decays into two e-h and an anion exciton. An elastic uniaxial stress of a crystal excited by VUV radiation decreases the mean free path of excitons before their self-trapping (KI) and increases the mean free path of hot holes before self-trapping (NaCl)

Inorganic hole conductor-based lead halide perovskite solar cells with 12.4% conversion efficiency

KAUST Repository

Qin, Peng; Tanaka, Soichiro; Ito, Seigo; Tetreault, Nicolas; Manabe, Kyohei; Nishino, Hitoshi; Nazeeruddin, Mohammad Khaja; Grä tzel, Michael

2014-01-01

Organo-lead halide perovskites have attracted much attention for solar cell applications due to their unique optical and electrical properties. With either low-temperature solution processing or vacuum evaporation, the overall conversion efficiencies of perovskite solar cells with organic hole-transporting material were quickly improved to over 15% during the last 2 years. However, the organic hole-transporting materials used are normally quite expensive due to complicated synthetic procedure or high-purity requirement. Here, we demonstrate the application of an effective and cheap inorganic p-type hole-transporting material, copper thiocyanate, on lead halide perovskite-based devices. With low-temperature solution-process deposition method, a power conversion efficiency of 12.4% was achieved under full sun illumination. This work represents a well-defined cell configuration with optimized perovskite morphology by two times of lead iodide deposition, and opens the door for integration of a class of abundant and inexpensive material for photovoltaic application. © 2014 Macmillan Publishers Limited.

High Pressure Optical Studies of the Thallous Halides and of Charge-Transfer Complexes

Science.gov (United States)

Jurgensen, Charles Willard

High pressure was used to study the insulator -to-metal transition in sulfur and the thallous halides and to study the intermolecular interactions in charge -transfer complexes. The approach to the band overlap insulator -to-metal transition was studied in three thallous halides and sulfur by optical absorption measurements of the band gap as a function of pressure. The band gap of sulfur continuously decreases with pressure up to the insulator -to-metal transition which occurs between 450 and 485 kbars. The results on the thallous halides indicate that the indirect gap decreases more rapidly than the direct gap; the closing of the indirect gap is responsible for the observed insulator -to-metal transitions. High pressure electronic and vibrational spectroscopic measurements on the solid-state complexes of HMB-TCNE were used to study the intermolecular interactions of charge -transfer complexes. The vibrational frequency shifts indicate that the degree of charge transfer increases with pressure which is independently confirmed by an increase in the molar absorptivity of the electronic charge-transfer peak. Induction and dispersion forces contribute towards a red shift of the charge-transfer peak; however, charge-transfer resonance contributes toward a blue shift and this effect is dominant for the HMB-TCNE complexes. High pressure electronic spectra were used to study the effect of intermolecular interactions on the electronic states of TCNQ and its complexes. The red shifts with pressure of the electronic spectra of TCNQ and (TCNQ)(' -) in polymer media and of crystalline TCNQ can be understood in terms of Van der Waals interactions. None of the calculations which considered intradimer distance obtained the proper behavior for either the charge-transfer of the locally excited states of the complexes. The qualitative behavior of both states can be interpreted as the effect of increased mixing of the locally excited and charge transfer states.

Structural and Chemical Analysis of Gadolinium Halides Encapsulated within WS 2 Nanotubes

KAUST Repository

Anumol, E A

2016-05-18

The hollow cavities of nanotubes could serve as templates for the growth of size- and shape-confined functional nanostructures, giving rise to novel materials and properties. In this work, considering their potential application as MRI contrast agents, gadolinium halides are encapsulated within the hollow cavities of inorganic nanotubes of WS2 by capillary filling to obtain GdX3@WS2 nanotubes (where X = Cl, Br or I and @ means encapsulated in). Aberration corrected scanning/transmission electron microscopy (S/TEM) and spectroscopy is employed to understand the morphology and composition of the GdI3@WS2 nanotubes. The three dimensional morphology is studied with STEM tomography but understanding the compositional information is a non-trivial matter due to the presence of multiple high atomic number elements. Therefore, energy dispersive X-ray spectroscopy (EDS) tomography was employed revealing the three dimensional chemical composition. Molecular dynamics simulations of the filling procedure shed light into the mechanics behind the formation of the confined gadolinium halide crystals. The quasi-1D system employed here serves as an example of a TEM-based chemical nanotomography method that could be extended to other materials, including beam-sensitive soft materials.

Structural and Chemical Analysis of Gadolinium Halides Encapsulated within WS 2 Nanotubes

KAUST Repository

Anumol, E A; Enyashin, Andrey; Batra, Nitin M; Da Costa, Pedro M. F. J.; Francis, Leonard Deepak

2016-01-01

The hollow cavities of nanotubes could serve as templates for the growth of size- and shape-confined functional nanostructures, giving rise to novel materials and properties. In this work, considering their potential application as MRI contrast agents, gadolinium halides are encapsulated within the hollow cavities of inorganic nanotubes of WS2 by capillary filling to obtain GdX3@WS2 nanotubes (where X = Cl, Br or I and @ means encapsulated in). Aberration corrected scanning/transmission electron microscopy (S/TEM) and spectroscopy is employed to understand the morphology and composition of the GdI3@WS2 nanotubes. The three dimensional morphology is studied with STEM tomography but understanding the compositional information is a non-trivial matter due to the presence of multiple high atomic number elements. Therefore, energy dispersive X-ray spectroscopy (EDS) tomography was employed revealing the three dimensional chemical composition. Molecular dynamics simulations of the filling procedure shed light into the mechanics behind the formation of the confined gadolinium halide crystals. The quasi-1D system employed here serves as an example of a TEM-based chemical nanotomography method that could be extended to other materials, including beam-sensitive soft materials.

Monitoring of fluoride and iodide levels in drinking water using ion selective electrodes

International Nuclear Information System (INIS)

Ahmed, R.; Viqar-Un-Nisa; Hussain, M.; Tanwir, R.; Qureshi, S.A.

2004-01-01

Fluoride and iodide, the most important constituents of drinking water are essential as well as toxic depending on their levels. For their analysis in water mostly ion-selective electrodes, spectrophotometry, titrimetry and coulometry etc; have been used and literature has been briefly reviewed. Ion-selective electrodes offer an efficient method for the measurement of the two halides and were mostly used during this work. Fabrication of these electrodes is briefly described. Comparison of results obtained by ion selective electrode and coulometry is given. Recoveries of the added fluoride ions from the samples were good. A large number of water samples from Rawalpindi-Islamabad area were analyzed for fluoride and iodide. Levels of fluoride and iodide from two main water reservoirs of Rawalpindi and Islamabad are reported before and after treatment. Both surface and ground water samples were analyzed and results are compared and discussed. Some samples from northern areas were also analyzed for iodide and fluoride and compared. Intake of fluoride and iodide from water of different areas is also compared. Water samples, which caused bone deformation in certain areas in Punjab due to excess fluoride, were also analyzed for fluoride and results are presented. (author)

The Study of Reducing Krypton-85 Activity in Metal Halide Lamp%降低金卤灯内氪-85活度的研究

Institute of Scientific and Technical Information of China (English)

叶碧君

2012-01-01

通过测试及分析不同氪-85活度填充气体的同规格金卤灯的各项性能参数,研究了在确保金卤灯各项性能的前提下,降低金卤灯中氪-85活度的可行性及金卤灯中氪-85存在的必要性,可以为今后确定金卤灯中需添加的最低氪-85活度提供参考。%By analyzing the parameters of metal halide lamps which are filled with gas with different activity of krypton-85, the paper studies the feasibility of reducing krypton-85 activity in metal halide lamp while ensuring the lamp performance, and proves the necessity of its existence of krypton-85 in metal halide lamp. it can provide us a reference to determine the minimum krypton-85 activity to he added in metal halide lamps.

Evaluation of field test equipment for halide and DOP testing

International Nuclear Information System (INIS)

Schreiber, K.L.; Kovach, J.L.

1975-01-01

The Nucon Testing Services Department, field testing at power reactor sites, has performed tests using R-11, R-12, and R-112 in conjunction with gas chromatographs and direct reading halide detectors. The field operational experience with these detector systems, thus sensitivity, precision, and manner of field calibration, are presented. Laboratory experiments regarding 3 H-tagged methyl iodide for in place leak testing of adsorber systems indicate a low hazard, high reliability process for leak testing in facilities where atmospheric cross contamination occurs. (U.S.)

Photodissociation comprehensive study of OH- on alkali halides and their interaction with colour centers

International Nuclear Information System (INIS)

Gomes, L.

1985-01-01

This work shows that the OH - defect induces changes in the electronics processes of the alkali halides such as in radiation damage and optical cycles of colour centers. Two cases were considered: with the presence of an OH - ion in the (1) excited state and (2) in the ground state; 1) the comprehensive study of resonant OH - photodissociation in several hosts showed that deep traps (for electrons) can be produced from the OH - dissociation. These traps can be effective for the capture of electrons produced in the radiation damage of the lattice as well as for trapping electrons from ionized color centers. It was observed a second channel (new) for the de-excitation of the (OH - )* molecule in KI and RbI. This effect can be effective only when the lattice around the molecule holds a large enough interstitial space. This new mechanism is responsible for the strong production at LNT of F centers and OH 0 molecules at the expenses of OH - defects. Considering the complete investigation of the full cycle it was proposed a phenomenological model that would explain the observed behaviour when one covers a wide variation of lattice parameters (KCl -> RbI); 2) It was verified that the OH - ion present in the lattice induces strong changes in the de-excitation processes of electronic defects with a spread out wave function (like F centers). A change in the reorientation behaviour of excited F 2 and F + 2 centers was also verified. Two main effects should be mentioned: A) The induced de-excitation is very fast and non-radiative on F centers. B) Another type of system investigated (F 2 and F + 2 ) has shown an intense increase of the speed of reorientation of the F 2 and F + 2 excited centers. (autor) [pt

Electron magnetic resonance study of monovalent Na doping in Pr0.6Sr0.4−xNaxMnO3 manganites

International Nuclear Information System (INIS)

Thaljaoui, Rachid; Boujelben, Wahiba; Pękała, Marek; Szydłowska, Jadwiga; Cheikhrouhou, Abdelwaheb

2012-01-01

Highlights: ► New monovalent doped manganites Pr 0.6 Sr 0.4−x Na x MnO 3 (x = 0, 0.05). ► Comparison of electron magnetic resonance spectra in ferro- and paramagnetic phases. ► Double exchange interactions weakened by Na doping as indicated by activation energy. ► Magnetic susceptibility derived from resonance intensity obeys Curie–Weiss law. - Abstract: Effect of monovalent Na doping on the magnetic properties is studied in Pr 0.6 Sr 0.4−x Na x MnO 3 system (x = 0, 0.05) using X-band electron magnetic resonance and magnetization measurements. Temperature variation of magnetic resonance spectra of doped and undoped manganites is analyzed for paramagnetic and ferromagnetic states and compared to similar systems. In paramagnetic phase the magnetic susceptibility proportional to resonance signal intensity is found to obey the Curie–Weiss law. The effective magnetic moment becomes smaller in doped manganite. The paramagnetic Curie temperature derived from signal intensity equals to 312 and 306 K for the undoped and doped manganites, respectively, and is close to values obtained from magnetization variation in paramagnetic phase. The activation energy determined using the adiabatic small polaron hopping model is higher for the undoped than the doped manganite, which proves that the Na doping slightly reduces the Mn 3+ /Mn 4+ double exchange interactions.

Contribution to the coordination chemistry of penta, hexa and heptavalent ions of 5f elements

International Nuclear Information System (INIS)

Musikas, Claude.

1978-01-01

This report has two main parts in which are discussed results dealing with: - aquo and hydroxo complexes of penta, hexa and heptavalent ions of 5f elements - pseuso halides complexes of these ions (SCN - , N 3 - , CN - ). It has been shown, by spectrophotometric and electrochemical measurements that U (V) possesses an aquo ion more acid than the known UO 2 + ion. This form is observed as insoluble hydroxid near pH 3.0 or as soluble polynuclear hydroxo complexes at lower pH. Hydroxo anionic complexes of U (VI) have been observed and one can precise the mecanism of hydrolysis of UO 2 ++ ions beyond he hydroxid UO 2 (OH) 2 . At pH 9 to 12, polynuclear species with low negative charge have been observed. At pH 13, others OH - ions enter in the coordination sphere of UO 2 ++ and mononuclear species are obtained. Reduction of polynuclear species leads to mixed hydroxo complexes of 'blue type'. Studies of hydrolysis of NpO 2 + allow to propose an hydrolysis mechanism similar to UO 2 ++ one. With electrochemical methods that in acidic media Np (VII) is present as NpO 3 + ions. Solubility product of NpO 3 OH has been measured. The second part is devoted to pseudohalides complexes of UO 2 ++ , UO 2 + and NpO 2 + ions [fr

Conceptual design of an angular multiplexed rare-gas-halide laser-fusion driver. Final technical report, 1 August 1979-31 May 1980

International Nuclear Information System (INIS)

Parks, J.H.

1980-11-01

A conceptual definition for angular multiplexed rare gas halide drivers was formulated and several design examples analyzed. Angular multiplexed rare gas-halide lasers, in particular the KrF* laser, can be designed to meet ICF requirements. These lasers are scalable, emit at short wavelengths (KrF* 250 nm), and through the use of optical angular multiplexing, produce the required high energy (approx. 1 to 5 MJ) in a short pulse (approx. 10 nsec) with projected overall efficiency in the range of 5 to 7%

Solution and solid-state studies on the halide binding affinity of perfluorophenyl-armed uranyl-salophen receptors enhanced by anion-π interactions

Energy Technology Data Exchange (ETDEWEB)

Leoni, Luca; Mele, Andrea; Giannicchi, Ilaria; Mihan, Francesco Yafteh; Dalla Cort, Antonella [Dipartimento di Chimica and IMC-CNR, Universita di Roma La Sapienza (Italy); Puttreddy, Rakesh; Jurcek, Ondrej; Rissanen, Kari [University of Jyvaeskylae, Department of Chemistry, Nanoscience Center (Finland)

2016-12-23

The enhancement of the binding between halide anions and a Lewis acidic uranyl-salophen receptor has been achieved by the introduction of pendant electron-deficient arene units into the receptor skeleton. The association and the occurrence of the elusive anion-π interaction with halide anions (as tetrabutylammonium salts) have been demonstrated in solution and in the solid state, providing unambiguous evidence on the interplay of the concerted interactions responsible for the anion binding. (copyright 2016 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)